EP0965680A1 - Aqueous dispersions, their preparation and use thereof - Google Patents

Abstract

Aqueous dispersions (L) comprising: a) a wax which is (a1) a carboxyl-containing hydrocarbon wax or a mixture of such waxes or a mixture of (a1) and, (a2) at least one unmodified hydrocarbon wax; (b) a (co)poly(meth)acrylamide or (co)poly-(meth)acrylamide mixture which is (b1) at least one macro(co)poly-(meth)acrylamide, which optionally contains carboxyl-containing comonomers, having an average molecular weight <o>M</o>W = n.10<6>, where n >/= 10, or a mixture of (b1) and (b2) at least one (co)poly(meth)-acrylamide, which optionally contains carboxyl-containing comonomers, having an average molecular weight <o>M</o>W < 10.10<6>, and (d) a dispersant system consisting of amphoteric, anionic and/or nonionic surfactants, are surprisingly useful as highly effective crease mark inhibitors having an extremely surfacy effect and are also suitable for particularly short liquors, for example in winch becks and jet-dyeing machines.

Description

In the treatment of textile fabrics in strand form, essentially pretreatment, Coloring, optically brightening or aftertreatment, in an aqueous liquor under such conditions that in textile substrate creases can arise or friction from the substrate against neighboring Unwanted phenomena are the marking of the substrate or apparatus parts can take place Running creases and the emergence and marking of chafing points, which then as appropriate Irregularities in the product image and possibly also the physical properties of the treated Goods and consequently the finished goods. To counteract these disturbing phenomena act, wet lubricants are used in the corresponding process stages, the tendency to Reduce the formation or stabilization and consequently marking of wrinkles, in particular running folds and the substrate / substrate and substrate / metal friction and hence the tendency to form and Reduce the marking of chafe marks. Wax dispersions are known from GB-A 2282153, which are particularly suitable as electrolyte-resistant anti-wrinkle agents (lubricants). In the constant further development of processes and machines, with the aim of increasing performance and environmentally friendly procedures, machines and processes are developed that are designed for higher Speeds or higher outputs are designed and / or with shorter fleet ratios work. This also places higher demands on the lubricants used. So For example, they have to be resistant to particularly high shear forces and theirs Develop the effect as well as possible with short fleets. The shorter the fleet, the larger it has to be Concentration of the respective treatment agents and the greater the proportion Fleet, which - depending on the absorbency of the goods - is taken up by the goods, so that wet gliding of the goods and the achievement of a level, calm appearance of the goods without damaging the goods all the more is difficult.

It has now been found that the preparations (L) defined below surprisingly prove to be highly effective Wrinkle prevention agents are extremely superficial and also suitable for particularly short fleets are suitable, e.g. in reel runners and jet dyeing machines.

The invention relates to the preparations (L), their preparation and their use.

(a) ein Wachs welches

(a1) ein carboxygruppenhaltiges Kohlenwasserstoffwachs oder ein Gemisch solcher Wachse
oder ein Gemisch aus (a1) und

(a2) mindestens einem nicht modifizierten Kohlenwasserstoffwachs ist,

(b) ein (Co)poly(meth)acrylamid oder (Co)poly(meth)acrylamidgemisch, welches

(b1) mindestens ein Makro(co)poly(meth)acrylamid, das gegebenenfalls carboxygruppenhaltige Comonomeren enthält, mit einem durchschnittlichen Molekulargewicht M W = n·106 , worin n ≥ 10 ist,
oder ein Gemisch aus (b1) und

(b2) mindestens einem (Co)poly(meth)acrylamid, das gegebenenfalls carboxygruppenhaltige Comonomeren enthält, mit einem durchschnittlichen Molekulargewicht M _W < 10·10⁶,

ist,

und (d) ein Dispergiermittelsystem aus amphoteren, anionischen und/oder nicht-ionogenen Tensiden.

A first subject of the invention is therefore aqueous dispersions (L) containing:

(a) a wax which

(a1) a hydrocarbon wax containing carboxy groups or a mixture of such waxes
or a mixture of (a1) and

(a2) is at least one unmodified hydrocarbon wax,

(b) a (Co) poly (meth) acrylamide or (Co) poly (meth) acrylamide mixture, which

(b1) at least one macro (co) poly (meth) acrylamide, which optionally contains carboxy group-containing comonomers, with an average molecular weight M W = n · 10 6 , where n is ≥ 10,
or a mixture of (b1) and

(b2) at least one (co) poly (meth) acrylamide, which optionally contains carboxy group-containing comonomers, with an average molecular weight M _W <10 · 10 ⁶ ,

is

and (d) a dispersant system consisting of amphoteric, anionic and / or non-ionic surfactants.

Known waxes can generally be used as waxes (a).

Any hydrocarbon waxes (a1) containing carboxy groups are generally suitable synthetic waxes and / or oxidatively modified mineral and / or synthetic hydrocarbon waxes, which have a wax structure, e.g. by copolymerization (e.g. block copolymerization or mixed copolymerization) of olefins, in particular ethylene or propylene comonomers containing carboxylic acid groups, in particular (meth) acrylic acid and / or maleic acid, or by graft polymerization, or oxidation products of hydrocarbon waxes or waxes containing carboxylic acid groups which may be oxidative are synthesized, such as Fischer-Tropsch waxes and their partial saponification products.

The hydrocarbon waxes (a1) containing carboxylic acid groups are preferably oxidized and optionally partially hydrolyzed hydrocarbon waxes and generally include any synthetic and / or mineral waxes, which still have a wax structure in the oxidized form, in particular oxidized micro waxes or oxidized polyolefin waxes (mainly polyethylene waxes) or waxes, which are optionally synthesized directly in oxidized form, especially Fischer-Tropsch waxes, and also their oxidation waxes, the oxidized waxes mentioned, especially the oxidized polyolefin waxes and the Fischer-Tropsch waxes, if appropriate can be partially saponified. Among the waxes mentioned are the oxidized and optionally partially saponified micro waxes, Fischer-Tropsch waxes and polyethylene waxes preferred. Such Waxes are generally known and can be characterized by common parameters such as the needle penetration (e.g. according to ASTM-D 1321 or -D 5), the solidification point, the dropping point, the Density, the acid number or / and possibly also the saponification number. Among the above Waxes (a1) are preferred to those whose needle penetration is 20 20 dmm, especially those whose needle penetration is in the range from 0.1 to 10 dmm, preferably 0.2 to 5 dmm, and their Acid number is in the range from 5 to 70, preferably 9 to 50. The density of the waxes (a1) lies advantageously in the range from 0.90 to 1.1, preferably 0.92 to 1.02, in particular 0.94 to 0.99. Under The waxes mentioned are especially the oxidized polyethylene waxes, primarily oxidized Low-pressure polyethylene, preferred, especially those with a needle penetration in the range of 0.2 up to 5 dmm.

The waxes (a2) are not modified, i.e. there are hydrocarbon waxes in which none functional groups or heteroatoms have been inserted.

As (a2) e.g. non-oxidized micro waxes or paraffin waxes can be used.

Paraffin waxes with a dropping point of ≥ 40 ° C., advantageously in the range of 40, come as (a2) up to 110 ° C, preferably 50 to 105 ° C, in particular table paraffin. Advantageous (a2) up to 130% by weight of (a1), preferably not more than 100% by weight, in particular not more than 50% by weight of (a1).

Although (a2) may be present, it is preferred that (a1) not be blended with (a2) will, i.e. that the entire wax (a) consists essentially only of (a1). Especially when the Dispersions (L) are used as wet lubricants in nozzle dyeing machines, it is preferred that the entire wax (a) consists essentially only of (a1).

(b') Acrylamid und/oder Methacrylamid
und Copolymere aus (b') und

(b'') einer äthylenisch ungesättigten Carbonsäure, welche vorzugsweise (Meth)acrylsäure, Maleinsäure und/oder Itaconsäure ist.

Known homopolymers and copolymers, in particular homopolymers and / or copolymers of, can be used as (b1) and (b2)

(b ') acrylamide and / or methacrylamide
and copolymers from (b ') and

(b ") of an ethylenically unsaturated carboxylic acid, which is preferably (meth) acrylic acid, maleic acid and / or itaconic acid.

The proportion of (b ') in (b1) is advantageously in the range from 50 to 100 mol%, preferably from 60 to 95 mol%, the remainder to 100 mol%. i.e. 50 to 0 mol%, preferably 40 to 5 mol%, in consists essentially of (b '').

The proportion of (b ') in (b2) is advantageously in the range from 50 to 100 mol%, preferably from 80 to 100 mole%, the remainder to 100 mole%. i.e. 50 to 0 mol%, preferably 20 to 0 mol%, in consists essentially of (b '').

According to the invention, (meth) acrylamide (co) polymers with very high molecular weight are used as (b1), which are referred to here as macro (co) poly (meth) acrylamides. The average molecular weight M _W of (b1) can be of any size, for example n can be in the range from 10 to 80, primarily n is in the range from 10 to 40, preferably 12 to 30, particularly preferably 15 to 25. According to a particular embodiment of the invention n ≥ 16.

Polymers are used as (b2) which have a lower molecular weight than (b1), namely in which the average molecular weight is <10 million. The average molecular weight is advantageous M _W of (b2) in the range from 100000 to 8 · 10 ⁶ , preferably in the range from 200000 to 5 · 10 ⁶ .

The polymers (b) are known or can be prepared by methods known per se. The copolymers from (b ') and (b' ') can be prepared by conventional copolymerization processes are produced, dicarboxylic acids such as e.g. Maleic acid, optionally also as cyclic Anhydrides can be used. Those in which (b '') the comonomer from acrylic acid or methacrylic acid, can also by hydrolysis of a portion of the amide groups corresponding homopolymers or copolymers that only consist of acrylamide and / or methacrylamide units is made.

The weight ratio (b2) / (b1) can vary within a wide range. Per part by weight (b1) e.g. 0 to 30, advantageously 0 to 20, preferably 0 to 10 parts by weight (b2) are used. If (b2) is used, at least 1 part by weight (b2) per part by weight (b1) is advantageously used.

The carboxy groups can be in the form of the free acid and / or in the form of salts, cations known per se, preferably hydrophilizing cations, being suitable for salt formation, for example alkali metal cations (for example sodium, potassium) or ammonium cations {for example unsubstituted ammonium, mono- , Di- or tri- (C _1-2 -alkyl) -ammonium, mono-, di- or tri- (C _2-3 -hydroxy-alkyl) -ammonium, mono-, di- or tri - [(C _{1 -2-} alkoxy) - (C _2-3 alkyl)] - ammonium or morpholinium}.

The weight ratio (b) / (a) is e.g. in the range from 1: 1 to 1: 200, advantageously 1: 2 to 1: 100, preferably 1: 3 to 1:40.

(d1) ein nicht-ionogenes Tensid oder ein Gemisch nicht-ionogener Tenside, mit HLB ≥ 7.

(d2) ein anionakatives Tensid, welches eine Carbonsäure oder Sulfonsäure oder ein Schwefelsäure- oder Phosphorsäureteilester oder ein Salz davon ist, oder ein Gemisch solcher anionaktiver Tenside, mit HLB ≥ 7,
oder

(d3) ein amphoteres Tensid, welches eine amino- oder ammoniumgruppenhaltige Carbonsäure oder Sulfonsäure oder ein amino- oder ammoniumgruppenhaltiger Schwefelsäure- oder Phosphorsäure-teilester, oder ein Salz davon ist, oder ein Gemisch solcher amphoterer Tenside, mit HLB ≥ 7,

oder Gemische von zwei oder mehreren der Tenside (d1) bis (d3), insbesondere ein Gemisch von mindestens einem Tensid (d2) mit mindestens einem Tensid (d1).The following are primarily considered as surfactants (d):

(d1) a non-ionic surfactant or a mixture of non-ionic surfactants with HLB ≥ 7.

(d2) an anionic surfactant which is a carboxylic acid or sulfonic acid or a sulfuric acid or phosphoric acid partial ester or a salt thereof, or a mixture of such anionic surfactants, with HLB ≥ 7,
or

(d3) an amphoteric surfactant which is a carboxylic acid or sulfonic acid containing amino or ammonium groups or a partial ester of sulfuric acid or phosphoric acid containing amino or ammonium groups, or a salt thereof, or a mixture of such amphoteric surfactants, with HLB ≥ 7,

or mixtures of two or more of the surfactants (d1) to (d3), in particular a mixture of at least one surfactant (d2) with at least one surfactant (d1).

The surfactants (d1), (d2) and (d3) generally have the character of dispersants.

R

einen aliphatischen, gesättigten, linearen Kohlenwasserstoffrest mit 11 bis 22 Kohlenstoffatomen
und

m

2 bis 16

bedeuten, oder Gemische solcher Tenside.Known compounds are generally considered as surfactants (d1), essentially those with an emulsifier or dispersant character. Emulsifiers or dispersants with a non-ionic character are well known in the art and are also described in the specialist literature, for example in MJ SCHICK "Non-ionic Surfactants" (Volume 1 of the "Surfactant Science Series", Marcel DEKKER Inc., New York , 1967). Suitable nonionic dispersants (d1) are primarily oxyalkylation products of fatty alcohols, fatty acids, fatty acid mono- or dialkanolamides (in which "alkanol" stands especially for "ethanol" or "isopropanol") or fatty acid partial esters of tri to hexafunctional aliphatic polyols or else Interoxalkylation products of fatty acid esters (for example of natural triglycerides), C _2-4 alkylene oxides and optionally styrene oxide being suitable as the oxalkylating agent and preferably at least 50% of the oxakylene units introduced being oxyethylene units; at least 80% of the oxyalkylene units introduced are oxyethylene units; all oxalkylene units introduced are particularly preferred oxyethylene units. The starting products for the addition of the oxalkylene units (fatty acids, fatty acid mono- or dialkanolamides, fatty alcohols, fatty acid esters or fatty acid polyol partial esters) can be any conventional products used for the preparation of such surfactants, especially those with 9 to 24, preferably 11 to 22 , particularly preferably 16 to 22 carbon atoms in the fat residue. The fat residues can be unsaturated or preferably saturated, branched or preferably linear; the following fatty acids may be mentioned, for example: lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, arachidic acid and behenic acid, and technical fatty acids, for example tallow fatty acid, coconut fatty acid, technical oleic acid, tall oil fatty acid and technical soy oleic acid, and their hydrogenation and / or distillation products; the fatty acid mono- or dialkanolamides which may be mentioned are, for example, the mono- or di-ethanol or isopropanolamides of the acids mentioned; the fatty alcohols which may be mentioned are the derivatives of the respective fatty acids mentioned and synthetic alcohols (for example tetramethylnonanol). Examples of partial esters of the polyols mentioned are the mono- or difatty acid esters of glycerol, erythritol, sorbitol or sorbitan, in particular the sorbitan mono- or di-oleates or stearates. Of the products mentioned, the alkoxylated fatty alcohols are preferred, especially the oxyethylation products of saturated, linear fatty alcohols, in particular those of the following average formula R ― O― (CH ₂ ―CH ₂ ―O) _m ―H wherein

R

an aliphatic, saturated, linear hydrocarbon residue with 11 to 22 carbon atoms
and

m

2 to 16

mean, or mixtures of such surfactants.

The HLB value of the surfactants (d1) is advantageously in the range from 7 to 16, preferably in the range from 8 to 15. Of the compounds of the formula (I), those are particularly those in which R 12 to 22 Contains carbon atoms, especially 14 to 22 carbon atoms, preferred.

As anionic surfactants (d2) there are generally known acids with a surfactant character considered as such as dispersants, e.g. as emulsifiers or as detergents, usually Find use. Such surfactant anionic compounds are known in the art and described in numerous technical literature, e.g. in "Surfactant Science Series", Volume 7 ("Anionic Surfactants "). In particular, such anionic surfactants come into consideration that have a lipophilic Contain residue (especially the residue of a fatty acid or an aliphatic hydrocarbon residue a fatty alcohol) of, for example, 8 to 24 carbon atoms, advantageously 12 to 22 carbon atoms, contains in particular 14 to 22 carbon atoms and can be aliphatic or araliphatic and wherein the aliphatic radicals can be linear or branched, saturated or unsaturated. Preferably in carboxylic acids the lipophilic residues are purely aliphatic and unsaturated, while in Sulfonic acids the lipophilic residues preferably saturated purely aliphatic or araliphatic residues are, in particular as described above for the non-ionic surfactants. The carbon or Sulphonic acid group can be attached directly to the hydrocarbon residue (especially as Fatty acid, e.g. in the form of soaps, or as alkanesulfonic acid) or via at least one a heteroatom interrupted bridge, which is preferably aliphatic. The introduction of Carboxy groups can e.g. by carboxyalkylation of hydroxy groups or monoesterification a hydroxy group with a dicarboxylic anhydride, e.g. in such a molecule as above mentioned as a starting product for the oxyalkylation to non-ionic surfactants or also from Oxyalkylation products thereof, it being possible to use oxiranes for the oxyalkylation, primarily ethylene oxide, propylene oxide and / or butylene oxide and optionally styrene oxide, and preferably at least 50 mol% of the oxiranes used is ethylene oxide; for example, these are Addition products of 1 to 12 moles of oxirane with 1 mole of hydroxy compounds, especially as above Starting product called oxyalkylation. Haloalkane carboxylic acids are primarily used for carboxyalkylation used, advantageously those in which the halogenoalkyl radical has 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, contains halogen primarily for chlorine or bromine stands and the acid group can optionally be in salt form. A carboxy group can e.g. also be introduced by monoesterification of an aliphatic dicarboxylic acid, e.g. by Reaction of a hydroxy compound with a cyclic anhydride, e.g. with phthalic anhydride or an aliphatic anhydride with 2 or 3 carbon atoms between the two carboxy groups, e.g. Succinic anhydride, maleic anhydride or glutaric anhydride. Analog can by esterification e.g. phosphoric acid or sulfuric acid partial ester groups are also introduced. The sulfonic acids are essentially sulfonation products from paraffins (e.g. produced by sulfochlorination or sulfoxidation), of α-olefins, of alkylbenzenes and of unsaturated Fatty acids into consideration. The anionic surfactants are advantageously used in the form of salts, hydrophilizing cations are particularly suitable for salt formation, in particular Alkali metal cations (e.g. sodium, potassium) or ammonium cations [e.g. the above] or also alkaline earth metal cations (e.g. calcium or magnesium). Among the anionic mentioned Surfactants (d2) which are free of ester groups are preferred, primarily soaps, in particular amine soaps, and the carboxymethylation products of oxyethylated fatty alcohols and the sulfonic acids, preferably in salt form as mentioned above, especially as alkali metal salts.

Known compounds which are active as dispersants also come in as amphoteric surfactants (d3) Consider, especially those that are introduced by introducing at least one anionic group into a cationic surfactant containing a reactive hydroxy or amino group are available [e.g. by Carboxyalkylation of amino groups, by esterification of hydroxy groups for the introduction of Sulfato or phosphato groups, by monoacylation of amino or hydroxy groups Cyclic dicarboxylic anhydrides analogous to (d2) described above, by sulfomethylation of amino groups, e.g. by reaction with formaldehyde and sodium bisulfite or by Reaction of an amino group with the adduct of sodium bisulfite with epichlorohydrin] or still amphoteric compounds of betaine type. Suitable cationic surfactants as starting materials well-known compounds, e.g. Fettamines, Fettaminoalkylamine and amidation products of alkylenediamines or polyalkylenepolyamines with a fatty acid residue, or acylation products of alkanolamines or alkanolaminoalkylamines, and their oxyalkylation products and / or quaternization products. The fat residues in (d3) are e.g. as described for (d1) above. The alkylene bridges between two nitrogen atoms in the alkylenediamines, polyallcylenepolyamines and alkanolaminoalkylamines are advantageously those with 2 to 6, preferably 2 to 4, carbon atoms; the alkanol groups in the alkanolamines and Alkanolaminoalkylamines are advantageously those with 2 or 3 carbon atoms. Preferred Alkylenediamines, polyamines, alkanolamines and alkanolaminoalkylamines are ethylenediamine, Propylene diamine, N, N-dimethylaminopropylamine, hexamethylene diamine, diethylene triamine, ethylene propylene triamine, Dipropylenetriamine, monoethanolamine and 3- (β-hydroxyethylamino) propylamine. For oxyalkylation, ethylene oxide is preferably added, e.g. 2 to 20 moles of ethylene oxide per mole Amino compound, or per mole of fat residue.

The surfactants (d) are preferably free of easily ridable groups, in particular ester groups.

Of the surfactants (d1), (d2) and (d3), the surfactants (d1) and especially (d2) are dispersants prefers.

According to a particularly preferred embodiment of the invention, (d) consists exclusively of (d2).

The surfactants (d) are expediently used in amounts which are sufficient for the waxes (a) can be well dispersed in the aqueous phase and an aqueous dispersion of (a) can arise. The weight ratio (d) / (a) is e.g. in the range from 10/100 to 80/100, preferably 20/100 to 60/100.

(c) ein Vernetzungsmittel,

(e) ein Hydrotropikum und/oder Schutzkolloid

und/oder (f) ein Mittel zur Bekämpfung der schädigenden Wirkung von Mikroorganismen.

In addition to the components (a), (b) and (d) mentioned, the aqueous dispersions (L) according to the invention can contain further additives, in particular

(c) a crosslinking agent,

(e) a hydrotrope and / or protective colloid

and / or (f) an agent to combat the harmful effects of microorganisms.

Suitable crosslinking agents (c) are those which are capable of reacting with or crosslinking amide groups of (b), in particular low molecular weight aliphatic compounds, for example an aliphatic aldehyde or an aliphatic diamine, in which both amino groups are primary. Suitable (c) aliphatic crosslinking agents are, for example, those with up to six carbon atoms, for example formaldehyde and acetaldehyde, and alkylenediamines with 2 to 6 carbon atoms, for example of the formula H ₂ N― (CH ₂ ) _p ―NH ₂ where p is 2 to 6,
among which preferred are those wherein p is 2 or 3.

The crosslinking agents (c) are advantageously used in such amounts that they are sufficient existing amide groups in (b) can be at least partially crosslinked. The molar ratio of (c) to the amide groups of (b) present is advantageously in the range from 0 to 10, preferably 0.01 to 5. Among the crosslinking agents, the aldehydes are preferred.

(e) ein Schutzkolloid (e1) und/oder ein Hydrotropikum (e2)

eingesetzt. According to a particular embodiment of the invention, in addition to (d),

(e) a protective colloid (e1) and / or a hydrotrope (e2)

used.

Protective colloids (e1) here are both highly hydrophilic polymers and highly hydrophilic surfactants meant that a protective effect on the aqueous two-phase system, especially on the dispersed Particles, exercise. These highly hydrophilic surfactants differ from (d) in particular in that they are not dispersants per se, insofar as they alone are not suitable for the Disperse waxes finely, but have a stabilizing effect on the (d) -containing dipersion.

Protective colloids (e1) are any highly hydrophilic products known per se Consider, preferably non-ionic or amphoteric compounds.

Non-ionic protective colloids are, for example, to increase the hydrophilicity, chemically modified polysaccharides [eg hydroxy- (C _1-4 -alkyl) - and / or carboxymethyl- and optionally methyl-modified polysaccharides], hydrophilic vinyl polymers (eg polyvinyl alcohols or polyvinylpyrrolidones) or oxethylation products of higher aliphatic alcohols. The HLB of the non-ionic protective colloids is advantageously> 15, preferably ≥ 16.5, especially in the range from 16.5 to 19.

R₁

einen aliphatischen Kohlenwasserstoffrest mit 11 bis 18 Kohlenstoffatomen
und

q

20 bis 100

bedeuten, und können als Einzelverbindungen oder auch als Gemische solcher Verbindungen vorliegen.Preferred non-ionic protective colloids (e1) are oxyethylation products of aliphatic fatty alcohols or synthetic alcohols, for example those as described above as the starting product for the preparation of (d1). Particularly preferred non-ionic protective colloids correspond to the average formula R ₁ ―O― (CH ₂ ―CH ₂ ―O) _q ―H wherein

R ₁

an aliphatic hydrocarbon residue with 11 to 18 carbon atoms
and

q

20 to 100

mean, and can be present as individual compounds or as mixtures of such compounds.

In the formula (III), q preferably denotes 30 to 70, in particular 35 to 60.

Suitable amphoteric protective colloids are e.g. those which are produced analogously to (d3) above may differ from (d3) by a higher hydrophilicity, e.g. through a polyglycol ether chain, a quaternization or protonation, in relation to the lipophilic residue. They are suitable in particular quaternary amphoteric surfactants, which are a fat residue and a preferably quaternary Ammonium group and an anionic radical and optionally a polyethylene glycol ether chain contain, especially those with a molecular weight of the internal salt form in the range of 300 to 3000 and wherein the fat residue advantageously contains 8 to 24, preferably 12 to 18 carbon atoms.

If a protective colloid (e1) is used, for example, per 100 parts by weight (a) 5 to 50, advantageously 10 up to 40 parts by weight, preferably 15 to 35 parts by weight of protective colloid (e1).

Optionally, the dispersions (L) as (e) may also contain a hydrotrope (e2), which also can serve as a solubilizer or antifreeze.

As a hydrotrope or anti-freeze (e2), products known per se can be used, in particular non-ionic, predominantly low molecular weight amides (e.g. acetamide or urea) and aliphatic oligohydroxy compounds [e.g. with 2 to 12, preferably 3 to 10, in particular 4 to 8, carbon atoms , for example glycerol, hexylene glycol and / or mono- or oligo- (C _2-4 -alkylene) -glycols] or their mono- (C _1-4 -alkyl) ether.

If (e2) is used, its proportion in (L) can vary within a wide range. The Weight ratio of (e2) to (L) is advantageously in the range of 0.5 to 15 parts by weight (e2) per 100 parts by weight (L), preferably in the range of 1 to 10 parts by weight (e2) per 100 parts by weight (L).

If necessary, the dispersions (L) to be used according to the invention can additionally at least contain an additive (f), which is expediently an anti-bacterial agent or Is microbicid. Fungicides and bactericides come into consideration as (f), e.g. for sale Products that can be used in the recommended concentrations.

The dispersions (L) according to the invention can be mixed in a very simple manner by suitable mixing of the components are produced, in particular in that an aqueous dispersion (w) of (a), which also contains (d), mixed with an aqueous solution of (b) and, if appropriate, further additives, in particular (c), (e) and / or (f).

The aqueous dispersion (w) can be prepared in a very simple manner by e.g. a corresponding (a) melt, which also contains (d) and optionally (e), and which optionally contains one suitable base for salt formation with the carboxy groups has been added (e.g. an alkali metal hydroxide or carbonate and / or an amine, as it corresponds to the above cations), with Diluted water.

The dispersant system (d) is expediently chosen so that a dispersion of (a) is formed; the Components (c), (e) and / or (f) can be mixed before and / or after the (a) dispersion has been mixed with the (b) solution are added, depending on the convenience. The components (e1) and (e2) are advantageously mixed with the (a) dispersion. Component (c) can be mixed before or after mixing (a) are added with (b). Component (F) is advantageously added last.

The pH of the dispersions (L) can vary widely, e.g. in the range of 3 to 12, preferably 4 to 11. The proportions of the respective components and additives, especially the anionic Components and optionally added base can be selected accordingly. A Crosslinking with (c) is particularly favored by alkaline pH values, e.g. in the range of 7.5 to 12, preferably 8 to 11.

The aqueous dispersions (L) can be diluted as desired. They are advantageous if possible concentrated, preferably so that a fine aqueous flowable dispersion is formed. Of the The content of (a) + (b) in (L) is e.g. in the range from 0.3 to 40% by weight, advantageously 0.6 to 20% by weight, preferably 1 to 5% by weight. The flow behavior can e.g. according to ASTM-D 1200, 73/050 can be determined. The flow time in the Ford cup (Ford cup) No. 4, at 22 ° C, is e.g. 5 to 60 seconds, advantageously 10 to 45 seconds.

The dispersions (L) obtainable as described above are very finely divided; e.g. Dispersions (L) in which the particle size of the dispersed particles is in the range of 0.01 to 10 µm, preferably 0.05 to 1 µm. The dispersions (L) can be made as they are have been handled and transported directly, they are particularly very stable and fine dispersions (L) available, even those that are very frost and heat resistant.

The dispersions (L) to be used according to the invention are advantageously essentially free of components other than (a), (b), (c), (d), (e), (f), water and any electrolytes [e.g. from the Preparation of (a), (b) or (d) or from pH adjustment]. Preferably there are Dispersions (L) according to the invention essentially of: (a), (b), (d) and water and, if appropriate (c) [crosslinked with (b)], (e) and / or (f) and any electrolytes.

The dispersions (L) described above are used as wet lubricants, i.e. as an aid when treating textile fabrics with treatment agents (T) (e.g. pretreatment, dyeing, optical brightening or post-treatment) under such conditions, under which otherwise Creases can arise or friction can take place in or on the substrate, the Dispersions (L) to be used according to the invention, in particular to prevent stabilization and Marking the wrinkles that develop during the treatment and to prevent harmful ones Serve friction. Such processes are essentially pull-out processes short liquor (liquor / substrate weight ratio e.g. in the range from 3: 1 to 40: 1, usually 4: 1 to 20: 1) under the usual treatment conditions and times (e.g. in the range of 20 minutes up to 12 hours).

The dispersions (L), or the components (a) and (b) optionally crosslinked with (c), are in the essentially non-substantive and are generally eliminated by lowering the fleet or / and eliminated by the process-related washing and / or rinsing cycles.

The treatment agents (T) are generally textile chemicals, which after the respective treatment of the substrate for which part which is not fixed on the substrate are removed from the substrate again, e.g. by washing and / or rinsing.

(T₁)

Vorbehandlungsmittel (hauptsächlich Netzmittel, Alkalien, Waschmittel, Bleichmittel),

(T₂)

Hauptbehandlungsmittel (hauptsächlich Netzmittel, Farbstoffe, Färbehilfsmittel, optische Aufheller),
und

(T₃)

Nachbehandlungsmittel (hauptsächlich Fixiermittel für Färbungen, Waschmittel, Abziehmittel, Alkalien);

wobei die jeweiligen Behandlungen in wäßrigem Medium durchgeführt werden.The following subgroups are particularly suitable as (T):

(T ₁ )

Pretreatment agents (mainly wetting agents, alkalis, detergents, bleaches),

(T ₂ )

Main treatment agents (mainly wetting agents, dyes, dyeing aids, optical brighteners),
and

(T ₃ )

Post-treatment agents (mainly fixatives for stains, detergents, stripping agents, alkalis);

the respective treatments being carried out in an aqueous medium.

The main processes in which creases can arise in the textile substrate are meant those in which the wet substrate by exposure and possibly interference various forces tend to fold. The wrinkles in such procedures can arise from stabilization in the course of the treatment process for marking of the kinks, which can lead to the disadvantages mentioned at the beginning. In such procedures the dispersions (L) serve as anti-crease agents, etc. insofar as it is a sliding of the favor or enable wet fabric or the wet folds and thus a harmful Can prevent stabilization of the creases. As a treatment procedure that causes wrinkles treatments mainly occur on a reel (especially in a reel runner) or especially in jet dyeing machines, where the substrate in each cycle is guided over the reel or through the nozzle, at which point the wrinkling or / and on the forces acting on the folds, which can stabilize the folds, are strongest.

As a method in which friction can take place in or on the textile substrate, the essentially meant those in which the wet substrate due to high running speed, guidance by nozzles or / and changing the direction or / and speed against apparatus parts or adjacent substrate parts rubs. The chafing spots that arise in such processes can in Course of the treatment process to mark them and to impair the physical Lead properties of the substrate. In such processes, the dispersions (L) serve as Wet lubricant insofar as it slides the wet fabric (especially on adjacent fabric or on metal) favor or enable and thus harmful friction of the substrate can prevent. Treatment processes that cause chafing mainly come Treatments in jet dyeing machines are contemplated, in which the substrate in each Cycle through the nozzle, at which point the relative acceleration and / or on the substrate angular forces are strongest, and wherein the substrate in each cycle of the own position in the fleet is dragged to the nozzle, so that the substrate-against-substrate at the respective points Acceleration or substrate-to-metal acceleration in places cause, which can lead to the abrasion points mentioned.

As substrates for the method according to the invention and for the wet lubricants according to the invention any substrates, such as those used in the processes mentioned, are generally suitable can, in particular those which contain modified cellulose fibers, e.g. Cotton, linen, jute, hemp, ramier and modified cotton (e.g. viscose rayon or Cellulose acetates) and cotton-containing fiber mixtures (e.g. cotton / polyester, cotton / polyacrylic, Cotton / polyamide or cotton / polyamide / polyurethane). The textile substrate can be in any form can be used, as they are treated in the methods mentioned can, e.g. as tubular goods, as open textile webs or as semi-finished goods, essentially in strand form, as it is suitable for reel or jet; it can be both knitwear as well Fabrics are used (e.g. fine to coarse simple knitwear or interlock, fine to coarse fabrics, terry goods, velvet and openwork and / or machine-embroidered textiles).

The wet lubricants (L) according to the invention are expediently used in such concentrations that that effective prevention of wrinkle marking and chafing in the respective process he follows. They are characterized by their effectiveness and extensiveness and can be very low concentrations show a very high effect; they are advantageous in such Concentrations used that 0.01 to 2 g [(a) + (b)] per liter of liquor, primarily 0.02 to 1.5 g [(a) + (b)] per liter of liquor, preferably 0.03 to 1 g of [(a) + (b)] per liter of liquor, particularly preferred Correspond to 0.04 to 0.5 g [(a) + (b)] per liter of liquor.

Since the wet lubricants (L) according to the invention are also distinguished by their great independence from temperature fluctuations and are largely resistant to electrolytes, they can also be used in a very wide range of treatment conditions as they occur in technology for treatment with textile chemicals (T), in particular for pretreatment with (T ₁ ), for dyeing or optically brightening with (T ₂ ) and for post-treatment with (T ₃ ), e.g. with (T ₁ ) when boiling (e.g. when beating), when desizing or bleaching, with (T ₂ ) in dyeing or optical brightening or also with (T ₃ ) in aftertreatment, in particular with cationic fixatives to improve the dyeing fastness (especially the wet fastness), but old when dyeing. Any dye or optical brightener (T ₂ ) suitable for the particular substrate and process and for the desired effect can be used for the dyeing or optical brightening. Any suitable dyes can be used for dyeing cellulose-containing substrates, for example reactive dyes, direct dyes, vat dyes, sulfur dyes or also basic dyes, it also being possible to use corresponding additional dyes, in particular, for dyeing substrates from fiber mixtures, in particular from cellulose fibers and synthetic fibers Disperse dyes. The processes can run through any temperature ranges, such as those for the respective substrate and the treatment agent used, as well as due to the apparatus and the desired purpose, e.g. from room temperature (e.g. at the start of dyeing) to HT conditions (e.g. in the range of 102 up to 140 ° C, in the closed apparatus). The electrolyte content of the liquors can also be of any type that is normally used for the respective processes, for example in accordance with the concentrations of alkali metal compounds used for boiling, bleaching or desizing, or the alkali metal salt (for example sodium chloride or sodium sulfate) ) concentrations or / and alkali metal hydroxide or carbonate concentrations, such as are used in dyeing with the dyes mentioned, be it as a blend component in commercially available dye preparations and / or as a raking aid in dyeing or optical brightening, or as alkalis in dyeing Sulfur dyes, vat dyes or reactive dyes are used.

Post-treatment agents (T ₃ ) for increasing the fastness of the dyeings are generally known polycationic products of high charge density, primarily aliphatic condensation products of dicyandiamide or epichlorohydrin with an aliphatic mono- or polyamine or of epichlorohydrin and ammonia, which may be in protonated form available. Such post-treatments advantageously use dispersions (L) in which (b) is essentially free of carboxy groups and (d) consists of (d1), while for pretreatment, coloring and brightening, the dispersion system (d) is preferably used in (L) (d1) or / and (d2).

The dispersions (L) are particularly advantageously used as wet lubricants for dyeing, preferably in nozzle dyeing machines, particularly preferred for dyeing cellulose-containing substrates.

Due to the great resistance to temperature fluctuations and high electrolyte concentrations The wet lubricants (L) according to the invention can be used under the conditions mentioned and come into their own without being impaired. By the big one Shear stability of the wet lubricants (L), especially those that do not have non-oxidized waxes (a2) contained, but only from (a1), (b), (d) and optionally (c), (e) and / or (f) in aqueous Dispersion exist, these are particularly suitable as wet lubricants in nozzle dyeing machines before especially in those in which the goods or the fleet have extremely high dynamic loads are exposed, or in which very high shear forces develop in the fleet.

The dispersions (L) also have very short liquors, e.g. for fleet / goods ratios ≤ 15/1, especially <10/1, a very good, extremely superficial wet sliding effect, in particular insofar as they cause the lubricant to accumulate on the surface of the goods and the liquor accumulates in the immediate vicinity of the lubricant and as a flowing liquor layer wet gliding of the goods is surprisingly much easier.

By using the wet lubricant (L) according to the invention, even when using very short ones Fleets, e.g. optimally pre-treated, optically brightened, colored or / and post-treated materials are obtained in which the effect of the respective treatment agent (pre-treatment agent, Dye, optical brightener or aftertreatment agent) is not impaired and that Product image is optimal.

The effectiveness of the preparations (L), especially in the sub-fleet area, can be determined by measuring the Friction coefficients e.g. can be determined as follows: A first piece of fabric is attached to the inside floor stretched against a low, flat tub, fastened with a clamp at one end and with a lot of fleet covered, which corresponds to the usual fleet conditions; then a 200th g Weight with smooth, flat, rectangular bottom on which a second piece of the same Fabric is stretched and fastened, placed horizontally. Now put on the second one Piece of fabric covered weight (= "slide") in the longitudinal direction of the tub and the first stretched piece of fabric (= "web") until it starts to move and until it is a constant Speed is reached, and it determines the pulling force needed to pull the "sled" on the "web", starting from the end fixed with the clamp, to move horizontally and to move horizontally in the direction of pull at a constant speed. This allows both static friction and kinetic friction and thus both static Coefficient of friction and the kinetic coefficient of friction can be determined.

One designates with N ₀ the normal force (ie the weight of the "slide" on the "track"), with Z _S the horizontal tensile force required to set the "slide" on the "track" in motion, and with Z _K the horizontal tensile force required to keep the "carriage" moving at a constant speed on the "track", the static friction coefficient µ _S can be calculated using the following formula µ S = Z. S N 0 and the kinetic coefficient of friction µ _K by the following formula µ K = Z. K N 0 be expressed.

By using (L) not only µ _K but also µ _S can be brought to very low values.

This can be visualized by the formation of a superficial fleet level on one of the (L) -containing Fleet hoisted, stretched fabric, effectiveness shown above the fleet by the Light reflection of the goods can be observed.

The overall effectiveness of the wet lubricant can be checked visually by checking the appropriately treated goods to determine chafing marks or marks on the creases (e.g. on a Staining).

In the following examples, parts are parts by weight and percentages are percentages by weight; the Temperatures are given in degrees Celsius. In the application examples, the dyes used in commercial form with an active substance content of about 25%, the specified Concentrations refer to this form. C.I. stands for Color Index. The sodium sulfate is as Glauber's salt is used and the amounts indicated relate to Glauber's salt. In the the examples in abbreviated form using only a letter and a number of waxes, Dispersants and protective colloids are the following:

Wax (A11)

Tropfpunkt

103-105°C

Säurezahl

25

Dichte

0,96

Nadelpenetration (ASTM D-1321)

5 dmm

Oxidized polyethylene with

Dropping point

103-105 ° C

Acid number

25th

density

0.96

Needle penetration (ASTM D-1321)

5 dmm

Dispersant (D11)

C ₁₈ , H ₃₇ - (OCH ₂ CH ₂ ) ₁₀ -OH

Protective colloid (E11)

Protective colloid (E12)

C ₁₈ H ₃₇ - (OCH ₂ CH ₂ ) ₄₀ -OH

Macrocopolyacrylamide (B11)

Partially hydrolyzed polyacrylamide with a molecular weight M _W of 20 · 10 ⁶ and 27 ± 3 mol% CH ₂ -CH-COONa monomer units.

Polyacrylamide (B21)

Polyacrylamide (homopolymer) with a molecular weight M _W of 2 · 10 ⁶ .

example 1

54.0 parts of wax (A11) are heated to 120 ° C. under nitrogen and then first reacted with 9.5 parts of oleic acid and then with 9.5 parts of 3-methoxypropylamine. The clear, homogeneous melt obtained is then added to 394.0 parts of water at 94-96 ° C. with stirring, a fine, almost transparent dispersion being formed which is cooled to 30 ° C. Now 73.0 parts of a 29% solution of (E11) in a mixture of 15% hexylene glycol, 65% dipropylene glycol and 20% water are added. 540.0 parts of wax dispersion (W1) are obtained, which are added to 2451.0 parts of an aqueous solution of 3.0 parts of macrocopolyacrylamide (B11) in 2448.0 parts of water, at room temperature, with stirring. Now 6.0 parts of a 37% aqueous formaldehyde solution are added, then 3.0 parts of a 1.5% aqueous solution of 2-methyl-4-isothiazolin-3-one, which still has 1 , 75% Mg (NO ₃ ) ₂ , 0.85% MgCl ₂ and 0.12% Cu (NO ₃ ) ₂ , is added as a microbicide and then unloaded. 3000.0 parts of an aqueous dispersion (L1) with a flow time (Erichsen, Ford Cup No. 4, ASTM-D 1200, 73/050) of 32 seconds (at 22 ° C.) are obtained.

Example 2

560.0 parts of a 3% aqueous solution of a polyacrylamide (B21) with 1894.9 parts Diluted water. Then 2.1 parts of macrocopolyacrylamide (B11) are stirred admitted. As soon as a homogeneous solution is present, 3.0 parts of a 37% strength aqueous solution Formaldehyde solution and then 540 parts of wax dispersion (W1) (as in Example 1) were added. 3000.0 parts of an aqueous dispersion (L2) with a flow time (Erichsen, Ford Cup No. 4, ASTM-D 1200, 73/050) of 38 seconds (at 22 ° C).

Example 3

76.6 parts of dipropylene glycol are heated to 120 ° C. under nitrogen and then with 112.4 parts Wax (A11) added. A clear, transparent solution is formed which is then 25.8 parts Dispersant (D11) is added. After adding 3.8 parts of potassium hydroxide, the homogeneous Add melt to 265.6 parts of water at 94-96 ° C with stirring. Then is at 30 ° C. cooled and the practically transparent dispersion 55.8 parts of a 30% added aqueous solution of the protective colloid (E12). 540.0 parts of wax dispersion (W2) contain the same as (W1) in Example 1. 3000.0 parts of an aqueous are obtained Dispersion L3 with a flow behavior (Erichsen, Ford Cup No. 4, ASTM-D 1200, 73/050) of 30 Seconds (at 22 ° C).

Application example A [dyeing pure cotton with reactive dyes - cold dyeing - in the reel runner]

In 1400 parts of an aqueous liquor heated to 40 ° C., the 120 parts of sodium sulfate and 3 parts Contains dispersion (L1), 100 parts of cotton fabric are entered. You add one to the bathroom Solution of 3.3 parts of C.I. Reactive Red 147 in 100 parts of water and leave the apparatus at 40 ° C. Run for 30 minutes. Then, at intervals of 5 minutes, 20 parts are made 5 times each 10% soda solution added. It is then heated to 60 ° C and the color is at this Temperature carried out for another 30 minutes. After the usual completion (rinsing, Washing), you get a very level red color with an excellent appearance.

Application example B [dyeing pure cotton with reactive dyes in the jet dyeing machine (Rotostream Thies)]

To 600 parts of an aqueous liquor heated to 80 ° C., the 70 parts of sodium sulfate and 2 parts Contains dispersion (L1), 100 parts of cotton fabric are entered. You add one to the bathroom Solution of 3.1 parts of C.I. Reactive Blue 52 in 100 parts of water and the liquor is heated to 95 ° C heated up. After 30 minutes at this temperature, at intervals of 5 minutes, 5 times 4 parts of a 3% NaOH solution are added and the coloring becomes even more 40 minutes. After completion in the usual way (rinsing, washing) you get a very level and calm blue color.

Instead of (L1) in application examples A and B, the same amounts of Dispersion (L2) or (L3) can be used.

Claims (9)

Aqueous dispersion (L) containing: (a) a wax which (a1) a hydrocarbon wax containing carboxy groups or a mixture of such waxes
or a mixture of (a1) and (a2) at least one unmodified hydrocarbon wax, (b) a (Co) poly (meth) acrylamide or (Co) poly (meth) acrylamide mixture, which (b1) at least one macro (co) poly (meth) acrylamide which optionally contains carboxy group-containing comonomers, with an average molecular weight M W = n · 10 6 , where n is ≥ 10,
or a mixture of (b1) and (b2) at least one (co) poly (meth) acrylamide, which optionally contains carboxy group-containing comonomers, with an average molecular weight M _W <10 · 10 ⁶ , is and (d) a dispersant system consisting of amphoteric, anionic and / or non-ionic surfactants. Aqueous dispersion (L) according to claim 1, wherein (b1) and / or (b2) with a bifunctional Crosslinking agent (c) is crosslinked. An aqueous dispersion (L) according to claim 2, wherein (c) is an aliphatic aldehyde or a aliphatic diamine is where both amino groups are primary Aqueous dispersion (L) according to one of claims 1 to 3 additionally containing at least one further additive, which (e) a hydrotrope and / or protective colloid and / or (f) an agent to combat the harmful effects of microorganisms. Aqueous dispersion (L) according to any one of claims 2 to 4, wherein (b) is crosslinked with (c). Process for the preparation of the aqueous dispersions (L) according to one of Claims 1 to 5, characterized in that an aqueous dispersion of (a) with (d) with an aqueous Mixing solution of (b) and optionally adding further additives (c), (e) and / or (f). Use of the aqueous dispersions (L) according to one of claims 1 to 5 as an auxiliary in the treatment of textile material with a textile treatment agent (T) from an aqueous liquor. Use according to claim 7 for dyeing or optically brightening textile webs aqueous fleet. Use according to claim 7 or 8 as wet lubricant in dyeing or optical brightening in jet dyeing machines.