CH639444A5 - Quaternary imidazolinium salt fabric conditioner - Google Patents

Description

The present invention relates to a textile finishing agent which contains a quaternary imidazolinium salt of the formula:

3rd

639 444

r.

r-c

/ m — chr, "+ I 3

\

A.D,

I 1

D

(la)

or al — chr, '

R "<t I

D

(Ib)

wherein R is an aliphatic or cycloaliphatic hydrocarbon group having 10 to 22 carbon atoms, R2 is an alkyl, substituted alkyl or aralkyl radical having 1 to 8 carbon atoms. Rj and Ri are hydrogen, hydroxyl, alkyl having 1 to 4 carbon atoms or hydroxyalkyl with 1 to 4 carbon atoms, D is -COR, - (CH: CI-h) n -NH-COR, - (CH2CHa) „- 0-C0R or - (CH2CH:) m-CH! stands, n stands for an integer from 1 to 6, m stands for 5 or 6 and X- represents an anion, whereby the agent altogether less than 4% primary amines, secondary amines and cyclic tertiary amine salts, by weight of the imidazolinium salt.

Furthermore, the present invention relates to a method of finishing in laundry using the textile finishing agent.

In the usual household washing process, soiled textiles are subjected to cleaning with a detergent in the main washing section and rinsed with water in the end section. If desired, a textile finishing agent can be added during the rinsing section. Such agents contain a fabric softener or anti-static fabric to impart softness and anti-static properties to the rinsed fabrics. The rinsed textiles are often subsequently dried in an automatic tumble dryer.

Many different types of fabric finishers have been used in fabric finishing agents added in the rinse section. The most favored type of textile finishers were the quaternary ammonium compounds. These compounds can take the form of noncyclic quaternary ammonium salts which preferably have two long chain alkyl groups attached to the nitrogen atom. In addition, imidazolinium salts have been used as such or in combination with other agents in the treatment of textiles. U.S. Patent No. 2874074 describes the use of imidazolinium salts for finishing textiles. US Pat. Nos. 3,681,241 and 3,033,704 disclose textile finishing agents containing mixtures of imidazolinium salts and other textile finishing agents.

Although the literature describes the use of quaternary imidazolinium salts as a finishing agent for textiles, there is no information about the problems that arise in the manufacture of stable textile finishing agents containing such textile finishing agents and aldehydes. In the preparation of the imidazolinium salts, the reaction of a polyamine with an acyl group-containing material, such as an acid or an ester, generally takes place.

to form an imidazoline and then a quaternization of the imidazoline. US Pat. Nos. 2355837, 2267965 and 2520102 describe processes for the preparation of imidazolines which are used for the production of imidazulinium salts. It has now been found that in addition to the imi-dazoline compound which is formed in the reaction described, primary and secondary amines are also present. During the subsequent quaternization step, these amines cause part of the imidazoline compound to form the io imidazolinamine salt instead of the quaternary imidazolinium salt. If the imidazolinamine salt is in an aqueous medium that is nearly neutral or higher in pH, it may undergo ring opening to form free amines, which may then be combined with alde-15 hydric compounds in the fabric finishing agent in much the same way as free amines. that have not been converted to the salt form react. The result of this is that the smell of the agents is lost (perfumes generally contain aldehydes), that the color and pH change and that aldehyde protection substances are broken down. The above-mentioned US Pat. No. 2,874,074 describes the preparation of quaternary imidazolinium salts, but there is no indication of how the problems described can be overcome and yet an end product can be obtained which has a sufficiently high imidazolinium salt content to be of interest as a commercial product to be. It has now been found that the undesirable amines can be "scavenged" using an alkoxylating agent in an amount sufficient to scavenge the primary and secondary amines, but the cyclic tertiary amine that forms the imidazolinium salt , does not intercept to any significant extent.

In the context of the present description, all 35 percent and ratios, unless otherwise stated, mean percentages by weight and ratios by weight.

The imidazolinium salts used according to the invention can be prepared by using a polyamine of the formula:

H2N-CHR3-CHR4-NH2 (IIa)

H2N-CHRs-CHR4-NH - = (CH2CH2) n-NH2 (IIb)

H2N-CHR3-CHR4-NH- (CH: CH2) n-OH (Ile)

or

45 H2N-CHR3-CHR4-NH- (CH2CH2) m-CH.1 (Ild)

with an acylating agent of the formula:

50

R10-C0-R

(purple)

CH - 0-C0-R

I 2

or CH-O-CO-R

ch2-o-co-r

(Illb)

where R 1 is hydrogen or alkyl, the molar ratio of the acyl groups to the primary amino and hydroxyl groups being 0.33 to 1.5: 1:

B) the reaction mixture from step A during a bo bo space of 3 to 24 hours at a temperature of 100 to 250 C is converted to a treatment product and then the product by applying a vacuum of 0.4 to 10 mm Hg for a period of Cyclized for 1 to 8 hours to form an imidazoline product in a mixture with starting materials and intermediates, whereby, provided the molar ratio of acyl groups to primary amino and hydroxyl groups in step A is 0.33 to 0.66 to 1, the imidazoline product mixture from level B with a

039 444

4th

Acylating or esterifying agents] of the formula lilac or IIIb in a molar ratio of acyl groups to imidazoline product of 1: 1 to 1.5: 1 at a temperature of 100 to 250 C and for a period of 1 to 24 hours;

C) treating the imidazoline product mixture from Step B with an alkoxylating agent in an amount that is from 1 to 5% by weight of the imidazoline product mixture to scavenge the primary and secondary amines, the temperature being over a period of 0.5 to 8 hours is kept at 80 to 140 "C:

D) the mixture from stage C is quaternized with an alkylating agent in such an amount that the molar ratio of alkylating agent to imidazoline is at least 1: 1.

The molar ratio of acyl groups to primary amine and hydroxyl groups is preferably 0.67 to 1.50, in particular 1: 1 to 1.5: 1. The reaction in stage B can be carried out under reflux or at atmospheric pressure or slightly higher pressure. The resulting mixture contains, in addition to the desired imidazoline, some acylation or finishing agent used, some polyamine used, some non-cyclized amide intermediates and other mixed reaction products. The acylating or esterifying agent can be any acid or other acyl group-containing compound which has an aliphatic or cycloaliphatic hydrocarbon group having 10 to 22 carbon atoms per acyl group. Examples of such acylating or esterifying agents are the fatty acids lauric acid, decanoic acid, undecanoic acid, dodecanoic acid, tride-canoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid,

0

r — c — oh + nh “-ch” -ch

Palmitic acid and the like. Preferred fatty acids are the mixtures thereof, which are derived from tallow, soybean oil or coconut oil. The soft or hardened tallow fatty acids are particularly preferred. Other acylating or esterifying agents include the alkyl esters of the fatty acids and the naturally occurring glyceride esters. The latter, especially the glyceride esters of tallow fatty acid, are preferred.

Examples of polyamines include diethylenetriamine, ethylenediamine, hydroxyethylethylenediamine, etc. Diethylenetriamine is preferred.

If the amount of the acylating and esterifying agent used is not sufficient to form an amide or an ester with at least two of the amine or 15 hydroxyl groups present in the polyamine (the molar ratio of the acyl groups to primary amine or hydroxyl groups is 0.33 to 0, 66), the imidazoline formed will have only one aliphatic or cycloaliphatic hydrocarbon group with 10 to 22 carbon atoms, which is in the 2-position, instead of 20 such a group in both the 1- and the 2-position of the imidazoline ring. The monosubstituted material can then be reacted further with an acylating or esterifying agent. The reaction temperature is generally the same as in step B, while the molar ratio of 25 acylating agent or esterifying agent to monosubstituted imidazoline is 1: 1 to 1.5, the reaction time can range from 1 to 24 hours. If desired, a vacuum of 0.4 to 10 mm Hg can be applied. This reaction can be illustrated, for example, using 3o diethylenetriamine as the polyalkylene polyamine as follows:

nh-ch2-ch2-nh2

0

R — c — nh-ch2-ch2-nh-ch2-ch2-nh2 + h20

\ -ch_,

CH2-CH2-NH2

+ H20 (removed)

H20 removed

where R is an aliphatic or cycloaliphatic coal- The primary, in the imidazoline as formed above-

Substance group containing 10 to 22 carbon atoms, meaning 50 lying amino group, can then be tet in the following manner. an amide can be converted to the second long chain R-

Introduce group:

r-

yT2

'V' 2

ch0-ch0-nh.

+ r ^ —c-

-0h

->

R — C

/ N-CH2 \

+ H20

0

I 2 "

ch.-ch ^ -nh-c-r,

N-CH ^

2 4

5

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wherein Ri is an aliphatic or cycloaliphatic hydrocarbon group having 10 to 22 carbon atoms. The group of the formula:

0

ch;

■ ch,

-nh-

-r-,

in the above formula corresponds to group D in formulas la and ib. 1

If the amount of the acylating or esterifying agent used has a number of acyl groups sufficient to form an amide or an ester with at least two of the amine or hydroxyl groups (the ratio of acyl to primary amine or hydroxyl groups is 0.67 to 1.5: 1, preferably 1: 1 to 1.1: 1), the long chain group will be in the 1 position as a result of the initial imidazoline formation reaction. Such a reaction is given below:

ch_ — 0 c — r

I S

ch — 0 — c — r

I n c h 2-0-c-r

+ nh2-ch2-ch2-nh-ch2-ch2-nh2

.c-r

"/ + r-c-nh-ch2-ch2-n-ch2-ch2" nh2

0

r — c — nh-

-ch2-ch2-nh-ch2-ch2-nh-

0

T!

-c-

-r

R — C

I '

—Ch,

ch2-ch2-nh-

0

IT

-C — R

Some of the above amide intermediates, as well as some of the starting materials, other intermediates, water, and other complexes, may be present as diluents along with the desired substituted imidazoline. Some of the diluents can be removed during the vacuum stage of the reaction.

If the two-step reaction described above is used to form the imidazoline, the desired imidazoline will be obtained in a mixture which contains a proportion of the imidazole and fatty acid or other acylating or esterifying agent which are only substituted in the 2-position. Similarly, regardless of which pathway is used, the final mixture will have primary and / or secondary amines due to either unreacted starting amine or the amide intermediates. The by-products containing primary and secondary amine groups are undesirable because, in Step D discussed below, they cause the disubstituted imidazoline to be converted to an amine salt rather than a quaternary salt, the aminez being present in an aqueous fabric finishing agent, the one pH of about 5 or above is capable of converting back to a free amine. US Pat. No. 2,874,074 describes the preparation of the imidazoline by means of the two-stage fatty acid process. The 2-substituted imidazolines 45 which have been prepared according to US Pat. No. 2,355,837 or 2,267,965 can be used. The imidazoline product according to US Pat. No. 2,874,074 contains a mixture of 1,2-disubstituted imidazoline, 2-substituted imidazoline, other materials containing amino groups and fatty acid. The 2-substituted imidazoline and the other amines, as noted above, are undesirable because they have the ability to cause imidazoline salt formation.

It has now been found that the undesirable amino by-products present in the imidazoline reaction mixture can be effectively trapped by mixing the mixture with an alkoxylating agent, e.g. an alkylene oxide, preferably propylene oxide, is treated. The alkylene oxide serves to "catch" the amine by binding an alkylene oxide residue to the free amine. It is important that all of the primary and secondary amines be trapped, but only a minimum of the tertiary amine in the imidazoline. In order to achieve these goals, the mixture containing the desired imidazoline can be treated with an amount of an alkoxylating agent such as an alkylene oxide 65 which is 1 to 5% by weight of the mixture to be treated while the temperature is 80 to I40 ° C is maintained and, if desired, a vacuum that is 2 to 15 mm Hg, is applied. The vacuum supports the

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6

Process to rid the system of excess alkylene oxide, polyamine and other low-boiling diluents. The mixture containing imidazoline can also be diluted with an organic solvent such as isopropyl alcohol or ethylene glycol dimethyl ether to facilitate the alkylene oxide treatment. Such solvents can be used in an amount of 1 to 25% by weight of the imidazoline mixture. The reaction time is expediently in the range from 0.5 to 8 hours. US Pat. No. 2,713,582 describes the preparation of fully alkoxylated imidazolines as the starting material for carboxylate detergent products. Examples of alkoxylating agents other than propylene oxide include butylene oxide, glycide, ethylene oxide, cyclohexane oxide, etc.

The imidazolinium salt contains a total of less than 4%, preferably less than 2%, primary amines, secondary amines and cyclic tertiary amine salts and generally less than 25%, preferably 4%, of the alkoxylated form of the 5 imidazolinium salt, based on the weight of the The upper limit for the alkoxylated form results from the lack of the need to make the non-alkoxylated imidazolinium salts as pure as possible and is unrelated to amine / amine salt stability problems. The alkylating agent can be any of the known agents such as Methyl chloride, ethyl bromide, diethyl sulfate, dimethyl sulfate, hexadecyl chloride, which are given as examples of many others, for example, the reaction can be illustrated as follows:

R C

—CH-R,

X 3

'A.D,

+ (ch3) 2SO4

R-

D-R

X \

1

? H3

A.D.

N — CH-Rj D-R,

0

ch3so4

wherein D, R, Ri, Rjs and R4 have the meaning given above.

The amount of alkylating agent used is suitably at least equivalent to the amount of molar-based imidazoline treated. However, an excess of the alkylating agent is generally used to ensure maximum quaternization. The amount of excess used should preferably be sufficient so that the pH of the reaction medium is in the range from 5 to 7. The reaction time is generally in the range from 1 to 12 hours and the temperature in the range from 40 to

80 ° C. If desired, a base can be added during the alkylation to promote quaternization.

The imidazolinium salt formed as above has excellent textile finishing properties, a softening effect and has an antistatic effect and also makes it possible to produce textile finishing agents which have improved aldehyde stability. A preferred imidazolinium salt contains R and R groups having 14 to 20 carbon atoms, such as the following, in which the R groups represent tallow cuts:

'Tallow

CH, I 3

"H-CH,

I.

CH2-CH2-NH-

CHjSO ^

e

0

I!

-c — c

Tallow in which Cxuig means an aliphatic hydrocarbon group derived from tallow fatty acid.

Other quaternary imidazolimium salts which have the desired properties can be formed by using a different R group in the acylating or esterifying agent instead of CTa | g, using a different alkylene or polyalkylene polyamine instead of diethylene triamine and using a methyl group instead of the present one other optionally substituted alkyl or aralkyl and another anion are used in the alkylating agent.

The textile finishing agent according to the invention is defined in claim 1. It contains less than 2% primary bs amines, secondary amines and cyclic tertiary amine salts based on the weight of the imidazolinium salt. In addition, the textile finishing agents preferably contain less than 25%, in particular less than 4%, of the alkoxylated form of

7

639 444

Imidazolinium salt, based on "the weight of the non-alkoxylated form of the imidazolinium salt. The desired imidazolinium salt can be obtained using the method described above or another method which provides the imidazolinium salt and which does not result in higher than the above-stated proportions of the various undesirable compounds. getting produced.

Examples of the rest D are among many others

5

0

- (yW-CH3> -eCnH2n - * - NH-S-R or "fCH ^ O-C-R

0

where n and m have the above meanings. Examples of residues R2 are methyl, ethyl, benzyl etc. X- is an anion and can e.g. inter alia, chloride, bromide, methyl sulfate, ethyl sulfate. A preferred quaternary imidazolinium salt is the methyl sulfate salt shown above.

The textile finishing agents according to the invention are preferably aqueous agents and can contain any desired proportion of quaternary imidazolinium salt. However, the agents preferably contain 1 to 15% by weight, in particular 2 to 8% by weight, of the salt.

In addition to the preferred quaternary imidazolinium salt, the agents according to the invention can also contain other textile finishers (softening / antistatic agents). Such other agents can be described as cationic or nonionic organic materials, free of primary amines, secondary amines and cyclic tertiary amine salts, and generally used as fabric finishers during the rinse section of a household washing process. They are e.g. organic, waxy materials that have a melting (or softening) point between 25 ~ 'C and 115 ° C. Such materials have both fabric softening properties and antistatic properties for textiles.

In general, cationic nitrogen-containing additional fabric finishers such as quaternary ammonium compounds have one or two straight chain organic groups with at least 8 carbon atoms. They preferably have one or two such groups with 12 to 22 carbon atoms. Preferred cationic plasticizer compounds include the quaternary antistatic or plasticizing ammonium compounds which have the formula:

20th

R

r:

N

R,

where Ri 'represents hydrogen or an aliphatic group having 1 to 22 carbon atoms, R:' represents an aliphatic group having 12 to 22 carbon atoms, R3 'and R4' each symbolize alkyl groups having 1 to 3 carbon atoms and Xi represents an anion which is selected from the group consisting of halogen, acetate, phosphate, nitrate and methyl sulfate residues.

Because of their excellent plasticizer activity and easy availability, preferred cationic compounds with an antistatic or plasticizer effect are the dialkyldimethylammonium chloride, in which the alkyl groups have 12 to 22 carbon atoms, as additional textile finishers.

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35

point and are derived from long-chain fatty acids such as hydrogenated tallow. Instead of the alkyl radicals, there may also be unsaturated radicals such as those present in aliphatic groups which are derived from naturally occurring fatty oils. The term “tallow” refers to fatty alkyl groups that are derived from tallow fatty acids. Such fatty acids lead to quaternary plasticizer compounds, in which Ri and R: predominantly have 16 to 18 carbon atoms. The term “coconut” refers to fatty acid groups from coconut oil fatty acids. The coconut alkyl groups R 1 and R 2 have 8 to 18 carbon atoms and are predominantly C12 to C14 alkyl groups. Representative examples of quaternary plasticizers of the above formula include tallow trimethylammonium chloride, ditallow dimethylammonium chloride, ditallow dimethylammonium methyl sulfate, dihexadecyldimethylammonium chloride, di (hydrogenated tallow) dimethylammonium chloride, dioctadecyldimethyldammethyldimethyldimethylammonium chloride, cyldiethylammonium chloride, dihexadecyldimethylammonium acetate, di (tallow) dipropylammonium phosphate, di (tallow) dimethylammonium nitrate, di (coconut alkyl) dimethylammonium chloride.

A particularly preferred class of quaternary ammonium compounds which can be used as additional textile finishers and have an antistatic or plasticizer effect corresponds to the general formula:

Rï

CH.

N CH.

R2

+

X

wherein Ri "and R2" each represent straight chain aliphatic groups 50 having 12 to 22 carbon atoms and X is halogen, e.g. Symbolizes chloride, or methyl sulfate. Particularly preferred are ditallow dimethyl ammonium chloride, di (hydrogenated tallow alkyl) dimethyl ammonium chloride and di (coconut alkyl) dimethyl ammonium chloride, these compounds 55 being preferred from the standpoint of excellent plasticizer properties and easy availability.

The nonionic materials that give textiles antistatic properties or softness include a wide variety of materials including sorbitan boosters, fatty alcohols and their derivatives and the like. A preferred type of nonionic material that provides textiles with anti-static properties or softness comprises the esterified cyclic dehydration products of sorbitol, i.e. Sorbitan esters. Sorbitol, which as such e.g. prepared by catalytic hydrogenation of glucose can be dehydrated in a well known manner to form mixtures of cyclic 1,4- and 1,5-sorbitan hydrides and small amounts of isosorbides, see US Pat. No. 2,322,821. The emerging

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8th

Complex mixtures of cyclic anhydrides of sorbitol are collectively referred to as "sorbitan". This "sorbitan" mixture will also contain some free, uncyclized sorbitol.

Sorbitan ester materials which can be used as additional textile finishers and which impart textiles with antistatic or plasticizer properties can be prepared in a manner known per se by esterifying the “sorbitan” mixture with a fatty acyl group. e.g. by reaction with a fatty (Cio-C24) acid or a fatty acid halide.

The esterification reaction can attack any of the available hydroxyl groups and various mono, di, etc. esters can be made. In fact, such reactions almost always result in complex mixtures of mono-, di-, tri-, and tetraesters, and the stoichiometric ratios of the reactants can simply be adjusted so that the desired reaction product is favored.

The above complex mixtures of the esterified cyclic dehydration products of sorbitol (and small amounts of esterified sorbitol) are collectively referred to as "sorbitan esters". Sorbitan mono- and diesters of lauric, myristic, palmitic, stearic and behenic acid are particularly useful as additional textile finishers for the textiles to be treated. Mixed sorbitan esters, e.g. Mixtures of the above-mentioned esters, and mixtures which are produced by esterification of sorbitan with fatty acid mixtures, such as the mixed tallow and hydrogenated palm oil fatty acids, are valuable and economically interesting as additional textile finishers. Unsaturated Cm to Cis sorbitan esters, e.g. Sorbitan monooleate is usually present in such mixtures. All sorbitan esters and their mixtures, which are essentially water-insoluble and have fat-hydrocarbon “tails”, are materials which can be used as additional textile finishers for making antistatic or softening textiles.

The preferred alkyl sorbitan ester materials as anti-static or softening textiles as additional textile finishers include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan dilaurate, and sorbitan dandrone sorbate, mixtures of sorbitan sorbitene, and sorbitan diborbate with mixtures, sorbitan diporbitanate, mixed sorbitol, mixed sorbitol, mixed sorbitol, mixed sorbitol, mixed sorbitol mixed with it and the mixed tallow alkyl sorbitan mono- and diesters. Sorbitan's tri and tetra esters with lauric, myristic, palmitic, stearic and behenic acid, and mixtures thereof, are also useful as additional textile finishers.

Another useful type of nonionic material for anti-static or plasticization of textiles includes the essentially water-soluble compounds that are chemically classified as fatty alcohols. Monools, diols and polyols which have the required melting points and properties of water-insolubility, as stated above, can be used as additional textile finishers. Such textile finishers of the alcohol type also include the mono- and difatty glycerides which have at least one “free” OH group.

All types of water-insoluble high-melting alcohols (including mono- and diglycerides) can be used as additional textile finishers, since all such materials are textile substantive. Of course, it is desirable to use materials that are colorless so that there is no change in the color of the textiles to be treated. Toxicologically acceptable materials should be selected that are safe to use in connection with skin contact.

A preferred type of non-esterified alcohol, which can be used as an additional textile finishing agent, comprises the higher melting links of the so-called fatty alcohol class. Although the term "fatty alcohols" was once restricted to alcohols obtained from natural fats and oils, this term now means all alcohols that correspond to the alcohols obtained from fats and oils, and all of these alcohols can be produced by synthetic methods will. Fatty alcohols obtained from the mild oxidation of petroleum products can be used as additional textile finishers.

Another type of material that can be classified as alcohol and that can be used as a material for the antistatic or softening of textiles comprises various esters of polyhydric alcohols. Such "ester-alcohol" materials which have a melting point in the range given above and which are substantially water-insoluble can be used as additional textile finishers if they contain at least one free hydroxyl group, i.e. if they can be chemically classified as alcohols.

The alcoholic diesters of glycerin which can be used as additional textile finishers include both the 1,3-diglycerides and the 1,2-diglycerides. In particular, diglycerides which have two C8-C20, preferably C10-C18, alkyl groups in the molecule are useful textile finishers.

Non-limiting examples of ester alcohols which can be used as additional textile finishers include glycerol-1,2-dilaurate, glycerol-1,3-dilaurate, glycerol-1,2-dimyristate, glycerine-1,3-dimyristate, glycerol-1, 2-dipalmitate, glycerin-1,3-dipal-mitate, glycerin-1,2-distearate and glycerin-1,3-distearate. Mixed glycerides available from mixed tallow alkyl fatty acids, i.e. 1,2-Ditalgalkylglycerol and 1,3-ditalgalkylglycerol are economically interesting for use as additional textile finishers. The ester alcohols given above are preferred for this use because of their easy accessibility from natural fats and oils.

Mono- and diether alcohols, especially the cio-cis-di-ether alcohols, which have at least one free -OH group, also fall under the definition of alcohols, which are useful as additional textile finishers for the antistatic or softening of textiles. The ether alcohol holes can be produced using the classic Williamson ether synthesis. As with the ester alcohols, the reaction conditions can be selected such that at least one free, unetherified OH group remains in the molecule.

Ether alcohols useful as additional fabric finishers include glycerin-l, 2-dilauryl ether, glycerin-1,3-distearyl ether, and butanetetra-ol-l, 2,3-trioctanyl ether.

The above-mentioned additional anesthetics or plasticizers for textiles can be used as mixtures in combination with the imidazolinium compound. The amount of the refiners, if they are present in the compositions according to the invention, is normally 1 to 12% by weight of the composition, preferably 1 to 8% by weight.

Preferred mixtures are mixtures of the quaternary imidazolinium salt with a sorbitan ester, a fatty alcohol or a quaternary ammonium compound. Most preferred is a mixture of the quaternary imidazolinium salt with ditallow dimethyl ammonium chloride (DTDMAC). These two compounds are preferably used in a weight ratio of about 80/20 to about 20/80 and in particular in a weight ratio of 30/70 to 70/30 imidazolinium / DTDMAC.

Common components of liquid textile finishing agents can be dissolved or dispersed in the textile finishing agent. These common components include clay materials, aldehyde preservatives, emulsifiers, thickeners.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

9

639 444

agents, opacifiers, dyes, brighteners, fluorescent agents, pH regulators and perfume materials. Such optional materials generally make up 0.01 to 10% by weight of the composition.

The aqueous textile finishing agents according to the invention can be prepared by adding the imidazolinium salts to water using conventional methods. For example, the salt or salt and the additional fabric finisher can be heated to form a liquid oily phase which is added to water with mixing, which is maintained at elevated temperatures. Optional components can be added by methods known per se. The agent can then be adjusted to a pH of about 3 to 9, preferably about 4.5 to 7.

The agents according to the present invention are preferably used in the rinse cycle of the customary automatic washing programs. Generally, rinse water is at a temperature from about 15 to about 60 ° C.

If agents according to the present invention are added in the rinse cycle, an amount of the agent is generally used such that the imidazolinium salts are present in concentrations of 2 to 500 parts / million parts, preferably 10 to 100 parts / million parts. These concentration values enable superior results to be achieved in softening textiles and in combating static charges.

The inventive method for finishing textiles in laundry is defined in claim 15.

The textiles are preferably dried in an automatic dryer at a temperature of at least 38 ° C. This drying step facilitates the distribution of the imidazolinium salts over the textile surfaces and is particularly useful if a particulate sorbitan ester material is also used.

example 1

An imidazolinium salt which is essentially free of amines, amine salts and propoxylated imidazolinium salts is prepared in the following way:

A. Diethylene triamine and hardened tallow triglyceride in a molar ratio of amine / triglyceride of approximately 1.4 / 1 are added to a reaction vessel.

B. The amine and triglyceride are reacted over a period of 3 hours at a temperature of approximately 185 ° C and atmospheric pressure.

C. The pressure in the reaction vessel is reduced to approximately 10 mm Hg and maintained under this condition for a period of two hours. The product at this point in time is the imidazoline intermediate for the desired imidazolinium salt plus unreacted components and primary and secondary amines from the intermediate amide. The reaction mixture is analyzed using standard analytical methods to determine the amount of imidazoline and primary and secondary amines.

D. The reaction vessel is cooled to 80 ° C and isopropyl alcohol is added in an amount which corresponds approximately to 20 ° o of the contents of the vessel. The solvent helps to keep the reaction medium fluid.

E. Propylene oxide is added to the reaction vessel in an amount approximately equal to 2% of the imidazoline and the unreacted components. This amount is sufficient to convert unsaturated primary and secondary amines to propoxylated tertiary amine.

F. The reaction vessel is kept under a vacuum of approximately 10 mm Hg for a period of 1 hour.

G. Finally, the propoxylated reaction mixture is mixed with an alkylating agent in the form of dimethyl sulfate. The amount of the alkylating agent originally used is slightly less than the number of moles of imidazoline formed after step C above. As the alkylation progresses, the pH of the reaction medium is monitored and additional dimethyl sulfate is added until the pH is in the 5-7 range.

The product formed in the above reaction is 1-methyl-1-tallowamidoethyl-2-tallow-imidazolinium methyl sulfate, which is essentially free of amines and amine salts.

Example 2

The following formulations are made:

A

B

Imidazolinium salt of

26.25 g

Example 1

Imidazolinium salt of

-

26.25 g

Example 1

without using the

Propylene oxide stage

Aldehyde source

0.55 g

0.55 g

water

Rest to 1000 g

Rest to 1000 g

The pH of both samples was adjusted to 5.8 with sodium hydroxide.

Formulations A and B are tested for residual aldehyde after storage for one week at the temperatures indicated below. The amount of aldehyde originally contained in the formulation is 550 parts / million parts.

temperature

A

B

21 ° C

510 ppm

470 ppm

38 ° C

508 ppm

401 ppm

49 ° C

464 ppm

346 ppm

The above figures show the improved aldehyde stability with the imidazolinium product, which is essentially free of amines and amine salts. Similar results are obtained with other imidazolinium salts made using polyamines and acylating or esterifying agents other than the diethylene triamine and tallow triglyceride of Example 1.

5

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15

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Claims (18)

639 444 PATENT CLAIMS 1. Textile finishing agent, characterized in that it is a quaternary imidazolinium salt of the formula: r-c + -chr. Y A.D. I 1 d (Ia) or ai — chr / R-c + I r. 2! chr. d (Ib) 9. Composition according to claim 3, characterized in that the concentration of the imidazolinium salt is 2 to 8% by weight and the composition additionally contains further organic textile finishers in an amount corresponding to 1 to 12% by weight, that of primary Amines, secondary amines and cyclic tertiary amine salts is free. 10. Composition according to claim 9, characterized in that the additional textile finishing agent is selected from the group comprising non-ionic and cationic materials derived from fats. 11. Composition according to claim 10, characterized in that the additional textile finishing agent is selected from the group consisting of quaternary ammonium compounds, fatty alcohols and sorbitan esters. 12. Composition according to claim 11, characterized in that D for 0 -ch2-ch2-nh ' • cr in which R is an aliphatic or cycloaliphatic hydrocarbon group having 10 to 22 carbon atoms, R: an alkyl, substituted alkyl or aralkyl radical having 1 to 8 carbon atoms, Ri and Rt are hydrogen, hydroxyl, alkyl having 1 to 4 carbon atoms or hydroxyalkyl 1 to 4 carbon atoms, D represents -COR, - (CH: CH2) n-NH-COR, - (CH2CH2) n-0-CO or or (CHiCH2) m-CH3, n represents an integer from 1 to 6 represents, m represents 5 or 6 and X- represents an anion, the composition containing a total of less than 4% primary amines, secondary amines and cyclic tertiary amine salts, based on the weight of the imidazolinium salt. 2. Composition according to claim 1, characterized in that it is in aqueous liquid form and contains the imidazolinium salt in an amount of 1 to 15 wt .-%. 3. Composition according to claim 2, characterized in that D is the group 0 or - + CH2 + jr ° -C-R 40 is, R and Ra contain 14 to 20 carbon atoms and Rj and Ri are hydrogen. 13. Composition according to claim 12, characterized in that R represents a tallow residue, R2 represents methyl and X represents methyl sulfate. 14. Composition according to claim 13, characterized in that it contains dimethylditalgammonium chloride as an additional textile finisher and the weight ratio of the imidazolinium salt to the dimethylditalgammonium chloride is 20/80 to 80/20. 15. Process for finishing textiles in laundry, characterized in that it comprises the following stages: a) washing textiles in an aqueous washing bath which contains a surfactant; b) rinsing the textiles in an aqueous rinsing bath; c) adding a textile finishing agent according to claim 1 in an amount corresponding to 2 to 500 parts / million parts of the imidazolinium salt to the rinsing bath. d) drying the textiles. 16. The method according to claim 15, characterized in that D is the group 0 means. 4. Composition according to claim 3, characterized in that R is an aliphatic or cycloaliphatic hydrocarbon group having 14 to 20 carbon atoms. 5. Composition according to claim 4, characterized in that R.i and R4 are hydrogen. 6. Composition according to claim 5, characterized in that R is derived from tallow fatty acid. 7. Composition according to claim 6, characterized in that R2 is methyl and X is methyl sulfate. 8. Composition according to claim 7, characterized in that D for O 50 or —O-C-R O means. 55 17. The method according to claim 16, characterized in that R is an aliphatic or cycloaliphatic hydrocarbon group having 14 to 20 carbon atoms and R.i and R4 are hydrogen. 18. The method according to claim 17, characterized in that 60 R2 is methyl, X is methyl sulfate and R is a tallow residue. -ch2-ch2-nh-c-r, the concentration of the imidazolinium salt being 2 to 8% by weight and the pH of the composition being 4.5 to 7.