DE10036693A1 - Process for impregnating yarn - Google Patents

Abstract

The invention relates to a method for saturating threads 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 monovalent 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. The saturation is preferably carried out in cheese dyeing machines.

Description

The invention relates to a method for impregnating Yarns.

The high levels that occur in industrial sewing processes Sewing speeds and the associated high make mechanical and thermal stress on the sewing thread the use of agents to improve the sliding properties of sewing threads necessary.

The use of silicones as components in Sewing thread lubricant is known (see H. K. Rouette, Lexikon for textile finishing, 1995, vol. 2, p. 1314 "Sewing thread lubricants"). The ones in the market Sewing thread lubricants usually consist of mixtures of Waxes (polyethylene waxes, natural waxes, paraffin waxes) and a silicone component. This is usually Emulsions from those terminated with trimethylsilyl groups Polydimethylsiloxanes with a viscosity of 1,000 to 10,000 mPa.s at 25 ° C, non-ionic emulsifiers and water used.

The sewing thread lubricants are usually after dyeing the Yarn applied. The yarn is dyed in dyeing machines such as cross-winder dyeing machines, which are described in Ullmann's Encyclopedia of Industrial Chemistry Vol. A25, chap. 2.2.3.3. are described.

The object of the invention was now a lubricant for yarns especially sewing threads to provide that already at Room temperature can be applied to the sewing thread and with which a reduction in the friction of the sewing thread and a even application along the thread axis on the sewing thread is achieved. The object is achieved by the invention.  

The invention relates to a process for the impregnation of yarns with aqueous preparations containing amino-functional organosilicon compounds

• a) at least one siloxane unit of the general formula where R is identical or different and denotes a monovalent, optionally halogenated hydrocarbon radical having 1 to 18 carbon atoms per radical, R ^{1 is} identical 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 in each case at least three carbon atoms, which can optionally 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.

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 is a + b ≦ 2 and Y 'is a divalent organic radical having at least 2 positively charged nitrogen atoms, with the proviso that contain between the positively charged nitrogen atoms in the radical Y 'in each case at least three carbon atoms, which can optionally 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),
is where R 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 h 0 or an integer from 1 to 250 and stable in aqueous solution
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 than 0, preferably greater than 2, more preferably greater than 3 has larger,
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 R ⁷ 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 O) _s C ₃ H ₆ NR ¹ ₂ or - (C ₂ H ₄ O) _s (C ₃ H ₆ O) _s C ₃ H ₆ N ⁺ HR ¹ ₂ .X ^- ,

where s, 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 preferably represents 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 epoxy group-containing organosilicon compounds (2) containing units of the general formula

where 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,
be implemented
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 stage the organosilicon compounds having amino groups obtained in the first stage by adding acids (4),
preferably with a _pK a of greater than 0, preferably greater than 2, more preferably greater than 3, are partially completely protonated or, preferably completely protonated with the proviso that ammonium-containing organosilicon compounds are obtained, which at least one grouping 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.

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 (SiREO) _p SiR _3-d E _d ,

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 having 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 However, temperatures above 60 ° C. are preferred in the course of the reaction, especially in the range of 80 to 180 ° C, particularly preferred between 100 and 150 ° C. The polyaddition is preferably at Pressure of the surrounding atmosphere, i.e. at about 1000 hPa, carried out, especially with volatile (poly) amines (1) an increased pressure is advantageous to avoid losses of N-H Evaporation functions and thus a change in stoichiometry to avoid.

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 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.

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.

Contain the aqueous preparations according to the invention preferably 0.1 to 50% by weight, preferably 0.1 to 25% by weight organosilicon compounds according to the invention, in each case related on the total weight of the aqueous preparations.

To stabilize the aqueous according to the invention Preparations can be non-aqueous, but compatible with water Solvents, such as isopropanol, diethylene glycol monomethyl ether, Diethylene glycol monobutyl ether, dipropylene glycol or Dipropylene glycol monomethyl ether can also be used.  

The organosilicon compounds according to the invention are preferably as a lubricant for yarns, especially sewing threads, used.

The yarns are preferably treated in Cross-wound dyeing machines, the in the Ullmann's Encyclopedia of Industrial Chemistry Vol. A25, chap. 2.2.3.3. are described.

Examples of yarns are sewing threads, threads, sewing threads, threads and Sewing threads.

The yarns can be made of cotton, mercerized cotton, Polyester and polyester / cotton blends, d. H. like from the above list shows the yarns be of natural or synthetic origin.

The method according to the invention is preferably used in a Temperature from 20 to 100 ° C, preferably from 20 to 50 ° C and preferably at the pressure of the surrounding atmosphere, i.e. approximately at 1020 hPa (abs.).

The inventive method has the advantage that the amino-functional organosilicon compounds according to the invention treated yarns, especially sewing threads, a reduced one Have friction and that a more even distribution of the amino-functional organosilicon compounds according to the invention on the thread, especially sewing thread.

Furthermore, the method according to the invention has the advantage that it can also be used at room temperature. This poses considerable energy and cost savings in the Sewing thread equipment.  

Preparation of the amino functional organosilicon compound Example A

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).

Sewing thread equipment example 1

With an aqueous solution of:
20% by weight of the organosilicon compound from Example A above
1% by weight acetic acid
15% by weight of isopropyl alcohol and
64% by weight water
two bobbins of a polyester sewing thread with a fineness of 43/2 denier were each impregnated on a cross winder dyeing machine, type Ahiba Turbocolor, under the following conditions:
pH: 5.5-6.5.

temperature program

Five minutes at room temperature
Heating up to 52 ° C with approx. 3 ° C / min
Ten minutes at 52 ° C
Heating up to 71 ° C with approx. 3 ° C / min
Five minutes at 72 ° C
Cool to room temperature.

A circulation (WOY) of 6% was achieved. After The drying and conditioning of the bobbins was the Friction determined on a Rothschild friction coefficient measuring device. This resulted in the following measured values, which are shown in Table 1 are summarized.

Comparative experiment 1

With an aqueous emulsion of:
20% by weight of a polydimethylsiloxane terminated with trimethylsilyl groups and having a viscosity of 5000 mPa.s at 25 ° C.,
7 wt .-% of a nonylphenol ethoxylate with ten ethylene oxide units (non-ionic emulsifier) and
73% by weight of water
As described in Example 1, two bobbins of a polyester sewing thread were each impregnated on a cross-winder dyeing machine under the conditions described in Example 1. As in Example 1, a print run (WOY) of 6% was achieved. After the coils had dried and been conditioned, the friction was determined in each case on a Rothschild friction coefficient measuring device analogously to Example 1.

This resulted in the following measured values, which are shown in Table 1 are summarized.  

Table 1

The polysiloxane according to the invention from Example 1 thus shows not only greatly reduced friction values compared to Comparative experiment 1, but also a lower one Fluctuation range (amplitude) of the friction values, which is a more uniform distribution of the polysiloxane according to the invention on the thread means.

Example 2

With the aqueous solution of Example 1, as in Example 1, two bobbins of a polyester sewing thread each on a cheese package for 20 minutes at room temperature treated.

As in Example 1, a print run (WOY) of 6% was reached. After drying and conditioning the coils was the friction on a Rothschild friction coefficient Measuring device determined analogously to Example 1.

This resulted in the following measured values, which are shown in Table 2 are summarized.

Comparative experiment 2

With the emulsion of comparative experiment 1, as in Example 2 described, two spools of a polyester sewing thread in each case on a cheese package at room temperature treated.  

The emulsion did not stick to the sewing thread at room temperature, so the attempt had to be stopped.

Table 2

The polysiloxane according to the invention again shows very strongly reduced coefficients of friction and a greatly reduced Effect fluctuation range compared to the prior art (Comparative experiment 1). In addition, this effect can be even without heating the treatment liquor to reach. This represents a significant energy and Cost savings in sewing thread equipment.

Claims (6)

1. A method for impregnating yarns with aqueous preparations containing amino-functional organosilicon compounds

• 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 + ≦ 3,
  Y represents 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 can optionally 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

• a) 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,

2. The method according to claim 1, characterized in that the Impregnation is carried out in cheese package dyeing machines. 3. The method according to claim 1 or 2, characterized in that sewing threads are used as yarns. 4. The method according to claim 1, 2 or 3, characterized characterized that sewing threads are used as yarns. 5. The method according to any one of claims 1 to 4, characterized characterized in that as aqueous preparations aqueous Solutions or microemulsions are used. 6. The method according to any one of claims 1 to 5, characterized in that Y is a radical of the formula
-R ³ - (SZH) _k is (IV)
where R is a divalent linear or branched hydrocarbon radical with 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),
is where R 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.