EP0230565B1 - Laundry aftertreating agent - Google Patents

Description

The invention relates to a laundry aftertreatment agent serving in particular as an ironing aid.

It is known to use an aqueous dispersion of a water-insoluble lubricant, in particular a silicone oil, and a water-soluble film former, in particular a water-soluble starch derivative, as an ironing aid for laundry, in particular of cotton. This dispersion is sprayed onto the laundry to be ironed and enables the iron to slide more easily than an untreated laundry, the film former imparting a certain stiffness to the ironed laundry, which is particularly desirable for shirts and blouses.

Spraying the laundry using a spray can is expensive, however, and is therefore mainly limited to use with shirts and blouses. In addition, the sliding effect achieved with the known dispersion described above is still not entirely satisfactory. It is also difficult to spray the tissue evenly without completely soaking it. This can lead to undesirable stains or margins on the fabric. Another disadvantage is that the spray can often cannot be completely emptied despite an elaborate spray mechanism.

The object of the invention is therefore to provide a laundry aftertreatment agent for facilitating ironing which, in comparison to the known ironing aid described above, permits even easier ironing due to an increased sliding action and is less expensive to use.

This object is achieved by the laundry aftertreatment agent according to claim 1, which is preferably introduced in the last rinse cycle in the washing machine, so that the use of expensive spray cans is omitted.

The laundry aftertreatment agent according to the invention not only results in a higher sliding effect than the known ironing aid described above, but also increases the absorbency of the fabric against water and gives the fabric a soft, fluffy feel, while also giving the ironed laundry a slight finish. This effect of the laundry aftertreatment agent according to the invention is surprising insofar as it has hitherto been considered impossible to achieve the combination of the properties described above, in particular the combination of a fluffy feel with the absorbency of the fabric against water. To achieve a fluffy feel, so-called fabric softeners, which contain quaternary ammonium bases with long-chain alkyl residues as active ingredients, have hitherto been used as laundry after-treatment agents. These agents added to the last rinse of the washing machine give the laundry, in particular terry goods and jersey, a soft feel, but they are unsuitable for the aftertreatment of ironing despite a certain amount of easier ironing compared to untreated laundry. A serious disadvantage of fabric softeners is their hydrophobic effect on textile fabrics, especially cotton, combined with a strong reduction in the absorbency of the laundry.

The laundry aftertreatment agent according to the invention is therefore not only an improved ironing aid compared to the known ironing aid, but at the same time a means by which the body and the feel of the laundry are improved while at the same time achieving a softening effect, without thereby impairing the absorbency of the treated laundry becomes. In addition, the laundry aftertreatment agent according to the invention enables ironing of dry laundry, an even better sliding effect being achieved compared to moistened laundry. It is only necessary to slightly dampen the laundry if there are persistent creases. There are also no disadvantages when using steam irons. As is known, a steam iron cannot be used for ironing laundry which has been treated with the known ironing aid described above.

DE-OS 26 31 419 describes a laundry treatment agent which can also be introduced into the last rinse cycle of a washing machine and which has the use of a silicone oil in common with the laundry treatment agent according to the invention, but in the known case no alkoxylated starches and celluloses are used, when used according to the invention, not only the bulk and the lubricity, but also the absorbency of the treated tissues are surprisingly increased. In the known case, roasted dextrins are used which only act as thickeners.

According to the invention, fatty acid amides are used in contrast to the use of fatty acid amines in the known case. These require less dirt reduction and are easier to hydrolyze than amines and are therefore easier to wash out. In addition, they are more easily degradable and therefore more environmentally friendly than the amines used in the known case.

The cationically dispersed silicone oil (component A) is a textile-relevant silicone oil with a viscosity between 500 and 50,000 mm _, - _S - ¹ at 25 ° C, in particular 1000 to 10,000 mm _, - s ^-1 at 25 ° C, as it is described, for example, in “Textilveredelung”, 19 (1984) No. 5 on pages 144 and 145. In particular, alkyl silicone oils, very particularly methyl silicone oil with a viscosity of 1000 to 10,000 mm ² · _S - ¹ , are suitable.

The laundry aftertreatment agent according to the invention can preferably also contain a paraffin wax as a partial replacement for the silicone oil, which preferably has a melting point ≧ 40 ° C. and in particular from 50 to 60 ° C.

• worin bedeuten:
• R₁ = H R₂ = R₁ = -CH₂CH₃
• m =2bis3
• n = 1 bis 2
• M = 50 bis 2000
• N = 0,1 bis 2% Stickstoff

An amino-functional siloxane which preferably corresponds to the present formula can also be used as the silicone oil of component A)

• in which mean:
• R ₁ = HR ₂ = R ₁ = -CH ₂ CH ₃
• m = 2 to 3
• n = 1 to 2
• M = 50 to 2000
• N = 0.1 to 2% nitrogen

n = 50 bis 2000 m richtet sich nach dem Stickstoffgehalt von 1 bis 4%. Vorzugsweise besitzt dieses quaternäre Siloxan, das sich als Polysiloxan-dimethylalkylammoniumacetat-Copolymeres bezeichnen lässt, in einer 30%igen wässerigen Lösung eine Dichte bei 20° C von 1,053 g/cm³ und eine Viskosität bei 20° C von 60 bis 100 mPa·s, während der pH-Wert einer 30%igen Lösung 6 bis 7 beträgt.Furthermore, the silicone oil of component A) can be a quaternary siloxane, which preferably corresponds to the following formula

n = 50 to 2000 m depends on the nitrogen content of 1 to 4%. This quaternary siloxane, which can be referred to as a polysiloxane-dimethylalkylammonium acetate copolymer, preferably has a density at 20 ° C. of 1.053 g / cm ³ and a viscosity at 20 ° C. of 60 to 100 mPa · s in a 30% aqueous solution , while the pH of a 30% solution is 6 to 7.

In addition, the silicone oil of component A) can consist of a silicone elastomer, as described in “Textilpraxis International” (1983), December, on pages 1342 and 1343. A component of the substances mentioned can also be used as component A).

worin bedeuten:

• R, = Alkyl oder Alkylen mit 9 bis 21 Kohlenstoffatomen O
• R₂ = -C-R₁ oder Wasserstoff
• R₃ = Wasserstoff oder Methyl
• m = 1 bis 4
• n = 0 bis 3

Component B) is a condensation product of an aliphatic, saturated or unsaturated C ₁₀ -C ₂₂ monocarboxylic acid with a polyamine or an addition product of a polyamine with ethylene oxide or propylene oxide. The condensation product preferably corresponds to the formula

in which mean:

• R, = alkyl or alkylene with 9 to 21 carbon atoms O
• R ₂ = -CR ₁ or hydrogen
• R ₃ = hydrogen or methyl
• m = 1 to 4
• n = 0 to 3

In particular, stearic acid or oleic acid are suitable as monocarboxylic acids and diethylenetriamine and diethylenetriamineethanolamine as polyamines.

Component C) is a cationic alkoxylated starch, as described for example in DE-PS 21 55941, or a cationic alkoxylated cellulose.

• worin bedeuten:
• R = H oder CH₃
• m = 1 bis 3
• n = 0 bis 3

The cationic alkoxylated starch preferably corresponds to the formula

• in which mean:
• R = H or CH ₃
• m = 1 to 3
• n = 0 to 3

The alkoxy content is preferably between 4 and 10% and the nitrogen content between 0.1 and 0.5%.

worin R³ ein langkettiger Kohlenwasserstoffrest, der gesättigt oder ungesättigt sein kann und insbesondere 10 oder mehr Kohlenstoffatome aufweist, ist, R⁴ Wasserstoff oder einen Alkylrest, insbesondere mit 1 bis 5 Kohlenstoffatomen, wobei der AIkylrest substituiert und insbesondere an seinem Ende einen Hydroxyrest tragen kann, bedeutet, R⁵ ein niederer Alkylrest, insbesondere ein C₁-C₄-Alkylrest, ist, X ein anionischer Rest, vorzugsweise Halogenidrest, oder eine anionische Gruppe, insbesondere die Gruppe

worin R⁶ für eine C₁-C₄-Alkylgruppe steht, oder die Acetatgruppe ist. Das kationaktive Dispergiermittel wird vorzugsweise in einer Menge von 2 bis 10%, bezogen auf den Siliconanteil, verwendet.The cationic dispersant for the silicone oil of component A) can be any cationic emulsifier. According to the invention, a cation-active imidazolinium salt, in particular a compound of the formula, is particularly preferred

in which R ^{3 is} a long-chain hydrocarbon radical which may be saturated or unsaturated and in particular has 10 or more carbon atoms, R ^{4 is} hydrogen or an alkyl radical, in particular having 1 to 5 carbon atoms, the alkyl radical being substituted and in particular having a hydroxy radical at its end , means R ^{5 is} a lower alkyl radical, in particular a C ₁ -C ₄ - Is alkyl radical, X is an anionic radical, preferably a halide radical, or an anionic group, in particular the group

wherein R ^{6 represents} a C ₁ -C ₄ alkyl group, or is the acetate group. The cationic dispersant is preferably used in an amount of 2 to 10% based on the silicone content.

Component A) also contains an alkoxylated, in particular ethoxylated, fatty amine in an amount of up to 10% by weight, based on the silicone content.

The laundry aftertreatment agent according to the invention preferably contains component A) in an amount of 0.5 to 20% by weight, in particular 3 to 8% by weight, component B) in an amount of 0.5 to 15% by weight, in particular 2 to 8% by weight, and component C) in an amount of 1 to 15% by weight, in particular 2.5 to 7.5% by weight (balance water).

In addition, the laundry aftertreatment agent according to the invention preferably contains fragrances, preservatives, dyes and organic acids, in particular organic aliphatic carboxylic acids, such as acetic acid or citric acid, for setting a pH of preferably 3 to 5.

The components of the laundry aftertreatment agent according to the invention are distinguished by a relatively high substantivity to the textile fiber, i.e. they are drawn from a cold and long liquor, in particular onto cotton, so that the laundry aftertreatment agent according to the invention is particularly suitable for treating laundry consisting of cotton or laundry containing a proportion of cotton.

Since the components of the laundry aftertreatment agent according to the invention can easily be washed out again, there is no risk that they will accumulate on the fibers when the agent is used repeatedly and thus influence the laundry properties.

Furthermore, the laundry aftertreatment agent according to the invention does not cause increased re-soiling of the treated laundry, and likewise does not promote laundry yellowing, which can occur in the case of conventional softeners.

The laundry aftertreatment agent according to the invention is expediently added to the last rinse after the washing process in an amount of 50 to 80 grams, the water volume of the last rinse being about 20 liters.

The laundry aftertreatment agent according to the invention can be produced by the following two methods:

Method 1

Cation-active alkoxylated starch is dispersed in water. This dispersion is heated to 80 to 90 ° C. with vigorous stirring, a moderately viscous solution being formed. The mixture is then cooled to 20 to 25 ° C and the solution is mixed with the cationic fatty acid condensation product, dispersed in water. As soon as a uniform dispersion has been obtained, the silicone oil dispersion dispersed with a cationic disperser is carefully added with slow and vigorous stirring. The dispersion is adjusted to an acidic pH using an acid. Finally, color, fragrance and a preservative are added.

Method II

The starch solution is prepared in the manner described above. The cationic fatty acid condensation product in pure solid form is added to the solution heated to 90 ° C. with vigorous stirring. The mixture is stirred until a stable dispersion has formed. Then it is cooled to 20 to 25 ° C and proceed as described above.

Example 1 :

• 1) 50%ige, wässerige Dispersion aus einer 1:1-Mischung eines Dimethylpolysiloxans mit einer Viskosität von 5000 mm²· _S ^-1 und eines Paraffinwachses mit einem Schmelzbereich von 50 bis 55° C, emulgiert mit einem Dioleylimidazoliniumsulfat und einem Cocosaminethylenoxidaddukt mit 5 bis 10 Mol Ethylenoxid 6,00 Gew.-Teile
• 2) 30%ige Dispersion eines Propylaminoethylamindimethylpolysiloxans mit einer Aminzahl von 0,1 bis 0,5 kationisch emulgiert mit Dioleylimidazoliniumsulfat und Cocosaminethylenoxidaddukt mit 5 bis 10 Mol Ethylenoxid 4,50 Gew.-Teile
• 3) 20%ige wässerige, mit Essigsäure auf pH 3 eingestellte Dispersion von Distearinsäuredipropylentriaminethanolaminkondensat 10,00 Gew.-Teile
• 4) Hydroxypropyltrimethylammoniumchloridhydroxypropylstärkeether mit einem N -Gehalt von 0,25% und einem Propoxygehalt von ca. 7% 7,50 Gew.-Teile
• 5) Farbstoff, Duftstoff, Konservierungsmittel 0,20 Gew.-Teile
• &) Wasser

This example describes a recipe with which a laundry aftertreatment agent according to the invention is produced according to method I.

• 1) 50% aqueous dispersion of a 1: 1 mixture of a dimethylpolysiloxane with a viscosity of 5000 mm ² · _S ^-1 and a paraffin wax with a melting range of 50 to 55 ° C, emulsified with a dioleylimidazolinium sulfate and a cocosamine ethylene oxide adduct with 5 up to 10 moles of ethylene oxide 6.00 parts by weight
• 2) 30% dispersion of a propylaminoethylamine dimethyl polysiloxane with an amine number of 0.1 to 0.5 cationically emulsified with dioleylimidazolinium sulfate and cocosamine ethylene oxide adduct with 5 to 10 moles of ethylene oxide, 4.50 parts by weight
• 3) 20% aqueous dispersion of distearic acid dipropylenetriaminethanolamine condensate 10.00 parts by weight, adjusted to pH 3 with acetic acid
• 4) Hydroxypropyltrimethylammoniumchloride hydroxypropyl starch ether with an N content of 0.25% and a propoxy content of approx. 7% 7.50 parts by weight
• 5) Colorant, fragrance, preservative 0.20 parts by weight
• &) Water

71.80 parts by weight The pH of this agent is 4. It is a thin, milky-looking dispersion and with a viscosity of 120 mPa - s.

Example 2:

• 1) wie Beispiel 1 (Silicon/Wachs-Mischung) 6,20 Gew.-Teile
• 2) Distearinsäurediethylentriaminkondensat (Fp: 90° C) 3,25 Gew.-Teile
• 3) wie 4) in Beispiel 1 (Stärkeether) 5,00 Gew.-Teile
• 4) Zitronensäuremonohydrat 3,00 Gew.-Teile
• 5) Farbstoff, Duftstoff, Konservierungsmittel 0,20 Gew.-Teile
• 6) Wasser

Using the following recipe, a laundry aftertreatment agent according to the invention is produced using method 11:

• 1) As example 1 (silicone / wax mixture) 6.20 parts by weight
• 2) Distearic acid diethylenetriamine condensate (mp: 90 ° C.) 3.25 parts by weight
• 3) as 4) in Example 1 (starch ether) 5.00 parts by weight
• 4) Citric acid monohydrate 3.00 parts by weight
• 5) dye, fragrance, preservative 0.20 parts by weight
• 6) water

82.35 parts by weight The pH of this agent is 3 to 4. It is a thin, milky-looking dispersion with a viscosity of 80 mPa 's.

Example 3:

Determination of the ironing values:

Using the agent produced in Example 2, which is added to the last rinse of a conventional household washing machine in an amount of 50 to 80 g, laundry items made of cotton and cotton / polyester blended fabrics, which were previously washed using a conventional detergent at 95 ° C. were. treated to determine the ironing values. The prick test is carried out as follows:

An iron with a temperature of 200 ± 10 ° C is pulled over the test fabric with constant tensile force that can be adjusted by weights along a constant measuring path. This slide test breaks down into two phases, namely the "ironing" of the fabric adjusted to 30% moisture and the "final ironing" of the dry, smooth fabric.

For comparison purposes, untreated fabric and fabric treated with a conventional ironing aid were subjected to the ironing test. The results obtained are summarized in Table I below.

The ironing values for the untreated fabric fluctuate around the mean values given in the table by + 10%. This applies in particular to the sliding values. The cause is to be found in the non-uniformity of the surface roughness of the fabric. The significantly lower ironing values determined with "ironing aid" and the agent according to the invention have a significantly smaller fluctuation range (maximum 5%), since the reproducibility is improved because of the decreasing surface roughness of the treated tissue.

Example 4:

Determination of the washability of the agent according to the invention:

Laundry samples made from 100% cotton fabric are washed 5 or 6 times at 95 ° C. and 60 ° C. using a conventional detergent and aftertreated in an amount of 80 g in each case in the last rinse cycle by adding the laundry aftertreatment agent according to Example 2.

For comparison purposes, untreated items washed in the same way and items treated with "ironing aid" are tested. The ironing test is used as the test method. The mean values, which are recorded in the attached FIGS. 1 and 2, are formed from 6 individual sliding tests.

The ironing values of FIGS. 1 and 2 represent the tensile force extrapolated at the same time t = 10 s of cotton fabric washed and post-treated or not post-treated at 95 ° C. (5 times) or 60 ° C. (6 times).

As shown in FIGS. 1 and 2, the ironing value that surprisingly deviates only slightly from the smoothness value of the first aftertreatment already arises with the first repetition of the aftertreatment.

It can be seen from this that the laundry aftertreatment agent according to the invention can be washed out of the laundry sample both when washing at 95 ° C. and when washing at 60 ° C. There are therefore no disadvantageous addition effects when using the laundry aftertreatment agent according to the invention.

Example 5:

Determination of bulk (fullness):

Terry towels (100% cotton) are washed in a conventional manner and in the last rinse once with the agent of Example 2 in a concentration of 50 to 80 g / 20 liters and once for comparison with a conventional fabric softener (based on distearyldimethylammonium chloride) treated with the same concentration. Untreated terry towels are also used for comparison purposes. A total of 15 terry towels are washed twice at 60 ° C. After air drying The terry towels of the three test groups are placed on top of one another in a stack on a drying rack. The stack heights are determined after 10 minutes and the results are shown in Table 11.

The height of the stack is a measure of the bulkiness of the terry towels and the loosening of the individual fibers. The agent according to the invention surprisingly brings about an even greater stack height than the known plasticizer.

Example 6:

Determination of absorbency (drying capacity):

The absorbency is a measure of the absorption capacity of moisture from textile fabrics (terry cloth). The absorbency is determined using the rising height method according to DIN 53294. The 3 cm wide and 25 cm long cotton strips (100% cotton fabric, not equipped, with a basis weight of 140 g / cm ² ) are immersed with one end in distilled water, which due to the capillary forces in the fabric more or less depending on the absorbency rises high. The climbing heights after a test period of 5 minutes are shown in Table III.

As Table III above shows, the absorbency compared to an untreated tissue sample is almost achieved by the agent according to the invention.

Claims (5)

1. Laundry aftertreatment composition consisting of

A) an aqueous dispersion, prepared by means of a cationic dispersant, of a silicone oil, which may have been partly replaced by a paraffin wax, from the group consisting of silicone oils which have a viscosity between 500 and 50,000 mm²· _S-¹ at 25° C and are relevant to textile applications, aminofunctional siloxanes, quaternary siloxanes, silicone elastomers and mixtures thereof, which component A) may additionally contain an alkoxylated fatty amine in an amount of up to 10% by weight, based on the silicone content,

B) a condensation product, of an aliphatic saturated or unsaturated C₁₀-C₂₂-monocarboxylic acid with a polyamine or an additional product of a polyamine with ethylene oxide or propyleneoxide,

C) a cationic film former from the group consisting of cation-active alkoxylated starches and cation-active alkoxylated celluloses,

D) water and optionally

E) further additives from the group consisting of scents, preservatives, dyestuffs and organic acids suitable for standardising the pH.

2. Composition according to Claim 1, characterized in that component A) is a silicone oil of a viscosity between 1,000 and 10,000 mm^{2 .} s^-1 at 25° C which is relevant for textile applications.

3. Composition according to Claim 2, characterized in that the silicone oil is an alkylsilicone oil, in particular a methylsilicone oil.

4. Composition according to any one of Claims 1 to 3, characterized in that the cationic dispersant forcomponentA) is a cation-active imidazolinium- salt of the formula

where R³ is a saturated or unsaturated hydrocarbon radical of 10 or more carbon atoms, R4. is hydrogen or a substituted or unsubstituted alkyl radical of 1 to 5 carbon atoms, R⁵ is a lower alkyl radical and X an anionic radical or an anionic group.

5. Composition of any one of Claims 1 to 4, characterized in that there are present, in each case based on the entire product, component A) in an amount of 0.5% to 20% by weight, component B) in an amount of 0.5 to 15% by weight and component C) in an amount of 1 to 15% by weight, the remainder being water.

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