DE10036694A1 - Process for the treatment of organic fibers with amino-functional organosilicon compounds - Google Patents

Abstract

The invention relates to a method for treating organic fibres in jet dyeing machines by means of aqueous formulations of aminofunctional organosilicon compounds containing (a) at least one siloxane unit of general formula (I) wherein R is the same or different and represents a monovalent, optionally halogenated hydrocarbon radical comprising 1 to 18 carbon atoms per radical; R<1> is the same or different and represents a hydrocarbon radical comprising 1 to 8 carbon atoms per radical; a represents 0, 1, 2 or 3, b represents 0, 1, 2 or 3, and c represents 1, 2 or 3, provided that the sum of a+b+c is less than or equal to 3; Y represents a monovalent organic radical comprising at least 2 positively charged nitrogen atoms, provided that at least three carbon atoms which can be optionally split or substituted by separate heteroatoms are found respectively between the positively charged nitrogen atoms in radical Y, and provided that the organosilicon compounds contain at least 0.35 wt. % of positively charged nitrogen atoms, and (b) at least one siloxane unit of general formula (II) wherein R, R<1>, a and b have the designation cited above, provided that the sum of a+b is less than or equal to 3.

Description

The invention relates to a method for the treatment of organic fibers with amino functional Organosilicon compounds.

Siloxanes bearing ammonium groups are already from the literature has been known for a long time Ways described. A synthesis route, such as B. in GB-A 2 201 433 described here is based on epoxy-functional silicones from a hydrosilylation reaction of Si-H groups bearing siloxanes with an epoxy bearing a vinyl group (e.g. allyl glycidyl ether) can be obtained and sets them epoxy-functional silicones with ammonium salts of tertiary amines to silicon-bearing silicones. Another The first possibility is an aminoalkyl group to produce load-bearing siloxane and then with To quaternize alkylating agents, as described, for example, in EP-A 436 359 is described.

In DE-A 196 52 524 the suitability is ammonium groups Siloxanes for textile equipment are described, the by Alkylation of classic aminosiloxanes with Alkylsulfonic acid esters obtained a polyorganosiloxanes improved running stability of the fleet, especially at pH Values greater than 7.

The ones used today in textile finishing as plasticizers The vast majority of aminosiloxanes contribute Aminoethylaminopropyl side groups or Aminopropylseitengruppen. The aminosiloxanes are usually applied in the form of emulsions. This poses the last step, the so-called equipment, at the Generation of textile fabrics and can by  so-called forced application (e.g. in the foulard) or due to of the cationic character of the aminosiloxanes in principle also happen in the pull-out procedure.

For dyeing textiles in the exhaust process different equipment can be used. Are in use here machines which are of the reel type and let those of the type dyeing machine be classified. In the The reel skid is left with the material to be treated Strand form by means of a roller system in the fleet circulate (see also Ullmann's Encyclopedia of Industrial Chemistry, Vol. A26, p. 368, chap. 2.2.4.2). Although through the Circulation of the strand sewn together at the ends through the Brisk uniform coloring can be achieved, this has however on the condition that the goods under the Fleet level can linger. But that in turn requires a very high fleet ratio (= ratio of fleet volume substance treated per unit weight). The remaining fleet must be as Waste water can be disposed of, which is a significant cost and Represents environmental problem, so this technology today as is outdated. In order to take this problem into account, Jet dyeing machines (jet dyeing machines) developed today the vast majority of those in the pull-out dyeing represent dyeing machines used (see also Ullmann's Encyclopedia of Industrial Chemistry, Vol. A26, p. 368, chap. 2.2.4.3). Here, not only the substance in the form of a circulated at both ends of the sewn strand, but also the fleet in a circle. This is under high pressure pumped onto the material passing through an annular nozzle, so that the treated textile is flushed through the liquor very homogeneously and so a level coloring is obtained. The excess Fleet gathers at the bottom of the fabric storage container and becomes pumped back to the nozzle in the circuit. in principle a distinction is made between nozzle dyeing machines "Overflow" and "Airflow" nozzle dyeing machines. With the former  the pure fleet is circulated, with the latter additional Air is blown into the ring nozzle, so that a Liquid / air mixture is pumped onto the fabric.

As advantageous as the strong liquor turbulence in the dyeing process is, the difficulties in equipping Textiles in jet dyeing machines with aminosilicone emulsions. The aminosilicone emulsions normally show due to their cationic charge has sufficient fiber affinity and can therefore be processed in reel runners.

In jet dyeing machines, the high liquor turbulence and the high shear forces occurring in the pump and ring nozzle very strong foam development, the pumping around and thus the Makes circulation of the fleet impossible. Beyond that is missing the surfactant concentrated in the foam in stabilizing the Aminosilicone emulsion so that it can become unstable released aminosilicon floated and so in the form of difficult to remove silicone stains on the treated Textile remains. This represents an unsustainable economic risk for the supplier, so that for one Finishing of textile dyed on jet dyeing machines Silicone soft grip means the goods in a further operation equipped on the foulard by forced application.

The task was to develop a procedure for the treatment of organic fibers with amino functional To provide organosilicon compounds, the amino-functional organosilicon compounds soluble in water or are self-dispersing and therefore aqueous preparations the aqueous ones are possible without the use of surfactants Preparations of amino-functional organosilicon compounds are sufficiently stable under the influence of shear forces and only a little foam and those with the amino functional ones  Organosilicon compounds treated organic fibers have a soft feel.

The task also consisted of a method for the treatment of organic fibers with amino functional To provide organosilicon compounds in which a Labor and cost savings are achieved The object is achieved by the invention.

The invention relates to a process for the treatment of organic fibers with aqueous preparations of amino-functional organosilicon compounds containing

• a) at least one siloxane unit of the general formula
  where R is the same or different and is a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
  R ^{1 is the} same or different and represents a monovalent hydrocarbon radical having 1 to 8 carbon atoms per radical,
  a is 0, 1, 2 or 3,
  b is 0, 1, 2 or 3,
  c is 1, 2 or 3
  with the proviso that the sum is a + b + c ≦ 3,
  Y is a monovalent organic radical having at least 2 positively charged nitrogen atoms, with the proviso that between the positively charged nitrogen atoms in the radical Y there are at least three carbon atoms, which may be interrupted or substituted by separate heteroatoms, and
  with the proviso that the organosilicon compound contains at least 0.35% by weight of positively charged nitrogen atoms, and
• b) at least one siloxane unit of the general formula
  where R, R ¹ , a and b have the meaning given above, with the proviso that the sum is a + b ≦ 3, in nozzle dyeing machines.

The organosilicon compounds according to the invention can furthermore (c) at least one bridge unit of the general formula

where R, R ¹ , a and b have the meaning given above, with the proviso that the sum a + b ≦ 2 and
Y 'denotes an organic radical having at least 2 positively charged nitrogen atoms, with the proviso that between the positively charged nitrogen atoms in the radical Y' there are at least three carbon atoms, which may be interrupted or substituted by separate heteroatoms.

Examples of radicals R are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n- Pentyl, iso-pentyl, neo-pentyl, tert-pentyl, Hexyl radicals, such as the n-hexyl radical, heptyl radicals, such as the n- Heptyl radical, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical, nonyl radicals, such as the n- Nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as  the n-dodecyl radical, and octadecyl radicals, such as the n-octadecyl radical, Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl residues, aryl residues, such as the phenyl, Naphthyl, anthryl and phenanthryl, alkaryl, such as o-, m, p-tolyl, xylyl and ethylphenyl, and Aralkyl radicals, such as the benzyl radical, the α- and the β- Phenylethyl radicals.

Examples of substituted radicals R are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexa fluorisopropyl, the heptafluoroisopropyl, and Halogenaryl radicals, such as the o-, m- and p-chlorophenyl radicals.

R is preferably a methyl radical.

Examples of radicals R ¹ are alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl -, neo-pentyl, tert-pentyl, hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl, such as the n-octyl and iso-octyl, such as the 2,2,4-trimethylpentyl, the methyl and ethyl radicals being preferred.

The amino-functional organosilicon compounds according to the invention which can be used are those which are prepared by graft copolymerization of ethylenically unsaturated monomers having amino groups on mercaptosiloxanes and which are described in DE-A 198 02 069 (incorporated by reference), in particular page 3, line 4 to page 4, line 30 and page 6, lines 33-46. Y is preferably a radical of the formula

-R ³ - (SZH) _k is, (IV)

where R ^{3 is} a divalent or trivalent linear or branched hydrocarbon radical having 2 to 10 carbon atoms, which can be interrupted or substituted by separate heteroatoms,
k 1 or 2,
and Z is a residue selected from the group of residues

and mixtures of the abovementioned radicals (A), (B) and (C),
where R ^{2 is} a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms,
R ^{4 is} a monovalent hydrocarbon radical with 1 to 10 carbon atoms,
R ^{5 is} a hydrogen atom or a monovalent hydrocarbon radical having 1 to 10 carbon atoms, W -NR ² - or -O- (where R ^{2 has} the meaning given above),
U is a linear or branched alkylene radical with 2 to 10 carbon atoms,
X ^- a negatively charged ion stable in aqueous solution
h 0 or an integer from 1 to 250 and
i is 0 or an integer from 1 to 400, with the proviso that the sum is h + i ≧ 5.

Between the positively charged nitrogen atoms in the Y radical there is therefore preferably a hydrocarbon radical with at least three carbon atoms, which can be substituted by a -C (= O) O or -C (= O) NR ² or -O group.

R ² is preferably a hydrogen atom or a methyl radical.

The radicals R ³ should have no easily hydrolyzable groups, such as, for example, ester groups, and also no unsaturated and / or no proton-releasing groups. Examples of radicals R ³ are alkylene radicals having 2 to 10 carbon atoms, such as propylene radicals, 2-methylpropylene radical, butylene radicals and decanyl radicals. Examples of radicals R ³ substituted by separate heteroatoms are alkylene radicals having 2 to 10 carbon atoms which are substituted by hydroxyl, halogen or alkoxy groups. Examples of radicals R ³ substituted by separate heteroatoms are alkylene radicals having 2 to 10 carbon atoms which are interrupted by one or two hetero groups selected from the group of ether, thioether, amino, carboxyl, carbamide and sulfonamide groups. An example of this is the

Examples of radicals R ⁴ are substituted or unsubstituted alkyl, aryl or alkaryl radicals.

Examples of radicals R ⁵ are substituted or unsubstituted saturated or unsaturated alkyl, aryl or alkaryl radicals. R ⁵ is preferably a hydrogen atom.

Examples of the remainder U is a linear or branched one Alkylene radical with 2 to 10 carbon atoms.

H is preferably 0 or an integer from 1 to 150, particularly h is preferably 0 or an integer from 1 to 100.

I is preferably 0 or an integer from 1 to 300, particularly i is preferably 0 or an integer from 1 to 200.

The production of these organosilicon compounds is in the DE-A 198 02 069 (incorporated by reference) mentioned above, Page 5, line 6 to page 6, line 46. The protonation of the nitrogen atoms then takes place through Reaction with acids.

Organosilicon containing quaternized nitrogen connections of this type can be created using quaternary Acrylates bearing ammonium groups, such as. B. Trimethylammoniumethylmethacrylat, or else through the subsequent alkylation of the amino groups described above bearing organosilicon compounds with common Alkylating agents, such as. B. butyl bromide, p-toluene sulfonic acid methyl ester or benzyl chloride. The organosilicon compounds thus obtained are preferred soluble in water or self-emulsifying.

Such as organosilicon compounds according to the invention are used by the reaction of (poly) amines with Obtained organosilicon compounds having epoxy groups become.

The (poly) amine contains only one nitrogen-bound Hydrogen atom takes place monoaddition.  

Monoaddition of (poly) amines with an N-linked Hydrogen atom with epoxy groups Organosilicon compounds are known and, for example, in US-A 3,389,160 (Union Carbide Corporation). Contains the (poly) amine at least two nitrogen-bound Hydrogen atoms undergo polyaddition. The Protonation of the nitrogen atoms then takes place by reaction with acids.

Are the ammonium groups according to the invention Organosilicon compounds by the above polyaddition manufactured, they then contain in addition to the units (a) and (b) the bridge units (c)

As an amino functional according to the invention Organosilicon compounds can also be used that are made by implementing Chloroalkylalkoxysilanes, such as chloroalkyldimethoxymethylsilanes, with (poly) amines, such as hexamethylene diamine, and equilibration the aminoalkylalkoxysilanes thus obtained, such as Aminoalkyldimethoxymethylsilane, or their hydrolysis and / or Condensation products, with organopolysiloxanes, such as linear, terminal triorganosiloxy groups Organopolysiloxanes, linear, terminal hydroxyl groups having organopolysiloxanes, cyclic Organopolysiloxanes or copolymers Diorganosiloxane and monoorganosiloxane units.

The protonation of the nitrogen atoms then takes place through Reaction with acids.

Such amino-functional organosilicon compounds and their Manufacture are known and described for example in US-A 2,971,864 (Dow Corning Corporation, issued February 14, 1961) and J.L. Speier et al., J. Org. Chem. 36, 3120 (1971).

If the amino-functional organosilicon compounds according to the invention are prepared by one of the abovementioned processes, the radical Y preferably contains at least one group of the general formula

where z is an integer from 1 to 20.

If the amino-functional organosilicon compounds according to the invention are prepared by one of the abovementioned processes, the radical Y is preferably a radical of the general formula

where R ^{6 is} a divalent organic radical,
R ^{7 represents} a hydrogen atom or a monovalent hydrocarbon radical with 1 to 60 carbon atoms per radical, which can be interrupted or substituted by one or more separate heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur or halogen atoms,
R ⁷ 'has the meaning of R ⁷ , is preferably a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 carbon atoms per radical,
R ^{8 is} a divalent hydrocarbon radical with 1 to 10, preferably 3 to 10, carbon atoms per radical,
n is 0 or an integer from 1 to 10
m is an integer from 2 to the total number of nitrogen atoms in (I), preferably an integer from 2 to the sum of n + 1 and the total number of all basic nitrogen atoms optionally contained in the radicals R ³ , and
x is the same or different and is 0 or 1,
X ^- has the meaning given above, preferably an acid anion whose corresponding acid has a _pK a of greater than 0, preferably greater than 2, more preferably greater than 3, has,
with the proviso that the formula (V) contains at least one group of two protonated nitrogen atoms which are connected to one another via at least three carbon atoms,

In the case of polyaddition, the organosilicon compound according to the invention additionally contains (c) at least one bridge unit of the formula (III), where Y 'is a radical of the formula

where R ⁶ , R ⁷ , R ⁸ , n, m, x and X ^{- have} the meaning given above,
with the proviso that the formula (VI) contains at least one group of two protonated nitrogen atoms which are connected to one another via at least three carbon atoms.

R ⁶ is preferably an organic radical selected from the group of

and
a divalent hydrocarbon radical with 1 to 10 carbon atoms per radical,
where (Si) - the bond to the silicon atom and - (N) the bond to the nitrogen atom,
R 'is a divalent hydrocarbon radical with 1 to 10 carbon atoms per radical, which can be substituted by an ether oxygen atom,
R "is a hydrogen atom or a monovalent hydrocarbon radical with 1 to 10 carbon atoms per radical, which may be substituted by an ether oxygen atom,
R '''is a trivalent hydrocarbon radical with 3 to 12 carbon atoms per radical and
t is 0 or 1.

Examples of radicals R ⁶ are aliphatic, cycloaliphatic and aromatic-containing divalent organic radicals which contain hydroxyl functions from the epoxy ring opening, such as

where r is an integer from 1 to 20, preferably from 2 to 8, and - (N) is the bond to the nitrogen atom and alkylene radicals, such as

- (CH ₂ ) -
- (CH ₂ ) ₂ -
- (CH ₂ ) ₃ -
-CH ₂ CH (CH ₃ ) CH ₂ -
-CH ₂ CH ₂ CH (CH ₃ ) -
- (CH ₂ ) ₄ -
- (CH ₂ ) ₆ -

Preferred radicals R ⁶ are

the first two residues and the residue - (CH ₂ ) ₃ - being particularly preferred.

Examples of hydrocarbon radicals R ⁷ are alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl -, neo-pentyl, tert-pentyl, hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl, such as the n-octyl and iso-octyl, such as the 2,2,4-trimethylpentyl, Nonyl residues such as the n-nonyl residue, decyl residues such as the n-decyl residue, dodecyl residues such as the n-dodecyl residue, and octadecyl residues such as the n-octadecyl residue, cycloalkyl residues such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl residues; Aryl radicals, such as the phenyl, naphthyl, anthryl and phenanthryl radical, alkaryl radicals, such as o-, m-, p-tolyl radicals, xylyl radicals and ethylphenyl radicals; and aralkyl groups such as the benzyl group, the α- and the β-phenylethyl group.

Examples of halogenated radicals R ⁷ are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, and halogenaryl radicals, such as the o-, m- and p-chlorophenyl.

Examples of radicals R ⁷ substituted by a nitrogen atom are

where Me is a methyl radical and Et is an ethyl radical.

Examples of radicals R7 substituted by an oxygen atom are

- (C ₂ H ₄ O) _s R
- (C ₃ H ₆ O) _s R,
- (C ₂ H ₄ O) _s (C ₃ H ₆ O) _s R
and
- (C ₄ H ₈ O) _s R

where s is an integer from 1 to 30, preferably 1 to 20
and R has the meaning given for it, preferably denotes a methyl or butyl radical.

Examples of radicals R ⁷ substituted by a nitrogen and an oxygen atom are

- (C ₂ H ₄ O) _s C ₃ H ₆ NR ¹ ₂ or - (C ₂ H ₄ O) _s C ₃ H ₆ N ⁺ HR ¹ ₂ .X ^-
- (C ₃ H ₆ O) _s C ₃ H ₆ NR ¹ ₂ or - (C ₃ H ₆ O) _s C ₃ H ₆ N ⁺ HR ¹ ₂ .X ^-
and
- (C ₂ H ₄ O) _s C ₃ H ₆ NR ¹ ₂ or - (C ₂ H ₄ O) _s C ₃ H ₆ N ⁺ HR ¹ ₂ .X ^-

where s and R ¹ and X ^{- have} the meaning given above and
R ^{1 is} preferably a methyl or ethyl radical.

Examples of radicals R ⁷ substituted by a sulfur atom are
- (C ₂ H ₄ S) _s R and
- (C ₃ H ₆ S) _s R,
where s and R have the meaning given above and R is preferably a methyl, ethyl or butyl radical.

Examples of radicals R ⁸ are

radicals with at least three carbon atoms are preferred and the radicals are particularly preferred

are.
n is preferably 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10.

The amino-functional organosilicon compounds obtained by polyaddition are preferably prepared by (poly) amines (1) of the general formula in a first step

where R ⁷ , R ⁸ , n and x have the meaning given above, with organosilicon compounds (2) containing epoxy groups and containing units of the general formula

wherein R, R ¹ , a and b have the meaning given above, E is the same or different and is a monovalent SiC-bonded organic radical which contains an epoxy group, and
c is 0 or 1,
with the proviso that the sum is a + b + c ≦ 3 and that at least one radical E is contained per molecule,
with the proviso that the ratio of N-bonded hydrogen in (poly) amine (1) to epoxy group in organosilicon compound (2) is such that toluene-soluble organosilicon compounds having amino groups are obtained,
and in a second step, the amino groups obtained in the first stage containing organosilicon compounds by the addition of acids (4), preferably with a _pK a value of greater than 0, preferably greater than 2, more preferably greater than 3, are partially completely protonated or, are preferably entirely protonated with the proviso that organosilicon compounds containing ammonium groups are obtained which contain at least one group of two protonated nitrogen atoms which are connected to one another via at least three carbon atoms.

In the polyaddition in the first stage as Organosilicon compounds containing amino groups obtained which are soluble in toluene, d. H. it will unlinked organosilicon compounds, in contrast to organosilicon compounds insoluble in toluene, the are networked. The organosilicon compounds obtained are soluble in toluene in any mixing ratio, preferably they are at a temperature of 25 ° C and a pressure of about 100% by weight soluble in toluene at 1020 hPa if Organosilicon compounds and toluene in a 1: 1 ratio (Parts by weight), preferably 1:10 (parts by weight,) mixed become.

The ammonium groups obtained after the polyaddition containing organosilicon compounds Siloxane blocks that have at least one two or polyvalent ammonium radical are interconnected.

Examples of (poly) amines (1) are primary amines of the general formula R ⁷ -NH ₂ ,
where R ^{7 is} a radical substituted by a nitrogen atom, such as

Me ₂ NC ₃ H ₆ NH ₂
Et ₂ NC ₃ H ₆ NH ₂
Me ₂ NC ₄ H ₈ NH ₂
Me ₂ NC ₂ H ₄ NMeC ₂ H ₄ NH ₂
Et ₂ NC ₃ H ₆ NEtC ₃ H ₆ NH ₂
4-amino-2,2,6,6-tetramethylpiperidine,
and
4-amino-1,2,2,6,6-pentamethylpiperidine,

and primary amines of the general formula R ⁷ -NH ₂ ,
wherein R ^{7 is} a radical substituted by an oxygen and a nitrogen atom, such as

Me ₂ NC ₃ H ₆ (C ₂ H ₄ O) _s C ₃ H ₆ NH ₂

and

Et ₂ N (C ₃ H ₆ O) _s (C ₂ H ₄ O) _s C ₃ H ₆ NH ₂ ,

where s has the meaning given above, Me is a methyl radical, Et is an ethyl radical and Bu is an n-butyl radical means.

Further examples of (poly) amines (1) are Propylenediamine, 1,6-diaminohexane, dipropylenetriamine, Isophoronediamine and neopentanediamine

The radicals E are preferably those of the formula

where R ', R ", R" "and t have the meaning given above to have.

In the polyaddition, organosilicon compounds (2) having epoxy groups are preferably those of the general formula

E _d R _3-d SiO (SiR ₂ O) _o (SiR ₂ O) _p SiR _3-d Ed,

where R and E have the meaning given above,
d 0 or 1, in particular 1,
o 0 or an integer from 1 to 1000, in particular 5 to 200, and
p is 0 or an integer from 1 to 10, in particular 0 or 1 to 6, particularly preferably 0,
used.

Organosilicon compounds containing epoxy groups (2) preferably have a viscosity of 1 to 100,000 mPa.s 25 ° C, preferably 10 to 2,000 mPa.s at 25 ° C.

Examples of radicals E are

3,4-Epoxibutyl,
5,6-Epoxihexyl,
7,8-Epoxioctyl,
glycidoxyethyl,
glycidoxypropyl,
2- (3,4-epoxycyclohexyl) ethyl,
2- (3-Epoxiphenyl) ethyl
as well as the epoxy residue itself,

the glycidoxypropyl and 2- (3,4-epoxicyclohexyl) ethyl are preferred, in particular the glycidoxypropyl radical.

Process for the preparation of epoxy groups Organosilicon compounds (2) are known to the person skilled in the art. Preferred embodiments are the epoxidation of aliphatic unsaturated organopolysiloxanes and by Precious metal (compounds) catalyzed addition terminal unsaturated organic epoxy compounds, such as Allyl glycidyl ether or 4-vinylcyclohexene oxide Organopolysiloxanes that contain Si-bonded hydrogen.

The epoxy groups used in the polyaddition Organosilicon compounds (2) preferably contain per molecule 1 to 10, especially 1 to 6 epoxy groups. A special one preferred embodiment is the use of α, ω- Diepoxypolysiloxanen.

In the polyaddition, (poly) amines (1) with 2 to 10 N-bonded hydrogen atoms, in particular with 2 to 6 N bonded hydrogen atoms used. The number of Nitrogen atoms per molecule is initially independent of this, but is preferably 2 to 4.

In the case of polyaddition, amines (3) can, if appropriate, be used with only of an N-H group per molecule can be used as these as Endstoppers act, making polyaddition more controllable do.

Optionally used amines (3) are preferably those of the general formula

wherein R ^IV and R ^{v are the} same or different and mean a monovalent hydrocarbon radical with 1 to 60 carbon atoms per radical, which can be interrupted by one or more separate heteroatoms selected from the group of nitrogen and oxygen atoms, or
R ^IV and R ^v together represent a divalent hydrocarbon radical with 4 to 10 carbon atoms.

Examples of amines (3) are
Dibutylamine, piperidine, diethanolamine, trimethylethylene diamine, bis (2-diethylaminoethyl) amine and bis (3-dimethylamino propyl) amine.

Amines (3) are optionally preferably in amounts of 5 up to 40 wt .-%, based on the total weight of the (poly) amines (1) used.

In the case of polyaddition, the ratio of (poly) amines is (1) organosilicon compounds containing epoxy groups (2) preferably 1: 1 to 10: 1, preferably 1: 1 to 5: 1 and especially preferably 1: 1 to 4: 1.

The polyaddition is based on the stoichiometry of the Reaction on the ratio of N-bonded hydrogen in (1) to Epoxy groups in (2) (N-H / Epoxy). This ratio N-H / Epoxi can be varied widely depending on the type of Feedstocks and target range of viscosities organosilicon compounds according to the invention. Preferably but an N-H / epoxy ratio greater than or equal to ≧ 1 adjusted so that all epoxy groups can react provided that toluene soluble products, i.e. H. uncrosslinked products can be obtained. It is in the knowledge of the Specialist depending on the number of N-H groups in (1) and Epoxy groups in (2), i.e. the functionality of the starting materials the N-H / epoxy ratio according to the inventive method  adjust z. B. experimentally about performing Try to obtain products that are soluble in toluene. There also side reactions as well as incomplete reaction sequences He knows that sales below 100% of theory have an impact Specialist that experimentally determine any limit values if particularly viscous products are manufactured should.

The polyaddition is preferably in the first stage Temperatures above 25 ° C are carried out, although at normal Ambient temperature, a detectable reaction already takes place. In the interest of a quick and complete reaction blue However, temperatures above 60 ° C. are preferred, especially in Range from 80 to 180 ° C, particularly preferably between 100 and 150 ° C. The polyaddition is preferably used when printing ambient atmosphere, i.e. at about 1000 hPa, with an increased especially in the case of volatile (poly) amines (1) Pressure is beneficial to avoid loss of N-H functions Evaporation and thus to avoid a change in stoichiometry.

All basic nitrogen atoms in the organosilicon compounds having amino groups are preferably protonated, the nitrogen atoms optionally present in the radicals R ⁷ also being protonated, so that the radical Y is preferably those of the formula

or in another spelling

and as the optionally contained radical Y ', preferably those of the formula

or in another spelling

where m is the sum of n + 1 and the total number of all basic nitrogen atoms which may be present in the radicals R ⁷ ,
[ie at most m = n + 1 + (n + 1) Σ (N atoms in R ⁷ )]
R ⁶ , R ⁷ , R ⁷ ', R ⁸ and X ^{- have} the meaning given above, with the proviso that the basic nitrogen atoms optionally contained in R ⁷ are protonated.

The organosilicon compounds thus obtained are preferred soluble in water or self-emulsifying.

The organosilicon compounds according to the invention have preferably a viscosity of 50-5,000,000 mPa.s 25 ° C, preferably 100-100,000 mPa.s at 25 ° C, particularly preferably from 100-30,000 mPa.s at 25 ° C.

The positively charged nitrogen atoms in the organosilicon compounds according to the invention are preferably obtained by reacting the amino-functional organosilicon compounds with acids. Preference is given to water-soluble acids are organic and inorganic acids, preferably with a _pK a value of greater than 0, preferably greater than 2, more preferably greater than 3, is used.

Examples of acids are monocarboxylic acids of the general formula R ¹⁰ -COOH,
where R ^{10 represents} a hydrogen atom or a hydrocarbon radical having 1 to 18 carbon atoms per radical, such as
Formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, sorbic acid, benzoic acid, salicylic acid and toluic acid,
and dicarboxylic acids of the general formula HOOC-R ¹¹ -COOH,
where R ^{11 has} the meaning given above, such as
Succinic acid, maleic acid, adipic acid, malonic acid and phthalic acid,
the monocarboxylic acids are preferred. Formic acid, acetic acid and propionic acid are particularly preferred.

Further examples of acids are sulfonic acids of the general formula R ¹⁰ -SO ₃ H,
where R ^{10 has} the meaning given above, such as methanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid and toluenesulfonic acid,
and also inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid and phosphoric acid. The use of these strong acids is not preferred.

Examples of hydrocarbon radicals R ¹⁰ are the hydrocarbon radicals R.

Accordingly, the organosilicon compounds according to the invention preferably contain as anions X ^- the corresponding anions of the acids used. Examples of anions X ^- are therefore

R ¹⁰ -COO ^- , ^- OOC-R ¹¹ -COO ^- and R ¹⁰ -SO ₃ ^- ,

where R ¹⁰ and R ^{11 have} the meaning given above.

The acids are preferably used in amounts of 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 5% by weight, based in each case on the total weight of the invention Organosilicon compounds used.

The organosilicon compounds according to the invention contain preferably at least 0.5% by weight, preferably at least 0.8% by weight positively charged nitrogen atoms, preferably at most 10 wt .-%, preferably at most 5 wt .-% positively charged nitrogen atoms

The organosilicon compounds according to the invention are preferably in the form of aqueous solutions or Microemulsions used in the method according to the invention.

The aqueous preparations preferably contain 0.1 to 50% by weight, preferably 0.1 to 25% by weight according to the invention Organosilicon compounds, each based on the Total weight of the aqueous preparations.

To stabilize such aqueous preparations non-aqueous, but water-compatible solvents, such as Isopropanol, diethylene glycol monomethyl ether, Diethylene glycol monobutyl ether, dipropylene glycol or Dipropylene glycol monomethyl ether can also be used.

According to the treatment method according to the invention, especially impregnation, organic fibers can all organic fibers, preferably in the form of textiles Fabrics, such as nonwovens, mats, strands, woven, knitted or knitted textiles are present in Nozzle dyeing machines are impregnated, which were previously also in Jet dyeing machines could be treated.

Examples of fibers using the method according to the invention can be impregnated are those made of keratin, especially wool, polyvinyl alcohol, copolymers of  Vinyl acetate, cotton, rayon, hemp, natural silk, Polypropylene, polyethylene, polyester, polyurethane, polyamide, Cellulose and mixtures of at least two such fibers. How The fibers can be seen from the above list be of natural or synthetic origin. The textile Flat structures are preferably in the form of panels or in the case of circular knitted goods as knitted fabric hoses.

Treatment of the organic fibers with the invention Organosilicon compounds are made in the beginning described nozzle dyeing machines.

The method according to the invention is preferably used in a Temperature from 5 ° C to 150 ° C, preferably from 10 ° C to 80 ° C and preferably at the pressure of the surrounding atmosphere, i.e. approximately at 1020 hPa (abs.).

Those treated by the method according to the invention organic fibers have a soft feel.

The inventive method has the advantage that the amino-functional organosilicon compounds according to the invention show self-dispersing behavior even with amine numbers, where classic aminosilicones are not self-dispersing are.

Furthermore, the method according to the invention has the advantage that considerable labor and cost savings are achieved because by equipping the textiles in jet dyeing machines additional intermediate drying and foulard passage avoided becomes. Furthermore, the method according to the invention Danger of staining on the textile fiber materials greatly minimized.

Production of the amino-functional organosilicon compounds and their aqueous preparations example 1

100 g of a trimethylsilyl end group polydimethylsiloxane and mercaptopropyl side groups with a viscosity of 1200 mPa.s at 25 ° C and a sulfur content of w (S) = 0.65% in one with stirrer, thermometer and reflux condenser equipped 250 ml three-necked flask with 20 g Dimethylaminoethyl acrylate and 0.25 g azobisisobutyronitrile slowly heated to 65 ° C under nitrogen. That temperature is held for eight hours, the viscosity of the increases to 7892 mPa.s at 25 ° C in the course of the reaction time. The product obtained is pale yellow in color and clear and has an amine number of 1.1 mmol / g (corresponds to 1.5% by weight Nitrogen).

15 g of the oil thus obtained are homogeneous with 15 g of 2-propanol mixed, 1 g of glacial acetic acid is added to this mixture and this is also mixed in homogeneously. Becomes this mixture 69 g of deionized water added, becomes a clear, weak yellowish solution obtained. The amino functional Organosilicon compound has 1.5 wt .-% positively charged Nitrogen.

Example 2

100 g of a trimethylsilyl end group polydimethylsiloxane and mercaptopropyl side groups with a viscosity of 1200 mPa.s at 25 ° C and a sulfur content of w (S) = 0.65% in one with stirrer, thermometer and reflux condenser equipped 250 ml three-necked flask with 20 g Dimethylaminoethyl methacrylate and 0.25 g azobisisobutyronitrile slowly heated to 65 ° C under nitrogen. That temperature is held for eight hours and the product after the addition of 8 g of methyl toluenesulfonate dissolved in 50 g of isopropanol  stirred for another four hours at 65 ° C. That at room temperature cooled clear product resulted in the titration with alcoholic HCl an amine number of 0.43 mmol / g (corresponds to 1.6% by weight Nitrogen).

22.25 g of the oil thus obtained are mixed with 7.75 g of 2-propanol homogeneously mixed, 1 g of glacial acetic acid is added to this mixture and mixed in homogeneously. Becomes this If 69 g of deionized water are added to the mixture, a clear, pale yellowish solution obtained. The amino-functional organosilicon compound has 1.6% by weight positively charged nitrogen.

Example 3

150 g of an α, ω-bis (glycidyloxypropyl) polydimethylsiloxane the average chain length Si-51 is 4.6 g 3-dimethylaminopropylamine in 17 g diethylene glycol monobutyl ether reacted at 150 ° C until the epoxy groups to more than 99% have reacted. It will be a 90% solution to one amino functional siloxane polyaddition product, the one Amine number of 0.58 mequ./g (corresponds to 0.8% by weight nitrogen) has received.

The mixture thus obtained is mixed with 6.0 g of glacial acetic acid and others 138 g of diethylene glycol monobutyl ether are added and homogeneous mixed. An aqueous solution from 30% of the solution produced and 70% deionized water is clear and colorless and stays at 50 ° C for 4 weeks unchanged. The amino-functional organosilicon compound has 0.8% by weight positively charged nitrogen.  

Example 4

100.0 g of a polydimethylsiloxane with trimethylsilyl end groups and glycidyl ether propyl side groups with a viscosity of 1420 mm ² / s at 25 ° C. and an epoxy content of 0.0307 mol / g, 6.1 are placed in a 250 ml three-necked flask equipped with a stirrer, reflux condenser and thermometer g 3,3-imino-bis (N, N-dimethylpropylamine) of the formula

(CH ₃ ) ₂ N- (CH ₂ ) ₃ -NH- (CH ₂ ) ₃ -N (CH ₃ ) ₂

and 15.9 g of 1-butanol weighed out and six hours at about 135 ° C. stirred under reflux. The slightly cloudy, slightly yellowish Solution is in a rotary evaporator at 150 ° C and full vacuum baked out and then filtered. The product obtained with an amine number of 0.91 mmol / g (corresponds to 1.3% by weight Nitrogen) is pale yellow and clear.

The oil thus obtained is described in Example 1 Procedure solved. The amino functional Organosilicon compound has 1.3 wt .-% positively charged Nitrogen.

Example 5

150 g of an α, ω-bis (glycidyloxypropyl) polydimethylsiloxane with the average chain length Si-51 are mixed with 8.02 g of isophoronediamine of the formula

and 4.5 g of isopropanol are mixed homogeneously and kept at 110 ° C. for 24 hours. A siloxane polymer with 60 Pa.s at 25 ° C. is obtained, which clearly dissolves in the same amount of toluene and is free of gel components. No epoxy protons can be seen in the ¹ H-NMR spectrum (detection limit approx. 1%). The amino-functional siloxane polymer has an amine number of 0.59 mequ./g (corresponds to 0.8% by weight of nitrogen).

The oil thus obtained is described in Example 1 Procedure solved. The amino functional Organosilicon compound has 0.8 wt .-% positively charged Nitrogen.

Example 6

In one with stirrer, reflux condenser and thermometer equipped 500 ml three-necked flask are 116.0 g (1 mol) Hexamethylene diamine, 91.4 g (0.5 mol) Weighed chloropropyldimethoxymethylsilane and 200 g of toluene and stirred for eight hours at about 114 ° C under reflux. The approach quickly becomes cloudy and a voluminous precipitate forms. The precipitate is filtered off at room temperature and the Mother liquor in a rotary evaporator at 120 ° C and a pressure distilled from 20 mbar over an hour. Will the remaining liquid by filtration from its turbidity freed, the raw silane is a pale yellow, get easily moving liquid. In a 250 ml Three-necked flasks are now 15 g of this liquid with 100 g Octamethyltetrasiloxane mixed and 0.1 g Tetrabutylphosphonium hydroxide (40% by weight in water) added. This mixture is brought to 100 ° C. under nitrogen inerting heated and held at this temperature for four hours.

Then another 0.1 g of tetrabutylphosphonium hydroxide (40% by weight in water) and added for a further two hours 100 ° C tempered. The slightly yellow product has one Viscosity of 320 mpa.s at 25 ° C and one with Alcoholic HCl titratable amine number of 0.99 mmol / g (corresponds to 1.4% by weight of nitrogen).

The oil thus obtained is described in Example 1 Procedure solved. It will be a bluish, light Obtain an opalescent but transparent solution. The  amino-functional organosilicon compound has 1.4% by weight positively charged nitrogen.

Comparative experiment 1

15 g of a siloxane with methoxy end groups and Aminoethylaminopropyl side chains (0.84% by weight nitrogen; Viscosity at 25 ° C: 1000 mpa.s) with 15 g of 2-propanol homogeneously mixed, a 1 g of glacial acetic acid was added to this mixture and mixed in homogeneously. Becomes this Mixture 69 g of deionized water is first added a white dispersion that quickly dissolves in the oil and water phase separates, received.

Comparative experiment 2

15 g of a siloxane with methoxy end groups and Aminoethylaminopropyl side chains (0.84% by weight nitrogen; Viscosity at 25 ° C: 1000 mpa.s) with a 10 g Isotridecylethoxylpolyethylenglykoles with average seven ethylene oxide units, 1 g acetic acid (100% by weight) and 15 g Stir isopropanol until a clear mixture was obtained. A total of 69.5 g of water were then added small portions added to the mixture with stirring. It became a clear to slightly bluish-tinted microemulsion receive.

Finishing of textiles Example 7

The aqueous preparations obtained in Examples 1 to 6 and in Comparative Experiment 2 were used to equip a substance in a Mathis Labor Overflow Jet dyeing machine type JFO. In each case 1 kg of a cotton / polyester woven fabric (40% / 60%) with a fabric weight of approx. 220 g / m ^{2 was placed} in ten liters of liquor which had been mixed with 30 g of the respective aqueous preparation and with 5 g of glacial acetic acid. treated at 40 ° C and a liquor circulation of approx. 4000 l / h. The aqueous preparations obtained from Examples 1 to 6 showed slight foaming only in the first minutes of the treatment. The fleets obtained contained lint from the finished fabric, but were otherwise clear. In contrast, the aqueous preparation obtained after comparative experiment 2 foamed so strongly that the experiment had to be stopped after about five minutes. The liquor obtained was grayish-cloudy and in the jet silicone deposits were recognizable on the sight glass and on the heated surfaces. After drying at 120 ° C and subsequent conditioning for eight hours at 25 ° C and 65% humidity, all of the samples showed a greatly improved feel and softness compared to the unfinished fabric.

Claims (10)

1. Process for the treatment of organic fibers with aqueous preparations of amino-functional organosilicon compounds containing

• a) at least one siloxane unit of the general formula
  where R is the same or different and is a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical,
  R ^{1 is the} same or different and denotes a monovalent hydrocarbon radical with 1 to 8 carbon atoms per radical,
  a is 0, 1, 2 or 3,
  b is 0, 1, 2 or 3,
  c is 1, 2 or 3
  with the proviso that the sum is a + b + c ≦ 3,
  Y is a monovalent organic radical having at least 2 positively charged nitrogen atoms, with the proviso that between the positively charged nitrogen atoms in the radical Y there are at least three carbon atoms, which may be interrupted or substituted by separate heteroatoms, and
  with the proviso that the organosilicon compounds contain at least 0.35% by weight of positively charged nitrogen atoms, and
• b) at least one siloxane unit of the general formula
  where R, R ¹ , a and b have the meaning given above, with the proviso that the sum is a + b ≦ 3, in nozzle dyeing machines.

2. The method according to claim 1, characterized in that the organosilicon compounds

• a) at least one bridge unit of the general formula
  where R, R ¹ , a and b have the meaning given above, with the proviso that the sum a + b ≦ 2 and
  Y 'denotes a divalent organic radical having at least 2 positively charged nitrogen atoms, with the proviso that between the positively charged nitrogen atoms in the radical Y there are in each case at least three carbon atoms, which can optionally be interrupted or substituted by separate heteroatoms.

3. The method according to claim 1 or 2, characterized in that as organic fibers textile. Fabrics used become. 4. The method according to claim 1, 2 or 3, characterized characterized in that as aqueous preparations aqueous Solutions or microemulsions are used.   5. The method according to any one of claims 1 to 4, characterized in that Y is a radical of the formula
-R ³ - (SZH) _k is, (IV)
where R ^{3 is} a divalent linear or branched hydrocarbon radical having 2 to 10 carbon atoms, which can be interrupted by separate heteroatoms,
k 1 or 2,
and Z is a residue selected from the group of residues
and mixtures of the abovementioned radicals (A), (B) and (C),
where R ^{2 is} a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms,
R ^{4 is} a monovalent hydrocarbon radical with 1 to 10 carbon atoms,
R ^{5 is} a hydrogen atom or a monovalent hydrocarbon radical having 1 to 10 carbon atoms,
W -NR ² - or -O- (where R ^{2 has} the meaning given above),
U is a linear or branched alkylene radical with 2 to 10 carbon atoms,
X ^- a negatively charged ion stable in aqueous solution
h 0 or an integer from 1 to 250 and
i is 0 or an integer from 1 to 400,
with the proviso that the sum h + i ≧ 5. 6. The method according to any one of claims 1 to 4, characterized in that Y is a radical of the formula
where R ^{6 is} a divalent organic radical,
R ^{7 represents} a hydrogen atom or a monovalent hydrocarbon radical with 1 to 60 carbon atoms per radical, which can be interrupted or substituted by one or more separate heteroatoms selected from the group consisting of nitrogen, oxygen, sulfur or halogen atoms,
R ⁷ 'has the meaning of R ⁷ ,
R ^{8 is} a divalent hydrocarbon radical with 1 to 10 carbon atoms per radical,
n is 0 or an integer from 1 to 10,
m is the sum of n + 1 and the total number of all basic nitrogen atoms which may be present in the R ⁷ radicals,
with the proviso that the basic nitrogen atoms contained in R ⁷ are protonated,
x is the same or different and is 0 or 1 and
X ^{- is} a stable, negatively charged ion in aqueous solution,
with the proviso that the formula (V) contains at least one group of two protonated nitrogen atoms which are connected to one another via at least three carbon atoms. 7. The method according to claim 6, characterized in that R ⁷ 'is a hydrogen atom. 8. The method according to claim 6 or 7, characterized in that the organosilicon compound

• a) contains at least one bridge unit of the general formula
  wherein R, R ¹ , a and b have the meaning given in claim 1, with the proviso that the sum a + b ≦ 2 and Y 'is a radical of the formula
  is, wherein R ⁶ , R ⁷ , R ⁸ , X ^- , n, m and x have the meaning given for this in claim 6.

9. The method according to claim 6, 7 or 8, characterized in that R ^{8 is} a radical of the formula - (CH ₂ ) ₃ -. 10. The method according to any one of claims 6 to 9, characterized in that R ^{6 is} an organic radical selected from the group of
and
a divalent hydrocarbon radical with 1 to 10 carbon atoms per radical,
where (Si) - is the bond to the silicon atom and - (N) is the bond to the nitrogen atom,
R 'is a divalent hydrocarbon radical with 1 to 10 carbon atoms per radical, which can be substituted by an ether oxygen atom,
R "is a hydrogen atom or a monovalent hydrocarbon radical with 1 to 10 carbon atoms per radical, which may be substituted by an ether oxygen atom,
R '''is a trivalent hydrocarbon radical with 3 to 12 carbon atoms per radical and
t is 0 or 1.