WO2009112329A1 - Post-crosslinking wax and method for producing the same - Google Patents

Abstract

The invention relates to a cross-linkable wax which contains at least one amino functional silicon compound and at least one carboxy functional wax and optionally an organo functional silicon compound and/or the salts thereof, and to aqueous wax compositions. The invention further relates to methods for producing the same and to the use thereof.

Description

 Postcrosslinking wax and process for its preparation

The invention relates to a crosslinkable wax comprising at least one amino-functional silicon compound and at least one carboxy-functional wax and optionally an organofunctional silicon compound and / or salts thereof, and aqueous wax compositions. Furthermore, the invention relates to processes for their preparation and their use.

Wax is a collective name for a variety of products that may be of differing molecular structure and origin, but have similarities in their technological properties, such as mechanical-physical properties. There are animal and vegetable waxes of natural origin, which include waxes from petroleum, such as table paraffins and micro waxes, as well as the lignite-derived montan wax. The animal and vegetable waxes are based on esters of fatty acids with long-chain, aliphatic alcohols. Typical vegetable waxes are palm-derived carnauba wax, and jojoba oil can also be considered a liquid wax. Typical synthetic waxes are water-soluble polyethylene glycols, the polyethylene and polypropylene waxes prepared by olefin synthesis and Fischer-Tropsch waxes prepared by the Fischer-Tropsch synthesis. A detailed overview of the wax area, the types of wax available on the market, as well as their extraction and production processes, can be found in the Ullmann Encyclopaedia.

In the first stage of the production of synthetic waxes, such as the polyethylene, polypropylene and Fischer-Tropsch waxes, these are usually based on pure hydrocarbon compounds. Their usual molecular weights are in a range of 500 to 5000, in exceptional cases up to 10000 - according to the molecular weight determination by osmomethschen method.

These waxes are referred to as so-called hard paraffins, their melting ranges are usually from 85 ⁰ C to 120 ⁰ C; the melting point of a Polypropylene wax is usually at about 160 ⁰ C. Manufacturer of synthetic waxes are, for example, the companies Clariant AG, Honeywell Inc., BASF AG, Evonik Degussa GmbH, Shell AG or the Sasol Ltd.

In order to be able to supply these hard paraffins to a broader spectrum of applications, it is necessary for some applications to provide these non-polar hard paraffins, without functional groups, in an oxidation process with hydroxy, carboxy and carboxylic ester groups on the polymer backbone, to the polarity to increase the connections. Typically, the oxidation is carried out in a solid phase, or in a dispersant such as water, or in a molten phase.

For example, DE 31 12 163 A1 describes a process for the oxidation of polyethylene in the solid phase in a fluidized bed reactor. Also, US 3,463,767 discloses a solid phase oxidation of polyethylene. Oxidation in the liquid, aqueous phase is described in the published patent application DE 20 35 706 A1, which discloses a process for the oxidation of ethylene-containing homopolymers and copolymers. Oxidation in the molten phase is disclosed in DE 102 33 464 A1.

Due to the oxidative incorporation of the functional groups in waxes, their range of use can be extended. The increased polarity of the processed waxes extends their use as plastic lubricants, their use in printing inks and coatings, but especially their processing out of the aqueous phase out. The oxidized waxes, which are also referred to as wax oxidates, can be easily dispersed in water with suitable auxiliaries, for example emulsifiers. In addition, the carboxy groups can be easily further reacted with basic compounds such as calcium hydroxide, sodium hydroxide or lithium hydroxide to metal soaps. In this case, one speaks of so-called partially saponified waxes, which lead to a further change in the properties of the waxes and thus of a wax coating. The characterization of the waxes is usually carried out by the "German Society for Fat Science; For example, the melting behavior or dropping point according to DGF M-III-3, the hardness or penetration number according to DGF M-III-9b and the acid, saponification and hydroxyl numbers according to titration according to DGF M-IV- 2 is measured. the viscosity of waxes is in the molten state at a temperature of 120 ⁰ C or 1 50 ⁰ C determined with a rotational viscometer. additional parameters for the characterization of the waxes are t he density and molecular weight. the density of hard paraffins based on polyethylene or Fischer-Tropsch waxes is approximately between 0.92 and 0.96 g / cm ³ , wherein the determined by the osmometric method molecular weight is usually between 500 and 5000, in exceptional cases up to 10,000.

The processing of waxes preferably takes place from an aqueous dispersion. Colloquially, this aqueous dispersion or aqueous

The form of expression is falsely referred to as waxing. These

Wax emulsions are used, for example, in the production of

Fruit coatings, as care products, in textile auxiliaries, in emulsions for

Paper production, in aqueous printing ink and coating systems as well as in emulsions for temporary corrosion protection.

In order to be able to disperse the said waxes in water, or to make them water-dispersible, it is necessary that the waxes have a certain polarity. This polarity is usually adjusted by the degree of oxidation of the waxes. Usually, additional emulsifiers are needed to make the waxes water-dispersible. As a rule, these emulsifiers are oligomeric or polymeric compounds having a hydrophilic and a lipophilic radical. The lipophilic radical generally consists of a long straight-chain or branched alkyl chain or alkyl / aryl chain. Depending on the hydrophilic radical, nonionic, anionogenic or cationogenic emulsifier systems are used. Typical non-ionic systems include as hydrophilic moiety polyalkyl ethers, anionogenic systems Carboxylate functional hydrophilic residues and cationogenic systems typically include ammonium salts. In principle, an emulsifier is anchored via its lipophilic radical in polymeric wax, so that the polymer or the wax is provided with hydrophilic groups by means of an emulsifier and in this way can be dispersed in water. In principle, the polymers themselves can also be modified so that they have a sufficient number of carboxylate or ammonium functions which make it possible to disperse the polymer in water. The additional use of an emulsifier is then not necessary. The modified polymers can then be reacted with alkali, alkaline earth metal hydroxides or amine or with acids such as formic acid or acetic acid, and then dispersed in water.

Depending on the structure, the emulsifier systems produced in this way have various disadvantages. For example, non-ionic emulsifiers usually have to be used in an increased concentration, which softens the waxes. The emulsifiers act as plasticizers. Coatings produced from this are usually sensitive to moisture. Also, non-ionic emulsifiers tend to diffuse to the surface, whereby the surface can become soft and greasy and the inter-layer adhesion deteriorates.

If alkali metal hydroxides or alkaline earth metal hydroxides are used as anionogenic emulsifiers, the wax film is on the one hand relatively hard, but on the other hand it is sensitive to moisture since alkali metal and / or alkaline earth metal hydroxides remain as non-volatile constituents in the wax film and can be dissolved by water. By using amines, alone or in combination with oleic acid in anions systems, their volatilization eliminates this disadvantage and achieves greater water resistance, but undesirably releases amines to the environment. The same applies to cationogenic systems in which the emulsifier and / or the emulsifying polymer or the wax is provided with primary, secondary and / or tertiary amino groups and has been emulsified with an appropriate acid. Usually, when Drying the cationogenic systems released a volatile acid such as acetic acid or formic acid, and then released into the environment.

In addition to the emulsifying system used and the amount of emulsifier, the hardness and resistance of a wax film formed are also dependent on the molecular weight of the wax used itself.

The object of the present invention was to develop a slightly dispersible or colloquially slightly emulsifiable wax which crosslinks after application, in particular from an aqueous composition, to increase the structure and / or increases its molecular weight by crosslinking and in position is to crosslink to higher molecular weight wax films.

To solve the problem described above, the present invention proposes a crosslinkable wax according to claim 1 or 21 and a manufacturing method thereof according to claim 12 before. Further objects of the present invention are also a wax composition according to claim 10 or 22 and their preparation according to claim 18 or 19 as well as the use of the wax and / or the wax composition according to claim 24. Further advantageous embodiments are the subject of respective subclaims.

The invention according to a first aspect of the invention is a crosslinkable wax containing at least one amino-functional silicon compound, in particular an aminoalkyl, diaminoalkyl or thaminoalkyl group-containing silicon compound and at least one carboxy-functional wax and optionally an organofunctional silicon compound and / or salts thereof. Another aspect of the invention relates to a wax composition comprising the crosslinkable wax and water.

As a carboxy-functional wax in the crosslinkable wax according to the invention carboxy-functional waxes, which are also synonymous in the following also referred to as wax oxidates, with an acid number above 15 mg KOH / g wax, in particular above 20 mg KOH / g, particularly preferably understood with an acid number above 30 mg KOH / g wax. In particularly preferred embodiments, the carboxy-functional wax has an acid number above 45 mg KOH / g wax. To increase the number of carboxy groups or to increase the acid number of the crosslinkable wax, the crosslinkable wax may additionally contain oleic acid. The content of oleic acid in the crosslinkable wax should be at most 40% by weight, in particular not more than 20% by weight and preferably not more than 10% by weight, based on the total weight of crosslinkable wax and all auxiliaries and additives. Particularly preferably, the crosslinkable wax has no content of oleic acid. Suitable carboxyfunctional waxes are generally natural waxes, such as carnauba wax and ozokerite wax, mineral wax derivatives, such as oxidized table waxes and oxidized micro waxes, acid montan waxes, Montanwachsderivate, such as partially hydrolyzed or partially esterified montan waxes, fatty acid derivatives, oxidized Fischer-Tropsch waxes and oxidized polyolefin waxes and mixtures of said waxes the wax and / or the wax mixtures should have the abovementioned acid number and should have free carboxy groups. In particular, the drop points of these waxes or wax mixtures unterhal b 1 1 5 ⁰ C, preferably below 110 ⁰ C. In a dispersion or emulsification in an aqueous phase in an autoclave under pressure higher dropping points of the wax or wax mixtures are of course possible.

The carboxy wax, optionally in admixture with oleic acid, may, for example, at a temperature between 120 ⁰ C and 150 ° C with an aminofunctional silicon compound, in particular an amino group-containing organosilane to be implemented. This added amino-functional silicon compound has at least one amino group which may be present as a primary, secondary or tertiary amino group. These may be aminoalkyl, diaminoalkyl or triaminoalkyl group-containing silicon compounds. In particular, primary and / or secondary amino-functional silicon compounds are preferred, primary amino-functional silicon compounds are particularly preferred. According to a particularly preferred embodiment, only amino-functional silicon compounds having primary amino groups are present in the crosslinkable wax.

In general, the amines can increase the structure by reacting with the carboxy-functional waxes and / or increase their molecular weight by crosslinking with carboxy functions of the waxes, in these cases, for example - starting from the initially formed ammonium salt - at least one amide bond can be formed. To form the intramolecular amide bond between the amino-functional silicon compounds and a carboxy-functional wax, particular preference is given to primary amino-functional silicon compounds which are particularly easy to react with a free carboxy function of the wax to form an ammonium function.

The crosslinkable wax preferably contains at least one amino-functional silicon compound which may correspond to at least one aminosilane of the general formula Ia or Ib, its salt and / or a siloxane derived therefrom,

A ¹ _m SiY ¹ _n (Ia) (Y ^{1 *} ) ₃ Si-A ^{1 *} -Si (Y ^{1 *} ) ₃ (Ib)

where A ¹ and / or A ^{1 * can} independently of one another correspond to an unsubstituted or substituted aminoalkyl, diaminoalkyl or triaminoalkyl group, with m = 1 or 2 and n = 1, 2 or 3 with m + n = 4,

In particular, A ¹ in formula Ia is the same or different and may correspond to an amino-functional radical of the general formulas IIIa and / or IIIb,

R ¹ VNH _(2-h *) [(CH 2) _h (NH)] _J [(CH ₂ ) 1 (NH)] _c - (CH ₂ ) _k - (lilac)

wherein 0 ≦ h ≦ 6; h ^* = 0, 1 or 2, j = 0, 1 or 2; 0 ≤ I ≤ 6; c = 0, 1 or 2; 0 ≤ k ≤ 6 and R ^{10 is} a benzyl, vinylbenzyl, aryl, vinyl, formyl radical and / or a linear, branched and / or cyclic alkyl radical having 1 to 8 carbon atoms, and / or

[NH ₂ (CH ₂ ) e] ₂ N (CH ₂ ) d - (MIb)

where 0 ≦ e ≦ 6 and 0 ≦ d ≦ 6, in particular, e and / or d correspond to integers, and / or

In particular, A ^{1 *} in formula Ib is the same or different and may correspond to a bis-amino-functional radical of the general formula IMc,

- (CH ₂ ), - [NH (CH ₂ ) _f ] _g NH [(CH ₂ ) _f * NH] _g * - (CH ₂ V- (Never)

wherein i, i ^* , f, f ^* , g or g ^{* are the} same or different, with i and / or i ^* = 0 to 8, where i and / or i ^* independently correspond to an integer, f and / or f ^* = 1, 2 or 3, g and / or g ^* = 0, 1 or 2 correspond and / or

• Y ¹ and / or Y ^{1 *} may each independently be the same or different and may have one of the following groups -OH, -OM, -OR ¹ , -R ¹ , -O (CO) R ¹ , -N (R ¹ ) ₂ , -Cl, -Br, -J and / or -OSi (R ¹ ) _a (OR ¹ ) _b with a = O, 1, 2 or

3 and b = 0, 1, 2 or 3 and a + b = 3, wherein R ^{1 is} independently the same or different and is a hydrogen, a linear, branched and / or cyclic alkyl, alkenyl, alkynyl and / or alkylaryl group, an aryl and / or heteroaryl group having in each case 1 to 18 C atoms, which is in each case substituted or unsubstituted, where M comprises a metal cation, and in particular an alkali metal cation, such as Na ⁺ , K ⁺ or Li ⁺ and other common monovalent or divalent metal cations. Suitable cyclic alkyl, alkenyl and / or alkynyl groups are in particular cycloalkyl or cycloalkenyl and / or cycloalkynyl groups. In particular, Y ¹ and / or Y ^{1 *} in the formulas Ia and / or Ib independently of one another can correspond to -OH, -ONa, -OK, -OR ¹ , -R ¹ , -O (CO) R ¹ , where R ^{1 is} independent may be identical or different from one another and may correspond to a hydrogen, a linear, cyclic and / or branched alkyl radical having 1 to 4 C atoms, R ¹ particularly preferably a methyl, ethyl, propyl, iso -Propyl group can correspond.

Particularly preferably, the amino-functional silicon compound can correspond to an aminosilane or aminoalkylsilane, with aminoalkylalkoxysilanes being particularly preferred. Particularly preferred aminosilanes are 3-aminopropylthymethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, 2-aminoethyl-3-aminopropylthmethoxysilane and / or a triamine-functional propylthmethoxysilane. Typical compounds are also 2-aminopropyl-3-aminopropylthmethoxysilane, 2-amino-propyl-3-aminopropyltriethoxysilane, 2-aminoethyl-2-aminoethyl-3-aminopropyl-methoxysilane, 2-aminoethyl-3-aminopropyltriethoxysilane, 2-aminoethyl- 3-amino-propylmethyldimethoxysilane, 2-aminoethyl-3-aminopropylmethyldiethoxysilane, triaminofunctional s-propyltrimethoxysilane, bis (3-thmethoxysilylpropyl) amine, bis (3-thethoxysilylpropyl) amine, N-benzyl-N- (2- aminoethyl) -3-aminopropyl-thmethoxysilane hydrochloride, N-benzyl-N- (2-aminoethyl) -3-aminopropyl-thmethoxysilane-hydroacetate, N- (n-butyl) -3-aminopropyltrimethoxysilane, N-vinylbenzyl-N (2-aminoethyl) -3-aminopropylpolysiloxane and / or N- (2-aminoethyl) -3-aminopropylmethyl-d-imethoxysilane. Particularly preferred amino-functional silicon compounds are Dynasylan ^® AMMO, Dynasylan ^® AMEO, Dynasylan ^® 1505, Dynasylan ^® DAMO and / or Dynasylan ^® TRIAMO.

According to one embodiment, the crosslinkable wax may contain an organofunctional silicon compound and / or its salts, where the organofunctional silicon compound may correspond to an organofunctional silane of the general formula I I, its salt and / or a siloxane derived therefrom,

(R ² ) o (X ¹ ) _P SiY ² _q (II) wherein X ¹ is the same or different and X ¹ is oxy, carboxy, carboxyalkyl, silyl, alkylsilyl, alkoxysilyl, siloxy, especially -O-SiO3 / ₂ - group, silylalkyl, alkoxysilylalkyl, Alkylsilylalkyl-, haloalkyl; in particular an omega-haloalkyl, fluoroalkyl and / or perfluoroalkyl group; Epoxy, omega-glycidoxyalkyl, ester, blocked isocyanate, cyanatoalkyl,

May comprise isocyanatoalkyl, omega-methacryloxyalkyl, acrylate, methacrylate, mercapto, omega-mercaptoalkyl, nitrile and / or a phosphine group and / or

- wherein Y ^{2 is the} same or different and Y ^{2 is} a -OH, -OM, -OR ¹ , -O (CO) R ¹ , -OSi (R ¹ ) a (OR ¹ ) _b with a = O, 1, 2 or 3 and b = O, 1, 2 or 3 with a + b = 3, -Cl, -Br, -J and / or -N (R ¹ ) ₂ group, wherein R ^{1 is} independently the same or different is I and a hydrogen, a linear, branched and / or cyclic AI kyl, alkenyl, alkynyl and / or alkylaryl group, an aryl and / or heteroaryl group, each having 1 to 18

C atoms each substituted or unsubstituted, wherein M is a metal cation.

where o = 0, 1 or 2, p = 0 or 1 and q = 1, 2, 3 or 4, with o + p + q = 4 and

R ² independently of one another may be identical or different and is a hydrogen, a linear, branched and / or cyclic alkyl, alkenyl, alkynyl and / or alkylaryl group, an aryl and / or heteroaryl group having in each case 1 to 18 C atoms, preferably having 1 to 8 carbon atoms, which is in each case substituted or unsubstituted.

In particular, R ¹ may correspond to a linear, cyclic and / or branched alkyl radical having 1 to 4 C atoms, where R ^{1 may} particularly preferably correspond to a methyl, ethyl, propyl, iso-propyl group. Preferred organofunctional silicon compounds include organofunctional silanes, the salts thereof and / or siloxanes derived therefrom, preference being given to thalkoxysilanes, such as alkylthalkoxysilanes, of the general formula II type in which Y ^{2 is} an alkoxy group having 1 to 4 C atoms, in particular may correspond to a methoxy and / or ethoxy group, q can be 3 and R ^{2 is} an alkyl group having 1 to 5 C atoms, in particular an alkyl group having 2 to 4 C atoms, particularly preferably an alkyl group Group 3 C atoms can correspond.

Examples of preferred Alkylthalkoxysilane and / or Arylthalkoxysilane according to the general formula II are Isobutylthmethoxysilan (Dynasylan IBTMO ^®), Isobutylthethoxysilan, Propylthmethoxysilan (Dynasylan ^® PTMO) ethoxysilane Propyltri-, Ethylthmethoxysilan, ethyltriethoxysilane, Methylthmethoxysilan (Dynasylan ^® MTMS), methyltriethoxysilane, Octylthmethoxysilan, octyltriethoxysilane, Hexadecylthmethoxysilane, phenylthymethoxysilane and / or phenyltriethoxysilane.

Likewise preferred organofunctional silicon compounds of the general formula II are trialkoxysilanes of the general formula II in which X ¹ may correspond to a haloalkyl, a glycidoxyalkyl, mercaptoalkyl, acryloyloxyalkyl and / or AI kenyl group. Particularly preferred compounds are, for example, 3-Chlorpropylthmethoxysilan, 3-Glycidoxypropylthmethoxysilan (Dynasylan ^® GLYMO), 3-Glycidoxypropylthethoxysilan (Dynasylan ^® GLYEO), 3-mercapto propylthmethoxysilan (Dynasylan ^® MTMO), 3-Methacryloxypropylthmethoxysilan (Dynasylan ^® MEMO) are. According to a particularly preferred embodiment, Alkenylthalkoxysilane, (Dynasylan ^® VTMO) or Vinylthethoxysilan used such as Vinylthmethoxysilan be.

In addition, to adjust or modify the properties of the crosslinkable waxes, it is possible for haloalkyl-functional, organofunctional silicon compounds of the general formula II, in particular fluoro-functional silanes, to be present in the crosslinkable wax. Particularly preferred fluorine-functional silanes of the general formula II can have as X ¹ a radical with R ³ -Y ³ _r - (CH ₂ ) _S -, where R ^{3 is} a mono-, oligo- or perfluorinated alkyl radical having 1 to 13 carbon atoms or a mono-, oligo- or perfluorinated aryl radical may include, wherein further Y ^{3 is} a CH ₂ -, O, aryl or S radical and r = 0 or 1 and s may be an integer between 0 and 12 (s = 0 to 12). The modification of the crosslinkable waxes with fluorine-functional silicon compounds is particularly suitable for the hydrophobicization and / or oleophobization of the crosslinkable wax and / or the wax films obtainable therefrom.

Particularly preferred fluoroalkyltrialkoxysilanes correspond to the following formula CF ₃ ((CF ₂ ) (o to i ₂ ) ₍ CH ₂ ) ₍ o to i ₂ )) Si (OAlkyl) ₃ , such as 3,3,4,4,5,5,6 , 6,7,7,8,8,8- tridecafluoro-1, 1, 2.2-tetrahydrooctyltriethoxysilane (Dynasylan ^® F 8261).

The carboxy-functional waxes used to prepare the crosslinkable wax should have a molecular weight of at most 5000, which was determined by the osmometric method. Preferred waxes may be polyethylene wax oxidate or a Fischer-Tropsch oxidate, which should have a maximum osmometric molecular weight of 5,000.

According to the invention, the crosslinkable wax to form first ammonium functions and optionally later of amide bonds and / or

Siloxane bonds, especially with increase in molecular weight, crosslinkable. If it is assumed that an osmometric molecular weight of at most 5000, this applies in all cases, the pure carboxy-functional wax before Au formation of an amide bond with the amino-functional silicon compounds. Therefore, the crosslinkable wax according to the invention can have a significantly higher molecular weight after the crosslinking reactions have ended.

The crosslinkable wax according to the invention can be stored in the solid state. Advantageous for the storage stability of the crosslinkable waxes is a slight excess of carboxy groups (HOOC groups) in the wax in relation to the amino-functional groups, at most the molar ratio should be 1: 1. Preferably, the pH of the crosslinkable wax should be at a pH between 7 to 7.5, preferably between 6.5 to 7.5. This can be achieved by the carboxy-functional wax having an acid number above 15 mg KOH / g of the carboxy-functional wax, in particular above 20 mg KOH / g, preferably above 30 mg KOH / g and particularly preferably an acid number above 45 mg KOH / g carboxy-functional wax. Overall, it should be worked with an excess of the carboxy-functional wax with respect to the carboxy groups contained in relation to the amino-functional silicon compound used and the optionally added ammonia and / or the optionally added amine.

In addition to the amino-functional silicon compounds, the crosslinkable wax may also contain ammonia and / or an amine such as 2-amino-2-methyl-1-propanol (AMP) and / or 2-dimethylamino-2-methyl-1-propanol (DMAMP 80 ), contain.

The invention also provides a wax composition comprising a crosslinkable wax as defined above and water. The content of water in the wax composition may preferably be greater than or equal to 50% by weight, the content of water being determined to be 100% by weight, based on the total composition, if appropriate containing further auxiliaries and / or additives. In particular, the content of water in the composition may be greater than or equal to 30% by weight, preferably greater than or equal to 20% by weight. Alternatively, the proportion of amino functional silicon compounds, carboxy functional wax and optionally an organofunctional silicon compound and / or other ingredients in the wax composition may be at most 50% by weight relative to the total composition, with a maximum content of 30% or less preferred are.

The invention also provides a process for producing a wax, in particular a crosslinkable wax according to the above definitions, and waxes obtainable therefrom, where at least one amino-functional wax Silicon compound and at least one carboxy-functional wax and optionally at least one organofunctional silicon compound, in particular at elevated temperature, in particular between 120 ⁰ C and 150 ⁰ C, are reacted together. The compounds in the melt between 100 ⁰ C to 180 ⁰ C are preferred, preferably mixed between 120 ° C and 150 ⁰ C with each other and / or homogenized together.

According to a process alternative, a carboxy-functional wax can also be reacted with the amino-functional silicon compound according to the invention immediately after its preparation, still in the molten state, for example after completion of the oxidation and the achievement of the desired acid number. This step is similar to the production of partially hydrolyzed waxes, such as VESTOW AX 1550 ^® AS E (Degussa) - using alkali or alkaline earth metal hydroxides. According to this process alternative, care must be taken in the course of the process that the viscosity can increase somewhat as a result of the partial saponification with amino-functional silicon compounds, in particular with aminosilane, and this can have effects on the solidification step such as pastillation or granulation. The reaction water formed should be removed from the reaction mixture, for example by operating under a slight vacuum, for example by operating at 50 to 300 Torr, or by continuous purging with nitrogen. Preferably, the wax should be stored absolutely dry so that the humidity does not cause hydrolysis of the aminosilanes to silanols and subsequent condensation with crosslinking in the wax.

The amino-functional silicon compound used in the process may preferably comprise at least one aminosilane of general formula Ia or Ib, its salt and / or a siloxane derived therefrom according to the above definitions and / or a mixture of the compounds. The optionally at least one added organofunctional silicon compound may preferably be an organofunctional silane of the general formula II, its salt and / or a derived therefrom siloxane according to the above definition or a mixture of the compounds.

In order to produce storable, crosslinkable waxes, it may be preferable to separate off the water contained and / or formed by the process.

To prepare the wax composition of the invention comprising the crosslinkable wax, in particular comprising at least one amino-functional silicone compound and at least one carboxy-functional wax and optionally at least one organofunctional silicon compound as defined above, the crosslinkable wax can be dispersed in hot water or colloquially emulsified may be cooled, and may optionally be cooled, in particular the mixture obtained may be cooled, in particular a wax composition according to the invention is obtainable.

For example, n kan in a first Sch rode ei ne Sch melze from egg nem carboxy wax having an amino-functional silicon compound at a temperature between 120 ⁰ C and 150 ⁰ C are reacted. Subsequently, this melt, for example, at a temperature between 105 ° C to 130 ⁰ C with vigorous stirring, for example by means of a paddle stirrer, in hot water, at a water temperature of about 95 ° C, shrink. After slowly cooling to about 70 ° C, the stirring speed can be reduced, for example using a conventional paddle stirrer, and the wax composition, wax emulsion or wax dispersion, with further cooling in a water bath or using a cooling coil further cooled to room temperature. Suitably, the melted wax prior to dispersion in hot water or even after cooling of the resulting wax composition or emulsion additionally with ammonia and / or conventional amines, such as AMP (2-amino-2-methyl-2-propanol) or DMAM P 80 (2-dimethylamino-2-methyl-1-propanol) are reacted. The invention according to a further aspect of the invention, the preparation of a wax composition and a wax composition obtainable by this method by reacting in a first process step at least one carboxy-functional wax, in particular at elevated temperature, with ammonia and / or an amine and in a subsequent step at least one amino-functional silicon compound and optionally with at least one organofunctional silicon compound in the presence of water is dispersed.

In particular, the carboxy-functional wax can be conventionally optionally anionic dispersed with oleic acid and amine or only with an amine such as 2-amino-2-methyl-1-propanol or 2-dimethylamino-2-methyl-1-propanol, or colloquially emulsified become.

This wax emulsion or wax dispersion prepared in the first process step can be added in a subsequent step to an amino-functional silicon compound or else a composition containing an amino-functional silicon compound, such as an aminosilane, and optionally an organofunctional silicon compound or its hydrolysis and / or condensation products. These amino-functional silicon compounds containing compositions are available in the market and can be purchased under the trade name Dynasylan ^® HS or Hydrosil ™, for example, from Degussa. Useful compositions are the alkaline, adjusted to a pH of about 11 compositions of the type Dynasylan ^® HS 2627 (aqueous amino- / alkylfunktionelles siloxane cooligomer, non-alcoholic) and Dynasylan ^® HS 2776 (aqueous, non-alcoholic diamino- / alkylfunktionelles siloxane cooligomer). Also can acidic, for example to a pH of about 4, set type compositions Dynasylan ^® HS 2909 (aqueous, alkoholfreies- / alkylfunktionelles siloxane cooligomer) or Dynasylan ^® HS 2907 (aqueous, non-alcoholic amino- / vinyl-functional siloxane cooligomer) are used. These acidified Dynasylan ^® HS compositions should be prepared before Use in the process according to the invention, ie before mixing with the wax emulsion or wax dispersion prepared in the first process step are adjusted to a pH above 7. This can be done easily by carefully adding an amine such as 2-amino-2-methyl-1-propanol or 2-dimethylamino-2-methyl-1-propanol, conveniently with stirring with a paddle at room temperature. The immediate use of the acidified Dynasylan ^® HS composition is possible if in the first process step with a cationic wax emulsion whose pH is below 7, is carried out.

In general, the wax emulsion or wax dispersion prepared in the first process step from at least one carboxy-functional wax with ammonia and / or an amine can be dispersed in virtually any ratio with amino-functional silicon compounds in a subsequent step in the presence of water. Preferably, the amino-functional silicon compounds can be used as aqueous dispersion.

In particular, the mixing ratio of the wax emulsion prepared in the first process step or wax dispersion and the compositions of the type Dynasylan ^® HS on mixing ratios in the range from 0.1 to 99.9 wt .-% of wax emulsion extends with 99.9 wt .-% to 0, 1% by weight of the compositions of Dynasylan ^® HS type each with respect to 100% by weight in an inventive wax composition, which may optionally contain further auxiliaries and additives. In this case, the wax produced in the first process step is understood here as a wax emulsion. It may contain, in addition to the carboxy-functional wax, optionally oleic acid and ammonia and / or an amine. Preferred compositions can be based on a content of 10 to 80 wt .-% of wax emulsion and 90 to 20 wt .-% of a Dynasylan ^® HS composition, particularly preferred are 20 to 70 wt .-% wax emulsion with 80 to 30 wt. % Dynasylan ^® HS composition, or mixing ratios of 40 to 60 wt .-% wax emulsion and 60 bis 40 wt .-% Dynasylan ^® HS types, each resulting in total for a wax composition 100 wt .-%.

Of course, the use of aminofunctional silicon compounds is not limited to the use of Dynasylan ^® HS, generally comparable amino-functional silicon compounds containing compositions can be used in the inventive method. The skilled person is known, that the mixing or reacting of the wax emulsion or wax dispersion having an amino functional silicon compound in the presence of water, in particular a Dynasylan ^® HS composition, depending on the procedure and quantity of the compounds added by stirring together by means of a conventional paddle for example at room temperature ,

Because of their favorable physical and mechanical properties, such as dropping point, hardness, lubricity and hydrophobing effect, preferably synthetically prepared carboxy-functional waxes are used for the preparation of the crosslinkable wax and the wax composition. Oxidized Fischer-Tropsch waxes and polyolefin waxes, such as, for example, Ziegler polyethylene waxes, are particularly preferred.

By applying and drying the wax composition according to the invention as defined above to a substrate and / or a substrate surface, for example a textile, sewing thread, yarn, leather, fruits, minerals, concrete, plastics, plastic fibers, a wax film is available.

An object of the invention is also the use of the wax or the wax composition for the treatment and / or modification of substrates and / or substrate surfaces, in particular for the production of a wax film. The crosslinkable wax or wax composition is particularly suitable for use in the textile industry, such as sewing thread preparation, finishing of textiles, improving the sewability of textiles, crease-resistant finishing of textiles, self-gloss emulsions, leather care a leather care product or for the production of a leather care agent, for use as a form and release agent, aqueous printing ink and / or paint systems, for temporary corrosion protection or for use in temporary corrosion protection, for the production of fruit coatings, for the coating of minerals, concrete, plastics, Plastic semi-finished products, plastic granules and / or plastic fibers. In this context, textiles are understood as meaning, in particular, fabrics and / or yarns of natural and / or synthetic fibers.

The following examples illustrate the crosslinkable wax of the present invention, the wax composition, and the methods without affecting the invention

Restricting embodiments. The specific physical-mechanical

Wax parameters were determined by the following methods. Of the

Dropping point was measured according to DGF M-III-3, the hardness or penetration number according to DGF M-III-9b and the acid number was measured by titration to DGF M-IV-2.

Examples:

Example 1 (according to the invention)

Wax composition comprising a polyethylene wax oxidate (VESTOWAX AO 1570, Degussa, having an acid number of 43 mg KOH / g wax) and oleic acid and 2-dimethylamino-2-methyl-1-propanol:

100 g of carboxy-functional wax (VESTOWAX AO 1570) and 10 g of oleic acid (99% Aldrich) are melted at 125 ^° C. at a temperature in a melt casserole. Then, with stirring, by means of a paddle stirrer, at 125 ⁰ C, a mixture of 17.2 g of 3-aminopropylthethoxysilane (99%, Dynasylan ^® AMEO) and 5.5 g of 2-dimethylamino-2-methyl-1-propanol (80 %, Aldrich) over about 20 seconds. These wax melt is under strong Rü h ren m eans a paddle in 500 mlh SSES ei water, w ith egg ner water temperature of 95 ⁰ C, poured. After slow cooling to 70 ⁰ C is the stirring speed is reduced and, with cooling in a water bath, the wax composition is rapidly brought to room temperature. The resulting wax composition (emulsion) is finely divided and bluish. After application to a surface, the wax composition dries to form a clear film.

Example 2 (according to the invention)

Wax composition containing as carboxy-functional wax is a polyethylene wax (osmometric molecular weight of 1500 drip point 102 ⁰ C, hardness 4 mm x 10 ^"1, acid number 65 mg KOH / g wax):

200 g carboxy wax are melted at a he he Tem peratu r in a saucepan melting at 125 ⁰ C. A paddle at 125 ⁰ C 52 g of 3-Aminopropylmethylthethoxysilan (Dynasylan AMEO ^®) are then added over about 20 seconds using. This wax melt is added with vigorous stirring by means of a paddle stirrer in 1000 ml of hot water with a water temperature of 95 ⁰ C. After slow cooling to 70 ⁰ C, the stirring speed is reduced and while cooling in a water bath, the emulsion is rapidly cooled to room temperature. The resulting wax composition is very finely divided and bluish. Applied to a surface, the wax composition dries to a clear wax film.

Example 3 (according to the invention) Preparation of an aminosilane partially saponified polyethylene wax oxidate

a) Starting with (of a polyethylene wax osmometric molecular weight: 1500, dropping point 118 ⁰ C, acid value 0 mg KOH / g wax, penetration number of 1 mm x 10 ^"1, density of 0.94 g / cm ^3).

b) In a 2 l glass container with internal glass frit for the introduction of air - and an air flow rate of 15 l / h - are added with stirring by means of a paddle stirrer 3 to 5 revolutions per second 500 g of the polyethylene wax from a) with air with the addition of 0.1 wt .-% zinc stearate oxidized. The oxidation temperature is initially 30 M in utes at 1 70 ⁰ C and then held for the remaining reaction time of 8 hours at 140 ⁰ C. The reaction is then stopped with the completion of the air supply and simultaneous introduction of nitrogen. For expelling the water formed during the reaction, dry nitrogen at a temperature of 140 ⁰ C is passed through the resulting mixture for a further 2 hours. The acid number of the produced polyethylene wax oxidate is 55 mg KOH / g wax.

c) 200 g of the Polyethylenwachsoxidates prepared according to section b) are reacted at 125 ⁰ C in a melt casserole with 37.5 g of 3-aminopropylmethyldiethoxysilane (Dynasylan ^® 1505) with slow stirring using a paddle stirrer in the course of about 2 minutes. The prepared crosslinkable wax is stored under exclusion of moisture. The color of the wax is yellow.

d) Verification of emulsifiability

100 g of the crosslinkable wax from c) are reacted at a temperature in a casserole at 125 ^° C. together with 5 g of oleic acid (99% strength, Aldrich) and 2.8 g of 2-dimethylamino-2-methyl-1-propanol (80 %, Aldrich) melted and stirred by means of a paddle stirrer. Then, 1 g Trifluoroctylthethoxysilan (Dynasylan ^® F 8261) is added. Immediately after the addition, the melt is poured with vigorous stirring by means of the paddle stirrer in 500 ml of water at a temperature of 95 ⁰ C. After slow cooling to 70 ⁰ C, the stirring speed is reduced and while cooling in a water bath, the wax composition is rapidly cooled to room temperature.

The wax composition produced is finely divided and dry on a glass plate to form a clear film.

Example 4 (not according to the invention) A wax emulsion with a polyethylene wax oxidate from Example 2 and prepared using 2-dimethylamino-2-methyl-1-propanol alone without the use of an amino-functional silicon compound.

200 g of a carboxy Polyethylenwachsoxidates are melted at 125 ⁰ C in a melt saucepan. Using a paddle stirrer, 35 g of diethylamino-2-methyl-1-propanol (80%, Aldrich) are added at this temperature over about 20 seconds. These wax melt with vigorous stirring, using a paddle, in 1000 ml of 95 ⁰ C hot water Invitation Ufen g el according. After cooling down to 70 ^° C., the stirring speed is reduced and, while being cooled in a water bath, the emulsion is rapidly cooled to room temperature. The emulsion obtained is very finely divided. On a surface it dries to form a clear coat.

Example 5 (according to the invention)

100 ml of the - not according to the invention - wax emulsion from Example 4 are mixed with 50 ml of a 40% emulsion Dynasylan ^® HS 2627 at room temperature in a container by means of stirring. The resulting wax composition is very finely divided. Applied to a surface, the wax composition dries up clearly.

Example 6

Testing of water resistance and scratch resistance

a) water resistance

In each case 2 cm ^{3 of} the wax composition (emulsion) of Examples 1 to 5 are applied at room temperature with a pipette on a glass plate of a format of 5 cm x 2 cm. After a drying time of 2 hours at room temperature, 0.5 cm ³ of distilled water are applied as a drop on the wax coating and 30 minutes, the appearance of the treated Wax coating assessed visually. In cases where the wax film is not waterproof, it is dissolved and it forms a clear haze.

b) adhesion and hardness and scratch resistance A coated glass plate is stored for 7 days at room temperature and then checked. The test is carried out with a sharp-edged knife. Using a large contact force, the knife is used to scrape off the coating from the glass plate produced under a).

Rating: 1 = Scrape off the glass surface is not possible (impossible), it has formed a hard wax film and the knife can only remove chips from the wax film, 4 = separation of the wax film from the glass plate is easily possible.

Table 1 Testing the water resistance (a) and the scratch resistance (b) of the wax films

In summary, it should be noted that the wax compositions according to the invention of Examples 1 to 3 and 5 form waterproof and hard wax films, while the wax composition of Example 4 does not form a hard and a water-resistant wax film.

Claims

claims 1. wax, characterized in that the wax is crosslinkable and at least one amino-functional Silicon compound and at least one carboxy-functional wax and optionally contains an organofunctional silicon compound and / or salts thereof. 2. Wax according to claim 1, characterized in that the amino-functional silicon compound corresponds to at least one aminosilane of the general formula Ia or Ib, its salt and / or a siloxane derived therefrom, A ¹ _m SiY ¹ _n (Ia) (Y ^{1 *} ) ₃ Si-A ^{1 *} -Si (Y ^{1 *} ) ₃ (Ib) where A ¹ and / or A ^{1 *} independently of one another correspond to an unsubstituted or substituted aminoalkyl, diaminoalkyl or thaminoalkyl group, Y ¹ and / or Y ^{1 *} are each, independently of one another, identical or different and one of the following groups -OH, -OM, -OR ¹ , -R ¹ , -O (CO) R ¹ , -N (R ¹ ) ₂ , -Cl, -Br, -J and / or -OSi (R ¹ ) _a (OR ¹ ) _b with a = O, 1, 2 or 3 and b = 0, 1, 2 or 3 and a + b = 3, in which R ^{1 is} independently the same or different and is a hydrogen, a linear, branched and / or cyclic alkyl, alkenyl, alkynyl and / or alkylaryl group, an aryl and / or heteroaryl group each having 1 to 18 carbon atoms, each substituted or unsubstituted, wherein M comprises a metal cation, and where m = 1 or 2 and n = 1, 2 or 3, with m + n = 4. 3. wax according to claim 1 or 2, characterized in that the organofunctional silicon compound corresponds to an organofunctional silane of the general formula II, its salt and / or a siloxane derived therefrom,

wherein X ^{1 is the} same or different and X ^{1 is} an oxy, carboxy, carboxyalkyl, silyl, alkylsilyl, alkoxysilyl, siloxy, silylalkyl, Alkoxysilylalkyl, alkylsilylalkyl, haloalkyl, epoxy, omega-glycidoxyalkyl, ester, blocked isocyanate, cyanatoalkyl, isocyanatoalkyl, omega-methacryloxyalkyl, acrylate, methacrylate, mercapto, omega-mercaptoalkyl , Nitrile and / or a phosphine group, wherein Y ^{2 is the} same or different and Y ^{2 is} a -OH, -OM, -OR ¹ , -O (CO) R ¹ , -OSi (R ¹ ) a (OR ¹ ) _b with a = O, 1, 2 or 3 and b = O, 1, 2 or 3 with a + b = 3, -Cl, -Br, -J and / or -N (R ¹ ) ₂ group, wherein R ^{1 is} independently the same or different from each other I is and a hydrogen, a linear, branched and / or cyclic alkyl, alkenyl, Alkynyl and / or alkylaryl group, an aryl and / or heteroaryl group having in each case 1 to 18 C atoms, which is in each case substituted or unsubstituted, where M is a metal cation, where o = 0, 1 or 2, p = 0 or 1 and q = 1, 2, 3 or 4, with o + p + q = 4 and - R ^{2 is} independently the same or different and is a hydrogen, a linear, branched and / or cyclic alkyl, alkenyl, alkynyl and / or alkylaryl group, an aryl and / or heteroaryl group, each having 1 to 18 C atoms, which is in each case substituted or unsubstituted. 4. Wax according to one of claims 1 to 3, characterized that A ¹ in the form of el I agle is I or different and corresponds to an amino-functional radical of the general formulas IIIa and / or IIIb, R ¹ VNH _(2-h *) [(CH 2) _h (NH)] _J [(CH ₂ ) 1 (NH)] _c - (CH ₂ ) _k - (lilac) wherein 0 ≦ h ≦ 6; h ^* = 0, 1 or 2, j = 0, 1 or 2; 0 ≤ I ≤ 6; c = 0, 1 or 2; 0 ≤ k ≤ 6 and R ^{10 is} a benzyl, vinylbenzyl, aryl, vinyl, formyl Corresponding radical and / or a linear, branched and / or cyclic alkyl radical having 1 to 8 carbon atoms, and / or [NH ₂ (CH ₂ ) e] ₂ N (CH ₂ ) d - (Nlb) where 0≤e≤6 and 0≤d≤6 and / or A ^{1 *} in formula Ib is identical or different and corresponds to a bis-amino-functional radical of the general formula IMc, - (CH ₂ ), - [NH (CH ₂ ) _f ] _g NH [(CH ₂ ) _f * NH] _g * - (CH ₂ V- (Never) wherein i, i *, f, f *, g or g * are the same or different, with i and / or i * = 0 to 8, f and / or f * = 1, 2 or 3, g and / or g * = 0, 1 or 2 and / or - Y ¹ and / or Y ^{1 *} in the formulas Ia and / or Ib independently of one another -OH, -ONa, -OK, -OR ¹ , -R ¹ , -O (CO) R ¹ , wherein R ^{1 is} independently the same or different and is a hydrogen, a linear, cyclic and / or branched alkyl radical with 1 to 4 carbon atoms corresponds in particular to R ^{1 of} a methyl, ethyl, propyl, iso-propyl group. 5. Wax according to one of claims 1 to 4, characterized in that the amino-functional silicon compound 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-Aminpropylmethyldiethoxysilan, 2-aminoethyl-3-aminoproyltrimethoxysilane and / or a triamino-functional propyltrimethoxysilane corresponds. 6. Wax according to one of claims 1 to 5, characterized in that the carboxy-functional wax has an acid number above 15 mg KOH / g wax. 7. Wax according to one of claims 1 to 6, characterized in that the wax contains oleic acid. 8. Wax according to one of claims 1 to 7, characterized in that the carboxy-functional wax is a polyethylene wax oxidate or a Fischer-Tropsch-Oxidat having an osmometric molecular weight of at most 5000. 9. Wax according to one of claims 1 to 8, characterized in that it is crosslinkable to form amide bonds and / or siloxane bonds. 10. Wax composition characterized that it comprises a wax according to any one of claims 1 to 9 and water. 1 1. A wax composition according to claim 10, characterized in that the water content is greater than or equal to 50 wt .-%. 12. A process for producing a wax according to any one of claims 1 to 9, by at least one amino-functional silicon compound and at least one carboxy-functional wax and optionally at least one organofunctional silicon compound are reacted with each other at elevated temperature. 13. The method according to claim 12, characterized in that a freshly prepared, molten carboxy-functional wax is used. 14. The method according to claim 12 or 13, characterized in that the carboxy-functional wax has an acid number above 15 mg KOH / g. 15. The method according to any one of claims 12 to 14, characterized in that the amino-functional silicon compound at least one aminosilane of the general formula Ia or Ib, its salt and / or derived therefrom siloxane as defined in claim 2, 4 and / or 5 or corresponds to a mixture of compounds. 16. The method according to any one of claims 12 to 14, characterized the organofunctional silicon compound corresponds to an organofunctional silane of the general formula II, its salt and / or a siloxane derived therefrom as defined in claim 4 or a mixture of the compounds, 17. The method according to any one of claims 12 to 16, characterized in that contained and / or formed water is separated. A process for producing a wax composition according to claim 10 or 11, wherein a molten wax according to any one of claims 1 to 9 or 12 to 17 is dispersed in hot water and optionally cooled. 19. A process for producing a wax composition according to claim 10 or 11, in which at least one carboxy-functional wax is reacted at elevated temperature with ammonia and / or an amine in a first process step and in a subsequent step with at least one amino-functional silicon compound and optionally with at least one Organofun ktionel len silicon compound in the presence of water is dispersed. 20. The method according to claim 19, characterized in that a s s s A s s Am 2 n-2-amino-2-methyl-1-propanol and / or 2-dimethylamino-2-methyl-1-propanol is used. 21. Wax obtainable according to one of claims 12 to 17. 22. A wax composition obtainable according to any one of claims 18 to 20. 23. Wax film obtainable by applying and drying the wax composition according to any one of claims 10, 11 or 18 to 20 on a substrate and / or a substrate surface. 24. Use of the wax or the wax composition according to any one of claims 1 to 22 for the treatment and / or modification of substrates and / or substrate surfaces. 25. Use according to claim 24 for the preparation of a wax film. 26. Use according to claim 24 for sewing thread preparation, finishing of textiles, improving the sewability of textiles, crease-resistant finishing of textiles, for self-gloss emulsions, for leather care, in a leather care product, as mold release agents, for aqueous printing ink and / or paint systems, for temporary corrosion protection , for fruit coatings, for the Coating of minerals, concrete, plastics, plastic semi-finished products, plastic granules and / or plastic fibers.