DE102004023894A1 - Process for the treatment of flexible substrates - Google Patents

Abstract

Process for the treatment of substrates, wherein DOLLAR A (A) at least one substrate selected from substrates of DOLLAR A (A1) polyacrylic, polyester, silicone, polyamide or DOLLAR A (A2) one or more polymers based on a monomer of the general Formula I, DOLLAR F1 in which R · 1 · is selected from -Cl, C¶1¶-C¶10¶-alkyl, -CH = CH¶2¶, -C (Cl) = CH¶2¶, -C (CH¶3¶) = CH¶2¶ and -COOC¶1¶-C¶10¶-alkyl, DOLLAR A contacted with at least one aqueous formulation containing DOLLAR A (B) at least one ethylene copolymer wax, which 60 to 95 wt. % Of ethylene and 5 to 40 wt .-% of at least one ethylenically unsaturated carboxylic acid in copolymerized form, DOLLAR A further at least one colorant selected from DOLLAR A (C) at least one pigment and DOLLAR A (D) at least one dye.

Description

• (A) mindestens ein flexibles Substrat, gewählt aus Substraten aus (A1) Polyacryl, Polyester, Silikon, Polyamid oder (A2) einem oder mehreren Polymeren auf Basis von einem Monomer der allgemeinen Formel I
  
  in denen R¹ gewählt wird aus Cl, C₁-C₁₀-Alkyl, -CH=CH₂, -C(Cl)=CH₂, -C(CH₃)=CH₂ und -COOC₁-C₁₀-Alkyl, mit mit mindestens einer wässrigen Formulierung kontaktiert, enthaltend
• (B) mindestens ein Ethylencopolymerwachs, welches 60 bis 95 Gew.-% Ethylen und 5 bis 40 Gew.-% mindestens einer ethylenisch ungesättigten Carbonsäure einpolymerisiert enthält, weiterhin mindestens ein Farbmittel, gewählt aus
• (C) mindestens einem Pigment und
• (D) mindestens einem Farbstoff.

The present invention relates to a process for the treatment of flexible substrates, characterized in that

• (A) at least one flexible substrate selected from substrates of (A1) polyacrylic, polyester, silicone, polyamide or (A2) one or more polymers based on a monomer of general formula I.
  
  in which R ^{1 is} selected from Cl, C ₁ -C ₁₀ alkyl, -CH = CH ₂ , -C (Cl) = CH ₂ , -C (CH ₃ ) = CH ₂ and -COOC ₁ -C ₁₀ alkyl containing, contacted with at least one aqueous formulation containing
• (B) at least one ethylene copolymer wax which contains 60 to 95 wt .-% of ethylene and 5 to 40 wt .-% of at least one ethylenically unsaturated carboxylic acid in copolymerized form, further at least one colorant selected from
• (C) at least one pigment and
• (D) at least one dye.

method for coating, dyeing and printing on flexible substrates such as films or fibrous substrates such as fabrics, knitted or Nonwovens place high demands on the formulations. A particular challenge phrases concern, for example affect the printing of polypropylene. With conventional In many cases, formulations of polypropylene substrates have many features make inadequate Fastness on what, for example, the wash fastness and wet rub fastness concerns. Even with other flexible substrates, for example Polyvinyl chloride or silicone are in demand treatment procedures which allow, for example, a printing or dyeing with good fastness properties.

Farther For example, there are limits to the bonding of polypropylene. if, when bonding, temperatures above the melting or Wants to avoid softening point of polypropylene. Although you can Modify polypropylene by so-called corona treatment, so that afterwards holding an adhesive. However, corona treatments are common expensive, usually run only with low efficiency and have only a low storage stability the modification.

It Therefore, the task was to provide a method with which manages to treat flexible substrates and from the Prior art known disadvantages to avoid. Continue to exist the task to provide treated flexible substrates. Farther the task was to supply printing pastes and dyeing liquors, under their use, flexible substrates can be treated.

Accordingly the method defined at the beginning was found.

The inventive method is based on at least one substrate (A), wherein under substrates preferably flexible substrates are understood, i. substrates the one at room temperature at least once non-destructive can deform manually, for example buckling, rolling up or down, fold or bend. Preferred examples of flexible substrates are textiles, hereinafter also referred to as textile substrates, furthermore films and manually deformable hollow body such as bottles.

Under Textile or textile substrates are within the scope of the present Invention textile fibers, textile semifinished and finished products and thereof finished goods to be understood, in addition to textiles for the garment industry For example, carpets and other home textiles and technical For purposes of serving textile structures include such as awnings. This includes also unshaped structures such as flakes, linear formations like twine, threads Yarns, Linen, Cords, Ropes, threads and body structures such as felts, woven fabrics, knitted fabrics, nonwovens, nonwovens and cotton wool.

• (A1) Polyacryl, Polyester, Silikonen, Polyamid, beispielsweise Polykondensaten von α,ω-Diamiden mit α,ω-Dicarbonsäuren oder cyclischen Amiden wie beispielsweise ε-Caprolactam, oder bevorzugt
• (A2) einem oder mehreren Polymeren auf Basis von einem Monomer der allgemeinen Formel I
  
  in denen R¹ gewählt wird aus Chlor, C₁-C₁₀-Alkyl, verzweigt oder unverzweigt, wie beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl und ganz besonders bevorzugt Methyl, -CH=CH₂, -C(Cl)=CH₂, -C(CH₃)=CH₂ und -COOC₁-C₁₀-Alkyl, wobei C₁-C₁₀-Alkyl verzweigt oder unverzweigt sein kann und wie vorstehend definiert, hergestellt sind.

Flexible substrates (A) are selected from substrates that are made

• (A1) polyacrylic, polyesters, silicones, polyamide, for example polycondensates of α, ω-diamides with α, ω-dicarboxylic acids or cyclic amides such as ε-caprolactam, or preferred
• (A2) one or more polymers based on a monomer of general formula I.
  
  in which R ^{1 is} selected from chlorine, C ₁ -C ₁₀ alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert. Butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl , n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, and very particularly preferably methyl, -CH = CH ₂ , -C (Cl) = CH ₂ , -C (CH ₃ ) = CH ₂ and -COOC ₁ -C ₁₀ alkyl, wherein C ₁ -C ₁₀ alkyl may be branched or unbranched and are as defined above.

there are also substrates of any of the foregoing polymers such substrates includes a certain proportion, for example at least 30% by weight, preferably at least 50% by weight of at least one of the aforementioned polymer. Exemplary Blended fabric of cotton / polyester or cotton / polyamide called.

Under Polymers based on at least one monomer of the general Formula I are not only within the scope of the present invention To understand homopolymers, but also copolymers that are essential Proportion, for example at least 50 mol% of at least one Monomer of the general formula I may contain in copolymerized form. So For example, ethylene-propylene copolymers are also suitable. which may contain at least 50 mol% of copolymerized propylene.

All Particularly preferred are substrates of polyvinyl chloride (PVC) and Polypropylene (PP), which can be prepared by any method can. Polypropylene can be prepared, for example, by Ziegler-Natta catalysis or be prepared by metallocene catalysis.

According to the invention, at least one flexible substrate is contacted with at least one aqueous formulation containing at least one ethylene copolymer wax, which
60 to 95 wt .-%, preferably 65 to 85 wt .-% of ethylene and
5 to 40 wt .-%, preferably 15 to 35 wt .-% of at least one ethylenically unsaturated carboxylic acid in copolymerized form, wherein in wt .-% are based on the total ethylene copolymer.

At least one ethylenically unsaturated carboxylic acid is preferably a carboxylic acid of the general formula II

• R² gewählt aus Wasserstoff,
• – C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• – COOH, COOCH₃, COOC₂H₅.
• R³ gewählt aus Wasserstoff,
• – C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;

In formula II, the radicals are defined as follows:

• R ^{2 is} selected from hydrogen,
• - C ₁ -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• - COOH, COOCH ₃ , COOC ₂ H ₅ .
• R ^{3 is} selected from hydrogen,
• - C ₁ -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;

Most preferably, R ^{2 is} hydrogen and R ^{3 is} hydrogen or methyl.

• – Vinylacetat,
• – einen oder mehrere ethylenisch ungesättigte Carbonsäureester, bevorzugt der Formel III
  
• R⁴ gewählt aus Wasserstoff,
• – C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• R⁵ gewählt aus Wasserstoff,
• – C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• – COOH, COOCH₃, COOC₂H₅,
• R⁶ gewählt aus C₁-C₁₀-Alkyl, wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, n-Nonyl, n-Decyl; besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl.

Ethylene copolymer waxes contained in aqueous formulations used according to the invention may contain up to 40% by weight, preferably up to 35% by weight, based in each case in copolymerized form of the sum of ethylene and copolymerized or copolymerized ethylenically unsaturated carboxylic acid (s) of one or more further monomers , for example

• - vinyl acetate,
• - One or more ethylenically unsaturated carboxylic acid esters, preferably of the formula III
  
• R ^{4 is} selected from hydrogen,
• - C ₁ -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• R ^{5 is} selected from hydrogen,
• - C ₁ -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso -hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl;
• COOH, COOCH ₃ , COOC ₂ H ₅ ,
• R ⁶ selected from C ₁ -C ₁₀ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Most preferably, R ^{5 is} hydrogen and R ^{4 is} hydrogen or methyl.

Most preferably, R ^{5 is} hydrogen and R ^{4 is} hydrogen or methyl and R ^{6 is} selected from methyl, ethyl, n-butyl and 2-ethylhexyl.

above described ethylene copolymer waxes of ethylene and ethylenic unsaturated carboxylic acids can be advantageous by free-radically initiated copolymerization under high pressure conditions, for example in stirred high-pressure autoclave or in high pressure tube reactors. Production in stirred high pressure autoclave is preferred. stirred High pressure autoclave are known per se, a description will find one in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, keywords: Waxes, Bd. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996. They are predominantly related to the length / diameter ratio at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1. The same applicable high-pressure tube reactors can also be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p. 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996th

suitable Printing conditions for the polymerization is 500 to 4000 bar, preferably 1500 to 2500 bar. The reaction temperatures are in the range of 170 to 300 ° C, preferably in the range of 200 to 280 ° C.

oder Mischungen derselben.The polymerization can be carried out in the presence of a regulator. The regulator used is, for example, hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula IV

or mixtures thereof.

• – Wasserstoff;
• – C₁-C₆-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl;
• – C₃-C₁₂-Cycloalkyl wie Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl.

The radicals R ⁷ and R ^{8 are the} same or different and selected from

• - hydrogen;
• C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably C ₁ -C ₄ -alkyl, such as methyl, ethyl, n -propyl, iso -propyl, n -butyl, iso -butyl, sec -butyl and tert -butyl;
• C ₃ -C ₁₂ cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.

In a particular embodiment, R ⁷ and R ⁸ are covalently linked together to form a 4- to 13-membered ring. For example, R ⁷ and R ⁸ may be in common: - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ , - (CH ₂ ) ₇ -, -CH (CH ₃ ) -CH ₂ -CH ₂ -CH (CH ₃ ) - or -CH (CH ₃ ) -CH ₂ -CH ₂ -CH ₂ -CH (CH ₃ ) -.

Well suitable regulators are alkylaromatic compounds, for example Toluene, ethylbenzene or one or more isomers of xylene. Prefers it dispenses with the use of aldehydes and ketones of the general Formula IV as a regulator. Most preferably, no further doses Regulator with the exception of the so-called phlegmatizers, which are for the better Manageability organic peroxides can be added and also the function of a molecular weight regulator.

When Starter for The radical polymerization can be the usual radical starter for example, organic peroxides, oxygen or azo compounds be used. Also mixtures of several radical starters are suitable.

• – Didekanoylperoxid, 2,5-Dimethyl-2,5-di(2-ethylhexanoylperoxy)hexan, tert.-Amylperoxy-2-ethylhexanoat, Dibenzoylperoxid, tert.-Butylperoxy-2-ethylhexanoat, tert.-Butylperoxydiethylacetat, tert.-Butylperoxydiethylisobutyrat, 1,4-Di(tert.-butylperoxycarbonyl)-cyclohexan als Isomerengemisch, tert.-Butylperisononanoat 1,1-Di-(tert.-butylperoxy)-3,3,5-trimethylcyclohexan, 1,1-Di-(tert.-butylperoxy)-cyclohexan, Methyl-isobutylketonperoxid, tert.-Butylperoxyisopropylcarbonat, 2,2-Di-tert.-butylperox)butan oder tert.-Butylperoxacetat;
• – tert.-Butylperoxybenzoat, Di-tert.-amylperoxid, Dicumylperoxid, die isomeren Di-(tert.-butylperoxyisopropyl)benzole, 2,5-Dimethyl-2,5-di-tert.-butylperoxyhexan, tert.-Butylcumylperoxid, 2,5-Dimethyl-2,5-di(tert.-butylperoxy)-hex-3-in, Di-tert.-butylperoxid, 1,3-Diisopropylbenzolmonohydroperoxid, Cumolhydroperoxid oder tert.-Butylhydroperoxid; oder
• – dimere oder trimere Ketonperoxide der allgemeinen Formel Va bis Vc.

Suitable peroxides selected from the commercially available substances are

• Didecanoyl peroxide, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, tert-amylperoxy-2-ethylhexanoate, dibenzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxydiethylacetate, tert-butyl peroxydiethyl isobutyrate , 1,4-di (tert-butylperoxycarbonyl) cyclohexane as a mixture of isomers, tert-butyl perisononanoate 1,1-di- (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di- (tert .-butylperoxy) -cyclohexane, methyl isobutyl ketone peroxide, tert-butyl peroxyisopropyl carbonate, 2,2-di-tert-butylperoxy) butane or tert-butyl peroxyacetate;
• Tert-butyl peroxybenzoate, di-tert-amyl peroxide, dicumyl peroxide, the isomeric di- (tert-butylperoxyisopropyl) benzenes, 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, tert-butylcumyl peroxide, 2 , 5-dimethyl-2,5-di (tert-butylperoxy) -hex-3-yne, di-tert-butyl peroxide, 1,3-diisopropylbenzene monohydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; or
• - dimeric or trimeric ketone peroxides of the general formula Va to Vc.

• – C₁-C₈-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, sec.-Butyl, iso-Butyl, tert.-Butyl, n-Pentyl, sec.-Pentyl, iso-Pentyl, n-Hexyl, n-Heptyl, n-Octyl; bevorzugt lineares C₁-C₈-Alkyl wie Methyl, Ethyl, n-Propyl, n-Butyl, n-Pentyl, n-Hexyl, besonders bevorzugt lineares C₁-C₄-Alkyl wie Methyl, Ethyl, n-Propyl oder n-Butyl, ganz besonders bevorzugt ist Ethyl;
• – C₆-C₁₄-Aryl wie Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-Phenanthryl und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl.

The radicals R ⁹ to R ^{14 are} identical or different and selected from

• C ₁ -C ₈ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isobutyl, Pentyl, n-hexyl, n-heptyl, n-octyl; preferably linear C ₁ -C ₈ -alkyl, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, particularly preferably linear C ₁ -C ₄ -alkyl, such as methyl, ethyl, n-propyl or n Butyl, most preferably ethyl;
• C ₆ -C ₁₄ aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.

peroxides of the general formulas Va to Vc and processes for their preparation are known from EP-A 0 813 550.

When Peroxides are di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable. Azobisisobutyronitrile ("AlBN") may be mentioned by way of example as azo compound will be in for Polymerizations usual Doses are metered.

numerous commercially available organic peroxides are added to so-called phlegmatizers, before they are sold, to make them easier to handle. When Phlegmatizers are, for example, white oil or hydrocarbons such as especially isododecane suitable. Under the conditions of the radical High pressure polymerization can Such phlegmatizers have a molecular weight regulating effect to have. For the purposes of the present invention is intended to use of molecular weight regulators the additional use of further molecular weight regulators over the Use of phlegmatizers also be understood.

The ratio of the monomers ethylene and ethylenically unsaturated carboxylic acid (s) the dosage usually corresponds not exactly the relationship the units in the formulations used according to the invention contained ethylene copolymer waxes, because ethylenically unsaturated carboxylic acids in general easier to incorporate into ethylene copolymer waxes than ethylene.

The Monomers are usually dosed together or separately.

The Monomers can be compressed in a compressor to the polymerization pressure. In another embodiment the method according to the invention the monomers are first by means of a pump to an increased pressure of for example 150 to 400 bar, preferably 200 to 300 bar and in particular 250 bar and then with a compressor to the actual Polymerization.

The Polymerization may optionally be in the absence and presence of solvents be performed, being mineral oils, White oil and others Solvent, the while the polymerization in the reactor are present and to phlegmatize of the radical starter (s) used in the present invention Invention not as a solvent be valid.

In an embodiment the polymerization is carried out in the absence of solvents.

of course is it also possible To produce ethylene copolymer wax so that first with ethylene at least one ethylenically unsaturated carboxylic acid ester to copolymerize the general formula III and then the Ester groups in egg ner polymer-analogous reaction to be saponified, for example with Potash or caustic soda.

Used according to the invention aqueous Formulations preferably contain 0.05 to 40 wt .-%, preferably From 10 to 35% by weight of one or more ethylene copolymer waxes, preferably in complete or partially neutralized form.

To the Purpose of partial or complete neutralization included Aqueous formulations used according to the invention usually one or more basic substances, for example hydroxides and / or carbonates and / or bicarbonates of alkali metals, Ammonia, organic amines such as triethylamine, diethylamine, Ethylamine, trimethylamine, dimethylamine, methylamine, ethanolamine, Diethanolamine, triethanolamine, methyldiethanolamine, n-butyldiethanolamine, N, N-dimethylethanolamine. Preferably used according to the invention aqueous Formulations so much basic substance or basic acting Substances that at least half, preferably at least three quarters of the carboxyl groups of the or the ethylene copolymer waxes neutralized. Basic substances can be used according to the invention For example, during formulations the dispersion of ethylene copolymer wax enforce.

In an embodiment of the present invention contain used according to the invention aqueous Formulations so much basic substance or basic acting Substances that the carboxyl groups of or the ethylene copolymer waxes are quantitatively neutralized.

Used according to the invention aqueous Formulations usually have a basic pH, preferred are pH values of 7.5 to 14, more preferably 8 or higher, and most preferably from 8.5 or higher.

Aqueous formulations used according to the invention preferably contain no protective colloids. Aqueous formulations used according to the invention are stable even without such surface-active auxiliaries, ie at a shear stress of 100 cm ^-1 the light transmittance does not change by more than 2%, measured with a dispersion having a solids content of 0.1% by weight with pure water for reference.

• (C) mindestens einem Pigment und
• (D) mindestens einem Farbstoff.

Aqueous formulation used according to the invention contains, in addition to ethylene copolymer wax (B)
at least one colorant selected from

• (C) at least one pigment and
• (D) at least one dye.

Under Pigments (C) are useful in the present invention insoluble, dispersed finely divided, organic or inorganic colorants according to the definition in DIN 55944. Preferably, at least organic is chosen Pigment and / or metal pigment.

Exemplary selected organic pigments are - monoazo pigments: CI Pigment Brown 25; CI Pigment Orange 5, 13, 36 and 67; CI Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1 , 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251; CI Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183; - Disazo pigments: CI Pigment Orange 16, 34 and 44; CI Pigment Red 144, 166, 214 and 242; CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188; - Anthanthrone pigments: CI Pigment Red 168 (CI Vat Orange 3); - anthraquinone pigments: CI Pigment Yellow 147 and 177; CI Pigment Violet 31; - anthraquinone pigments: CI Pigment Yellow 147 and 177; CI Pigment Violet 31; - Anthrapyrimidine pigments: CI Pigment Yellow 108 (CI Vat Yellow 20); - Quinacridone pigments: CI Pigment Red 122, 202 and 206; CI Pigment Violet 19; - Quinophthalone pigments: CI Pigment Yellow 138; - Dioxazine pigments: CI Pigment Violet 23 and 37; - flavanthrone pigments: CI Pigment Yellow 24 (CI Vat Yellow 1); - Indanthrone pigments: CI Pigment Blue 60 (CI Vat Blue 4) and 64 (CI Vat Blue 6); - isoindoline pigments: CI Pigment Orange 69; CI Pigment Red 260; CI Pigment Yellow 139 and 185; - Isoindolinone pigments: CI Pigment Orange 61; CI Pigment Red 257 and 260; CI Pigment Yellow 109, 110, 173 and 185; - isoviolanthrone pigments: CI Pigment Violet 31 (CI Vat Violet 1); - metal complex pigments: CI Pigment Yellow 117, 150 and 153; CI Pigment Green 8; - Perinone pigments: CI Pigment Orange 43 (CI Vat Orange 7); CI Pigment Red 194 (CI Vat Red 15); - Perylene pigments: CI Pigment Black 31 and 32; CI Pigment Red 123, 149, 178, 179 (CI Vat Red 23), 190 (CI Vat Red 29) and 224; CI Pigment Violet 29; Phthalocyanine pigments: CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16; CI Pigment Green 7 and 36; - Pyranthrone pigments: CI Pigment Orange 51; CI Pigment Red 216 (CI Vat Orange 4); - Thioindigo pigments: CI Pigment Red 88 and 181 (CI Vat Red 1); CI Pigment Violet 38 (CI Vat Violet 3); Triaryl carbonium pigments: CI Pigment Blue 1, 61 and 62; CI Pigment Green 1; CI Pigment Red 81, 81: 1 and 169; CI Pigment Violet 1, 2, 3 and 27; CI Pigment Black 1 (aniline black); CI Pigment Yellow 101 (aldazine yellow); CI Pigment Brown 22.

Examples for special preferred pigments (C) are: C.I. Pigment Yellow 138, C.I. pigment Red 122, C.I. Pigment Violet 19, C.I. Pigment Blue 15: 3 and 15: 4, C.I. Pigment Black 7, C.I. Pigment Orange 5, 38 and 43 and C.I. Pigment Green 7.

Further Suitable pigments (C) are metallic pigments such as Gold bronze, silver bronze, iriodin pigments, glitter.

Of the average diameter of used in the process according to the invention Pigment (C) is usually in the range of 20 nm to 1.5 μm, preferably in the range of 300 to 500 nm.

In an embodiment The present invention is in the process of the invention used pigment (C) in spherical or near spherical particulate Form before, i. the ratio of the longest diameter to the smallest diameter is in the range of 1.0 to 2.0, preferably to 1.5.

In another embodiment The present invention is used in the method according to the invention Pigment (C) in the form of needles or pins.

suitable Dyes (D) are all textile dyes, for example vat dyes such as indigo and its derivatives, direct dyes, Disperse dyes, acid dyes, Metal complex dyes, naphthol dyes, sulfur dyes, Reactive dyes and pigment dyes.

The Production of inventively used aqueous For example, formulations can be described as follows carry out. It is possible to proceed in such a way that first one or more ethylene copolymer waxes dispersed in water. This can be done by one or more of starting from the above-described ethylene copolymer waxes. This placed one in a vessel, for example a flask, an autoclave or a kettle. In a variant heated the ethylene copolymer or waxes to a temperature above its Melting point. Advantageously heated to a temperature that is at least 10 ° C, particularly beneficial a temperature at least 30 ° C above the melting point of or Ethylene copolymer is located. If one sets several different ethylene copolymer waxes one, so warmed up you get to a temperature over the melting point of the highest Temperature melting ethylene copolymer wax is. Advantageous heated one in the case that one has several different ethylene copolymer waxes at a temperature at least 10 ° C above the melting point of the highest Temperature melting ethylene copolymer wax is. Especially heated advantageously one in the case that one has several different ethylene copolymer waxes used, at a temperature at least 30 ° C above the melting point of the the highest Temperature melting ethylene copolymer wax is.

Then there one water and one or more basic substances and optionally other ingredients such as ethylene glycol to, the order of addition of water and the addition of basic or basic substances and others Components is arbitrary. If the temperature is above 100 ° C, it is advantageous under increased Pressure to work and the vessel accordingly to choose. Homogenize the resulting emulsion, for example by mechanical or pneumatic stirring or by shaking. Then you can the aqueous one thus prepared Cool the formulation.

After that it is possible to add at least one colorant selected from (C) at least one Pigment and (D) at least one dye. Then you mix Water, ethylene copolymer wax (B) and colorants.

Do you wish as colorant to add at least one pigment (C), it is preferred Pigment (C) in the form of a so-called pigment preparation, i. in one with water and optionally at least one surface-active Fabric dispersed form.

to execution the method according to the invention for the treatment of flexible substrates one proceeds in such a way that one at least one flexible substrate (A) having at least one used according to the invention aqueous Formulation contacted.

In an embodiment In the present invention, (A) is contacted with aqueous Formulation at temperatures in the range of 20 to 100 ° C, preferably at room temperature.

In an embodiment The present invention is contacted at pressures in Range of 0.5 bar to 10 bar, especially at atmospheric pressure.

In an embodiment In the present invention, (A) is contacted with aqueous Formulation at temperatures in the range of 70 to 180 ° C, preferably 90 ° C to 120 ° C, and use pressures above atmospheric pressure on, for example, up to 10 bar.

Contacting according to the invention you can, for example, over a period of 0.1 seconds to 60 minutes, preferably 0.5 seconds up to 30 minutes.

The Contacting substrate (A) with aqueous used according to the invention Formulation can be, for example, by spraying, padding, Coating, impregnation and printing, for example, by the ink-jet method, perform.

you Substrate (A) can be used one or more times in succession according to the invention aqueous formulation to contact.

to execution the method according to the invention one prefers to proceed so that one flexible substrate with at least an inventively used aqueous Formulation contacted and then dried.

Especially Preferably, one proceeds in such a way that one before the actual drying treated according to the invention Pre-dried substrate, for example, a residual moisture in the area from 0.5 to 2% by weight.

The Pre-drying or drying leaves focus on common Perform equipment. So it is, for example, when treating textile substrates hopes on all usual in the textile industry fixing and drying units feasible. Suitable drying or predrying temperatures are, for example 50 to 300 ° C, preferably 70 to 180 ° C.

After that you can over a period of, for example, 10 seconds to 60 minutes, preferably 0.5 Minutes to 7 minutes at temperatures in the range of 50 to 300 ° C, preferably 100 to 160 ° C, more preferably 110 to 130 ° C thermally treat. Polyamide, polyester, polyvinyl chloride, modified Polyester, polyester blend, polyamide blend, polyacrylonitrile, Polycarbonate is treated thermally advantageously at temperatures in the range of 130 to 250 ° C. Polypropylene fabric preferably between 80 and 130 ° C, preferably 110 and 130 ° C. there In general, the temperature of the medium is below the temperature to understand that surrounds the flexible substrate to be treated.

In an embodiment of the present invention used according to the invention aqueous formulation at least one further substance (E), which may be selected from thickeners, Crosslinkers, fastness improvers, plasticizers, defoamers, wetting agents and leveling agents.

wobei die Variablen wie folgt definiert sind:
Y¹ gewählt aus N-R¹⁵, Sauerstoff und N-H,
Z¹ gewählt aus Wasserstoff und CO-O-R¹⁵,
R¹⁵ gleich oder verschieden und gewählt aus C₁-C₁₀-Alkyl, besonders bevorzugt sind Methyl und n-Butyl.Suitable crosslinkers are, for example, urea-formaldehyde and melamine-formaldehyde addition products, optionally in combination with inorganic salts such as MgCl ₂ .6H ₂ O or NH ₄ Cl. Other suitable crosslinkers are, for example, free or blocked isocyanates or polyisocyanates, for example compounds of the general formula VI

where the variables are defined as follows:
Y ¹ selected from NR ¹⁵ , oxygen and NH,
Z ¹ selected from hydrogen and CO-OR ¹⁵ ,
R ^{15 are} identical or different and selected from C ₁ -C ₁₀ -alkyl, particular preference is given to methyl and n-butyl.

Further suitable crosslinkers are polyfunctional epoxides such as Polyglycidyl ethers of polyols e.g. pentaerythritol polyglycidyl and polyfunctional aziridines such as trimethylolpropane tris (beta-aziridinylpropionate).

antiscalent For example, you can add to the while contacting the Formation of coverings to prevent rolls of example foulards. suitable Coating inhibitors are, for example, mixtures of multiply alkoxylated Alcohols, especially of polyethylenated fatty alcohols.

When Thickener (thickener) can be natural or synthetic thickener been set. examples for natural Thickeners are alginate, guar, starch, Core flour ethers, cassia, tamarind cellulose ethers, dextrins such as natural Gums, galactomannan, xanthan, polysaccharide and mixtures of the aforementioned substances. Preference is given to the use of synthetic Thickening, for example, solutions of liquid at room temperature synthetic (co) polymers in, for example, white oil or as aqueous solutions or as water-in-oil emulsions, preferably with about 40% by weight of (co) polymer.

mit Molekulargewichten M_w im Bereich von 100.000 bis 200.000 g/mol, in denen R¹⁶ für Methyl oder bevorzugt für Wasserstoff steht.Preferred examples of thickeners are copolymers having from 85 to 95% by weight of acrylic acid, from 4 to 14% by weight of acrylamide and from about 0.01 to 1% by weight of the (meth) acrylamide derivative of formula VII

with molecular weights M _w in the range of 100,000 to 200,000 g / mol, in which R ^{16 is} methyl or preferably hydrogen.

Formulations according to the invention can Contain 30 to 70 wt .-% white oil. aqueous Thickeners usually contain in total up to 25% by weight of (co) polymer, in some cases up to to 50 wt .-% (so-called thickener dispersions), based on the entire thickener. wishes one watery To use formulations of a thickener, so you put in general aqueous Ammonia too. The use of granular, solid formulations a thickener are conceivable, for example, emission-free To produce pigment prints.

suitable Authenticity improvers are, for example, liquid silicone oils and polysiloxanes at room temperature. In a preferred variant of the present invention can be refrain from the use of fastness improvers.

Examples for suitable Plasticizers are ester compounds selected from the groups of Alkanols completely esterified aliphatic or aromatic di- or polycarboxylic acids and the at least simply esterified with alkanol phosphoric acid.

In one embodiment of the present invention, alkanols are C ₁ -C ₁₀ alkanols.

preferred examples for with alkanol completely esterified aromatic di- or polycarboxylic acids are completely esterified with alkanol phthalic acid, isophthalic and mellitic acid; exemplified by its: di-n-octyl phthalate, di-n-nonyl phthalate, Di-n-decyl phthalate, Di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.

preferred examples for with alkanol completely esterified aliphatic di- or polycarboxylic acids are, for example, dimethyl adipate, adipate, Adipic acid di-n-butyl ester, adipate, glutarate, adipic, Glutarsäuredi-n-butyl ester, Glutarsäurediisobutylester, succinate, succinate, Bernsteinsäuredi n-butyl succinate and mixtures of the aforementioned compounds.

Preferred examples of phosphoric acid which is at least monoesterified with alkanol are C ₁ -C ₁₀ -alkyl-di-C ₆ -C ₁₄ -aryl phosphates, such as isodecyldiphenyl phosphate.

Further suitable examples of plasticizers are at least simple with C ₁ -C ₁₀ -alkylcarboxylic acid at least monoesterified aliphatic or aromatic di- or polyols.

Preferred examples of aliphatic or aromatic di- or polyols at least monoesterified with C ₁ -C ₁₀ -alkylcarboxylic acid is 2,2,4-trimethylpentane-1,3-diol monoisobutyrate.

Further suitable plasticizers are polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably with an M _w of 200 g / mol, and polypropylene glycol alkylphenyl ethers, preferably with an M _w of 450 g / mol.

Further suitable plasticizers are polypropylene glycols having a molecular weight M _w in the range from 400 to 800 g / mol, etherified with two different alcohols, wherein preferably one of the alcohols may be an alkanol, in particular a C ₁ -C ₁₀ -alkanol and the other alcohol is preferably one may be aromatic alcohol, for example o-cresol, m-cresol, p-cresol and in particular phenol.

Suitable defoamers are, for example, silicone-containing antifoams, for example those of the formula HO- (CH ₂ ) ₃ -Si [OSi (CH ₃ ) ₃ ] ₂ . Silicone-free antifoams are also suitable, for example polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-times ethoxylated preferably unbranched C ₁₀ -C ₂₀ -alkanols, unbranched C ₁₀ -C ₂₀ -alkanols and 2-ethylhexan-1-ol.

suitable Wetting agents are, for example, nonionic, anionic or cationic Surfactants, especially ethoxylation and / or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, further Ethoxylates of oleic acid or Alkylphenols, alkylphenol ether sulfates, alkyl polyglycosides, alkyl phosphonates, Alkylphenyl phosphonates, alkyl phosphates, or alkylphenyl phosphates.

Suitable leveling agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M _n in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol. Very particular preference is given to block copolymers of propylene oxide / ethylene oxide, for example of the formula EO ₈ PO ₇ EO ₈ , where EO is ethylene oxide and PO is propylene oxide.

One Another object of the present invention are substrates treated according to the inventive method. Inventive substrates contain at least one ethylene copolymer wax in optionally networked form. Inventive substrates have good performance properties, for example, good fastness properties, especially wash fastness and rubbing fastness such as Dry and wet rub fastness.

A special embodiment The present invention is a process for the preparation of printed flexible substrates and in particular printed textile by the method according to the invention, in Below also textile printing process according to the invention called.

to execution the textile printing process according to the invention For example, it is possible to proceed in such a way that at least one aqueous formulation according to the invention is present to a printing paste, hereinafter also printing paste according to the invention called, processed and then according to known methods printed textile substrates.

Advantageous If you are printing pastes invention by mixing at least one aqueous used according to the invention Formulation with tools common in the printing process and at least a pigment (C) ago. The color depth is advantageous Tuning the ratio Pigment (C) used according to the invention aqueous Formulation.

Pigment is added to the printing paste according to the invention preferably in the form of pigment preparations. Pigment preparations usually contain from 20 to 60% by weight of pigment, furthermore water and one or more surface-active compounds, for example one or more emulsifiers, by way of example multiply alkoxylated C ₁₀ -C ₃₀ -alkanols may be mentioned.

The ratio of pigment to aqueous formulation used according to the invention can be chosen within wide limits. For example, it is possible to choose pigment and aqueous formulation used according to the invention in a weight ratio of 20: 1 to 1: 100. In a preferred embodiment of the present invention, the ratio of pigment to aqueous For such that the weight ratio of pigment to solid content of aqueous formulation used according to the invention is in the range from 1: 1 to 1: 30.

of course is it also possible first Pigment and used according to the invention aqueous Formulation in a weight ratio in the range of 20: 1 to 10: 1 premix and only immediately before printing another used according to the invention aqueous Formulation or a conventional acrylate binder to mix.

Further common auxiliaries for printing pastes in textile printing are known from Ullmann, Handbuch der technischen Chemie und Verfahrenstechnik, see, for example, Ullmann's Encyclopaedia of Industrial Chemistry, 5th edition, keyword: Textile Auxiliaries, Vol. A26, p. 286 et seq. And 296 et seq., Verlag Chemie, Weinheim, Deerfield / Florida, Basel; 1996, and from the textile aid catalog, Konradin publishing house Robert Kohlhammer GmbH, D-70771 Leinfelden-Echterdingen. Thickeners, fixers, handle improvers, defoamers, rheology improvers, acid donors and emulsifiers are mentioned by way of example as common auxiliaries:
In a preferred embodiment of the present invention, printing pastes according to the invention also contain handle improvers selected from silicones, in particular polydimethylsiloxanes, and fatty acid C ₁ -C ₁₀ -alkyl esters. Examples of commercially available hand improvers which may be added to the inventive print pastes are Acramin ^® plasticizer SI (Bayer AG), Luprimol SIG ^®, Luprimol TX 4732 and Luprimol CW ^® (BASF Aktiengesellschaft).

In a preferred embodiment of the present invention, printing pastes according to the invention comprise one or more emulsifiers as further additives, in particular when the printing pastes comprise white oil-containing thickeners and are obtained as an oil-in-water emulsion. Examples of suitable emulsifiers are aryl- or alkyl-substituted polyglycol ethers. Commercially available examples of suitable emulsifiers are emulsifier W ^® (Bayer), Luprintol PE New ^® and Luprintol MP ^® (BASF Aktiengesellschaft).

to Production of printing pastes according to the invention You can, for example, so that you have water, if necessary a defoamer, for example, a defoamer Milled on a silicone basis and with mixing, for example with stirring, at least one used according to the invention aqueous Formulation adds. After that you can get one or more emulsifiers and that or the Add pigments.

When next You can add one or more handle improvers, for example one or more silicone emulsions.

Then you can Add one or more thickening agents and mix further, for example, stirring, homogenize.

A typical printing paste of the invention contains, in each case per kilogram of printing paste according to the invention
0.5 to 400 g, preferably 10 to 250 g of ethylene copolymer wax (B),
0 to 100 g, preferably 1 to 5 g emulsifier,
1 to 500 g, preferably 3 to 100 g of thickener,
0 to 500 g, preferably 0.1 to 250 g, preferably 0.5 to 120 g of pigment (C),
optionally further aids;
the rest is preferably water.

In an embodiment According to the present invention, printing pastes according to the invention have a viscosity in the range at 20 ° C. from 0.3 to 4000 dPa.s, preferably 20 to 200 dPa · s and more preferably 60 to 100 dPa · s. Let viscosities according to common Determine methods, in particular for example with a rotational viscometer, For example, the Viscotester VT02 or VT24 Fa. Haake Mess-Technik GmbH u. Co., Karlsruhe.

pigment printing using at least one printing paste according to the invention can according to various Procedure performed become known in themselves. Usually one uses one Template by which the printing paste according to the invention with a doctor blade pressed. This procedure belongs zur Siebdruckverfah Ren. Pigment printing process according to the invention under Use of at least one printing paste of the invention provide printed Substrates with particularly high brilliance and color depth of the prints at the same time good grip of the printed substrates. object The present invention therefore flexible substrates are printed according to the printing method according to the invention using the printing pastes according to the invention.

A other embodiment The present invention is a pigment dyeing method using of at least one formulation according to the invention, in the following also inventive pigment dyeing method called. The dyeing process according to the invention you lead preferably in such a way that at least one flexible substrate, preferably a textile substrate, with at least one dyeing liquor treated, which contains at least one formulation according to the invention. dye baths, containing at least one formulation according to the invention, are also called dyeing liquors according to the invention below.

Inventive dyeing liquors can as an additive wetting agents, preferably when the wetting agents as Low foaming, because of the high turbulence in the dyeing process Foaming the quality the coloring through the formation of vagueness impaired becomes.

dry textile woven, knitted or nonwoven, as in the continuous pigment dyeing used, contain a large amount of air. To carry out the Pigmenting process of the invention is therefore the use of deaerators advantageous. These are based, for example, on polyethersiloxane copolymers. You can in amounts of 0.01 to 2 g / l in the dyeing liquors according to the invention be included.

Furthermore, inventive dyeing liquors may contain anti-migration agents. Suitable anti-migration agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M _n in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol.

Farther you can the dye liquors of the invention Add one or more handle enhancers as an additive. in this connection they are usually polysiloxanes or waxes. polysiloxanes have the advantage of permanence, while the waxes slowly during the Washed out use.

The viscosities the dyeing liquors according to the invention are preferably in the range of less than 100 mPa · s. The surface tensions the dyeing liquors according to the invention should be adjusted so that wetting of the goods is possible. common are surface tensions of less than 50 mN / m.

In one embodiment of the present invention, a typical dyeing liquor according to the invention contains per liter
0.5 to 400 g, preferably 20 to 300 g of ethylene copolymer wax (B),
0 to 100 g, preferably 0.1 to 10 g of wetting agent,
0 to 100 g, preferably 0.1 to 10 g defoamer,
0 to 300 g, preferably 1 to 20 g anti-spread agent,
0 to 100 g, preferably 1 to 50 g of anti-migration agent,
0 to 100 g, preferably 1 to 50 g of leveling agent,
0.5 to 25 g, preferably 1 to 12 g of pigment (C).

One Another aspect of the present invention is a method for Preparation of inventive dyeing liquors. The inventive method comprises the mixing of colorants, for example pigment (C), preferably in the form of pigment preparations, in addition to pigment and water contain one or more surface-active compounds, listed above additives like other solvents, defoamers, Handle improvers, emulsifiers and / or biocides and filling with Water. To exercise the process for the preparation of dyeing liquors according to the invention is usually stirred the components of the inventive dyeing liquors in a mixing container, wherein Size and shape of the mixing container are not critical. Preferably, the stirring is followed by a clarification at.

One Another aspect of the present invention is a method for To dye of flexible substrates using the above described dyeing liquors according to the invention, hereinafter also as inventive dyeing method, in particular as a pigment dyeing process according to the invention designated. The dyeing process according to the invention can be used in common dyeing carried out become. Foulards are preferred, as the essential element two Contain cushioned rollers, through the flexible substrate and in particular textile led becomes. Above the rollers dyeing liquor according to the invention is filled in and wets flexible substrate or the textile. By the pressure of Rolling the flexible substrate or the textile is squeezed off and ensures a constant order.

The actual dyeing step is usually followed by a thermal drying and optionally a fixation. Preferably, it is dried at temperatures of 25 to 300 ° C over a period of 10 Seconds to 60 minutes, preferably 30 seconds to 10 minutes. If you want to fix, so fixed at temperatures of 150 ° C to 190 ° C over a period of 30 seconds to 5 minutes.

Prefers is a process for pigmentation after the padding process.

Printed according to the invention and colored Substrates are characterized by a special brilliance of the colors at the same time good grip of the printed or colored substrates. Another Aspects of the present invention are therefore substrates colored after the method described above using the dyeing liquors according to the invention.

One Another object of the present invention are colored flexible Substrates, available after the pigment dyeing process according to the invention. Dyed flexible according to the invention Substrates are characterized, for example, by good wash fastnesses, good dry and wet rub fastness and good fastness properties, in particular by low color depth losses in the Kochbürstwäsche.

In another embodiment The present invention is contacted flexible substrates (A) and in particular films or textile made of polypropylene with pigment-free aqueous Formulation and drying afterwards. On flexible substrate evenly distributed uncrosslinked ethylene copolymer wax acts as a primer and allows bonding with any other materials.

In another embodiment The present invention can be the method of the invention for printing on flexible substrates as a transfer printing method carry out. For this you print one with wax, for example with silicone wax coated paper with at least one printing paste according to the invention and then dry the printed paper at room temperature 300 ° C, preferably at room temperature to 180 ° C. The printed and dried Paper is placed on a hot press together with the textile material or a hot one Calender at 70 to 300 ° C, preferably 10 to 100 s at 100 to 120 ° C, treated. During this Process it comes to softening / melting of the printing paste and transfer and fixing paper on the 2- or 3-dimensional printable flexible substrate, for example textile substrate or film.

The Invention will be explained by working examples.

working examples

1. Production of ethylene copolymer wax

In a high pressure autoclave as described in the literature (Buback, M., et al., Chem. Ing. Tech., 1994, 66, 510), were ethylene and acrylic acid or methacrylic acid according to the table 1 copolymerized. To this was added ethylene (12.0 kg / h) under the reaction pressure of 1700 bar fed into the autoclave. Separated from that the stated in Table 1 amount of acrylic acid or methacrylic acid on compressed an intermediate pressure of 350 bar and then under the reaction pressure of 1700 bar fed. Separated from that Initiator solution consisting of tert-butyl peroxypivalate in isododecane (amount and Concentration s. Table 1), under the reaction pressure of 1700 bar fed into the autoclave. Separately, the table was in the 1 specified regulator consisting of propionaldehyde in isododecane, Concentration s. Table 1, first compressed to an intermediate pressure of 260 bar and then with Help another compressor fed into the high-pressure autoclave. The reaction temperature was 220 ° C. Ethylene copolymer waxes were obtained according to the table 1 with the analytical data shown in Table 2.

Of the Content of ethylene and acrylic acid or methacrylic acid in the ethylene copolymer wax was determined by NMR spectroscopy or by titration (Acid value) certainly. The acid number of the ethylene copolymer wax was determined by titrimetry according to DIN 53402. The KOH consumption corresponds to the acrylic acid or methacrylic acid content in 15 ethylene copolymer wax. The MFI was according to DIN 53735 at 160 ° C and a Load of 325 g determined.

Table 1: Preparation of ethylene copolymer waxes

T _Raktor is the maximum internal temperature of the high pressure autoclave to understand.

Table 2: Analytical data of ethylene copolymer waxes

Under "Salary" is the proportion of copolymerized ethylene or acrylic acid or methacrylic acid in the respective To understand ethylene copolymer wax.

Abbreviations:

• AS:

  Acrylic acid,

  MAS:

  methacrylic acid,

  PA:

  propionaldehyde,

  ID:

  Isodothekan,

  PO:

  t-butyl hydroperoxide,

  ECW:

  Ethylene copolymer.

2. Production of watery Dispersions of ethylene copolymer waxes

In A 2-liter autoclave with anchor stirrer was the in Table 3 given amount of ethylene copolymer wax according to Example 1 submitted. There were the indicated amounts in Table 3 deionized water and Ammonia added and stirred to 120 ° C heated. After 30 minutes at 120 ° was cooled to room temperature within 15 minutes. you received the dispersions 2.1 and 2.2 respectively.

Table 3: Preparation of aqueous dispersions of ethylene copolymer wax

The viscosity was determined using a 5 mm beaker at 23 ° C. to ISO 2431. The "amount NH ₃ " refers to the amount of 25% by weight aqueous ammonia solution.

3. Preparation of printing pastes according to the invention

3.1 Production of a blue pigment preparation

In a stirred ball mill of the type Drais Superflow DCP SF 12 were ground together: 2640 g Pigment Blue 15: 3 460 g nC ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₂₅ H 600 g glycerin 2300 g distilled water

The Milling was continued until the pigment particles became medium Diameter of 100 nm.

3.2. Production of stem pastes

you mulled in a mixing vessel, the ingredients according to the table 4 and received the master pastes 3.1 to 3.4, adding the ingredients in the list in Table 4 Sequence united and mingled. One is mingled afterwards 15 minutes with a fast stirrer Ultra-Turrax type with about 6000 revolutions / min and then tested the pH. When the pH was below 8, a pH was set of 8.5 by adding concentrated aqueous ammonia.

Table 4: Preparation of master pastes 3.1 to 3.4

Under 2.1 or 2.2, the respective aqueous dispersion is 2.1 or 2.2 understood from Example 2.

The thickener used was in each case:
Dispersion of
Copolymer of acrylic acid (92% by weight), acrylamide (7.6% by weight), methylenebisacrylamide (0.4% by weight), quantitatively neutralized with ammonia (25% in water), molecular weight M _w of approx 150,000g / mol
as a water-in-mineral oil dispersion (volume ratio 2.6: 1) (bp of the mineral oil: 19-230 ° C), solids content: 24 wt .-%; stabilized with sorbitan monooleate (2.5 wt .-%, based on total thickener).

3.3. Mixing of stem pastes with blue pigment preparation from example 3.2.

By Mixing each 970 g of stock paste according to Table 4 with 30 each g of blue pigment preparation from Example 3.1 were inventive printing pastes according to the table 5 produced.

you received printing pastes according to the invention 4.1 to 4.4 according to the table 5th

Table 5: Preparation of printing pastes according to the invention

4. Printing experiments, tests the prints

Substrate made of polypropylene fabric, basis weight, was screen printed 170 g / m ² .

The Printing parameters were: doctor blade 15 mm, stencil gauze ESTAL MONO E 55, Magnetic level 6, simple print, no pattern.

you dried in a drying oven at 80 ° C and then fixed on a fixing cabinet by heating for 5 minutes with hot air at 110 ° C.

you received the substrates according to the invention 5.1 and 5.2, also printed according to the invention Substrates 5.1 or 5.2 mentioned.

als Emulgator; Feststoffgehalt: 35 Gew.-%.For comparison, a printing was carried out with a comparative printing paste V4.5 which had been prepared analogously to the printing paste 4.1 according to the invention, but ethylene copolymer wax dispersion 2.1 was replaced by a dispersion (acrylate binder dispersion) of the following copolymer:
n-butyl acrylate (66% by weight),
Styrene (31% by weight),
Acrylic acid (1% by weight),
Methylolacrylamide (1% by weight), acrylamide (1% by weight), quantitatively neutralized with ammonia (25% strength by weight in water), with 2% by weight, based on the copolymer

as emulsifier; Solids content: 35% by weight.

you received reference substrate V5.5.

The inventive substrates were tested for dry and wet rubbing fastness according to DIN EN ISO 105-X12 and wash fastness tested according to DIN EN ISO 105-C03. best possible Result: Grade 5, worst possible result: Grade 1.

you obtained the following substrates and test results according to the invention according to the table 6th

Table 6: Substrates and test results printed according to the invention

6. Preparation of dyeing liquors according to the invention and pigmentation

6.1. Production of dyeing liquors according to the invention

General recipe:

In a stirred vessel mixed by stirring: Completely desalinated water 774 g Pigment preparation from Example 3.1 20 g / l (calculated on pigment preparation) Aqueous dispersion 2.1 or 2.2 180 g / l (calculated on solids content) EO ₈ PO ₇ EO ₈ 20 g / l as an anti-migration agent nC ₁₂ H ₂₅ O (C ₂ H ₄ O) ₇ H 4 g / l as anti-fouling agent HO- (CH ₂ ) ₃ -Si [OSi (CH ₃ ) ₃ ] ₂ 20 g / l as defoamer and filled to one liter with demineralized water. If aqueous dispersion 2.1 is used, the dyestuff liquor F6.1 according to the invention is obtained; If aqueous dispersion 2.2 is used, the dyestuff liquor F6.2 according to the invention is obtained.

Antimigration agent: In the anti-migration agent EO ₈ PO ₇ EO ₈ used in the general formulation, EO always stands for ethylene oxide and PO for propylene oxide. It has the following properties: a cloud point in water of 40 ° C, an average molar mass M _w of 1100 g / ml, solidification point <5 ° C, viscosity at 25 ° C: 175 mPa · s.

6.2. Dyeing of substrates with dyeing liquors according to the invention

With a foulard (manufacturer Fa. Mathis, type no. HVF12085) was a textile substrate (polypropylene fabric), each with a 6.1 prepared liquor according to the invention colored. The contact pressure of the rollers was 2.6 bar. It resulted in a Fleet intake of 55%. The application speed was 2 m / min. Subsequently the textile was at 80 ° C in a convection oven (manufacturer: Mathis, type no. LTF89534) Dried for 60 s (circulating air 50%). The final fixation took place 5 Minutes at 110 ° C below Circulating air (100%).

you obtained the following substrates according to the invention, also called dyed substrates according to the invention, and test results according to table 7th

The Comparative substrate was by staining prepared with a comparison liquor, the dye liquor of the invention F6.1 was the same except that instead of dispersion 2.1 a same amount of acrylate binder dispersion was used, which also was used to prepare the comparative printing paste V4.5.

Table 7: Substrates dyed according to the invention and test results

7. Preparation of transfer prints

7.1 Preparation of transfer printing inks according to the invention

Table 8: Preparation of transfer printing inks 8.1 to 8.2 according to the invention

7.2. Production of transfer prints

A coated with silicone wax paper was printed with the printing pastes according to the invention, eg 8.1 and 8.2 and then dried at 100 ° C. The printed and dried paper will be together treated with textile on a hot press at 120 ° C for one minute. During this process softening / melting of the printing paste and transfer and fixing of paper to the textile to be printed occurs.

Claims (10)

Process for the treatment of flexible substrates, characterized in that (A) at least one flexible substrate selected from substrates of (A1) polyacrylic, polyester, silicone, polyamide or (A2) one or more polymers based on a monomer of the general formula I

in which R ^{1 is} selected from -Cl, C ₁ -C ₁₀ -alkyl, -CH = CH ₂ , -C (Cl) = CH ₂ , -C (CH ₃ ) = CH ₂ and -COOC ₁ -C ₁₀ - Alkyl, contacted with at least one aqueous formulation, comprising (B) at least one ethylene copolymer wax which contains 60 to 95% by weight of ethylene and 5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid in copolymerized form, furthermore at least one colorant selected from ( C) at least one pigment and (D) at least one dye. Process according to Claim 1, characterized in that at least one ethylenically unsaturated carboxylic acid is a carboxylic acid of the general formula II

wherein the radicals are defined as follows: R ² selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl or COOH, COOCH ₃ , COOC ₂ H ₅ , R ³ selected from hydrogen, unbranched or branched C ₁ -C ₁₀ -alkyl. Method according to claim 1 or 2, characterized that flexible substrates are chosen are made of films and textile substrates. Method according to one of claims 1 to 3, characterized that flexible substrates out (A2) polypropylene to get voted. Method according to one of claims 1 to 4, characterized that flexible substrates are chosen made of woven, knitted and nonwovens. Method according to one of claims 1 to 5, characterized that at least one aqueous formulation (A) contains at least one further substance selected from thickeners, crosslinkers, Coating inhibitors, fastness improvers, plasticizers, defoamers, wetting agents and leveling agents. Method according to one of claims 1 to 6, characterized that treated flexible substrate after contacting dries. Flexible substrates treated by a process according to one of the claims 1 to 7. Printing pastes, containing (B) at least one aqueous A formulation containing at least one ethylene copolymer wax which 60 to 95 wt .-% of ethylene and 5 to 40 wt .-% of at least one ethylenic unsaturated carboxylic acid contains polymerized, and (C) at least one pigment. dye baths, containing (B) at least one aqueous formulation containing at least contains an ethylene copolymer wax, which comprises 60 to 95% by weight of ethylene and 5 to 40% by weight of at least an ethylenically unsaturated carboxylic acid contains polymerized, and (C) at least one pigment or (D) at least one Dye.