EP0846157A1

EP0846157A1 - Process for applying odoriferous substances to textiles

Info

Publication number: EP0846157A1
Application number: EP96930039A
Authority: EP
Inventors: Wilfried Umbach; Sandra Witt
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1995-08-23
Filing date: 1996-08-14
Publication date: 1998-06-10
Anticipated expiration: 2016-08-14
Also published as: WO1997008289A1; DE19530999A1; EP0846157B1; DE59603875D1; ES2142088T3

Abstract

A shaped body that contains odoriferous substances and that is produced by irradiating with micro-waves a mixture of porous carrier substances, hydrated substances and a partially liquid perfume mixture, is used to apply odoriferous substances to textiles in a washing machine. These shaped bodies contain 8 to 40 % by weight odoriferous substances.

Description

Process for applying fragrances to textile goods

The present invention relates to a method for applying fragrances to textile goods in a washing machine.

In the case of textile laundry, especially in the household sector, it is common today to add small amounts of perfume to the detergents and rinsing agents, which serve to give the washing or rinsing solution itself, but also the textile goods treated with the washing or rinsing solution, a pleasant fragrance lend. You can work the perfume directly into the detergent or add it to the detergent solution in an additional step.

DE 39 11 363 describes a process for producing fragrance-containing washing or rinsing liquors, in which a fragrance in the form of a capsule or a tablet is added to the washing or rinsing liquor. The capsules contain the fragrance together with an emulsifier in liquid form, while the tablets also contain fillers and carriers, for example sodium aluminum silicates or cyclodextrins. The tablets or capsules have a volume of more than 1 cm ³ and contain at least 1 g of fragrance. Tablets or capsules with more than 2.5 g of fragrance and a volume of at least 5 cm ³ are preferred. During storage, tablets or capsules of this type must be provided with a gastight and watertight covering layer in order to protect the contents. Further details on the production and the physical properties of suitable tablets are not contained in this publication.

Perfume-containing tablets which can be used to perfume a wash liquor are also described in German application 41 33 862. The tablets contain between 3 and 15% by weight of perfume oil and as a carrier material for the perfume oil between 15 and 40% by weight of sorbitol. In order to achieve good dissolving power, 20 to 70% by weight of a disintegrant, consisting of a mixture of carbonate / bicarbonate and an acid, are used. The high proportion of explosives means that tablets of this type are sensitive to atmospheric moisture and must be stored appropriately protected

Now, however, higher perfume oil proportions than mentioned in the above document are quite desirable in order to obtain smaller tablets that can be filled into the induction chambers of conventional washing machines without problems. In a conventional tablet pressing process, however, there is the danger that the liquid component is pressed out of the pores of the carrier material and the tablets become moist and greasy on the outside.

The international application WO 94/25563 describes a process for the production of washing and cleaning active moldings using microwave technology, which works without high pressure pressing. The moldings produced in this way are distinguished by an extremely high dissolving speed or disintegration speed with simultaneous breaking strength, without the need for an explosive. At the same time, they are stable in storage and can be stored without additional precautions. In this way it is also possible to produce moldings which have a perfume oil content which is customary for detergents and cleaning agents and between 1 and 3% by weight. Perfume oils are generally volatile and could therefore evaporate under the influence of microwave radiation. If higher proportions of volatile liquid substances are to be used, a two-component system consisting of a component produced using microwave technology and a component containing the sensitive liquid substances is therefore described.

The object of the present invention is to provide a method for applying fragrances to textile goods in a washing machine by means of an externally dry, quickly soluble, fragrance-containing molded body which is to be stored without special precautions.

It has been found that this object can be achieved with moldings containing fragrance, which are produced with the aid of microwave technology. The invention relates to a method for applying fragrances to textile goods in a washing machine by adding a solid, fragrance-containing molded body in the rinse cycle, characterized in that porous, at least predominantly water-soluble carriers are mixed with hydrated substances and at least partially liquid perfume preparations in this way that the perfume preparation is at least largely absorbed in the pores of the mixture and the resulting, dry powder is subjected to a sintering process by microwave radiation until a break-resistant molded body is formed which is wholly or in divided form in the rinse cycle of a machine washing process is given to wet laundry.

The moldings used according to the invention preferably contain water-soluble porous carrier substances, which can be of organic as well as inorganic origin. In the context of this application, porous carriers are understood to be substances which are capable of absorbing liquid components in substantial quantities without the individual particles sticking to one another. The proportion of these substances is preferably 10 to 80% by weight, based on the total weight of the molding.

Preferred porous carriers are selected from the group consisting of starches, silicas and silicates, preferably water glasses and in particular over-dried water glasses, as are described in German patent application P 44 00 024.3. Examples of suitable silicates are the products sold under the trade names Britesil (R) by Akzo, or the products sold under the trade names Gasil (R) 200 or Sorbsil (R) P 80 by Crosfield Chemicals and the products listed below the trade name Bentone ( ^R ) EW or Bentone (R) MA from Rheox. As an example of silicas, reference is made to the products sold by Degussa under the trade names Aerosil (R) 200 or Sipernat (R) 225.

Phosphates and disilicates, for example β- or sodium disilicate Na2Si £ θ5 or zeolites, preferably zeolite NaA in detergent quality but also zeolite P and X, may be present as further carriers. Usable organic carriers are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, amino carboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures of these.

Polymeric polycarboxylates, such as, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular weight of 800 to 150,000 (based on the acid) are also suitable. Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have also proven to be suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Also particularly preferred are biodegradable terpolymers, for example those which are salts of acrylic acid and maleic acid and vinyl alcohol as monomers or vinyl alcohol derivatives (DE 43 00 772) or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives (DE 4221 381).

Further carriers are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO 93/08251, or their preparation is described, for example, in international patent application WO 93/16110. The known polyaspartic acids or their salts and derivatives should also be mentioned.

The manufacture of the fragrance-containing molded articles according to the invention from powdered raw materials using microwaves takes place according to the teaching of international application WO 94/25563, to the disclosure of which reference is expressly made. An essential prerequisite here is that at least partially bound water is present, ie some of the starting materials are in hydrated form. In the context of this application, hydrated substances are understood to mean those substances which contain bound water of crystallization or which are able to bind at least partially water added from the outside as water of crystallization.

To produce the moldings used according to the invention, a mixture is used which contains a perfume preparation and carriers and hydrated substances which are selected from the group consisting of salts containing water of crystallization, preferably alkali metal carbonates, hydrogen carbonates, alkali metal sulfates and hydrogen sulfates, as well as acetates and citrates. This mixture preferably contains 2 to 20 and in particular 6 to 12% by weight of bound water, based on the total weight of the mixture.

First, the individual components, which are generally in powder form, but can also contain granular or liquid components, are mixed, brought into the desired spatial shape and then irradiated with microwaves.

In the context of the present invention, “microwaves” are understood to mean the entire frequency range between 3 and 300,000 MHz, which thus also includes the radio wave range of 3 to 300 MHz in addition to the actual microwave range of above 300 MHz. With regard to the radiation conditions, reference is explicitly made to WO 94/25563, e.g. can microwave generators, e.g. Send radiation with a wavelength of 2450 MHz and have a power of 250 watts or 1000 watts can be used.

The exposure time is e.g. depending on the set power of the microwave oven and on the weight and composition of the mixture to be irradiated. In general, an output of less than 1000 W / kg * h, depending on the mixture in question, preferably from 50 to 400 W / kg * h and in particular from 100 to 200 W / kg-h is necessary.

So-called macrosolids can be produced using this technique. The mixture of starting materials used in this application is referred to as a "premix" by a local melting / sintering caused by the microwave beams at the contact points. The cavities that exist between the individual premix components before the irradiation with microwaves bring about a high porosity of the resulting shaped bodies and thus contribute to improving the dissolving properties of the shaped bodies. In order for local sintering of the premix components to be possible, at least some of them must have sintering properties on the surface. For this purpose, it is necessary that the premix components themselves or their surfaces contain sufficient water so that heating of this water causes the contact points on the premix components to melt or crosslink.

In the context of the present invention, the term “shaped body” is not restricted to a specific spatial shape, although in general a tablet is understood in the conventional sense, i.e. a cylindrical body, the height of the cylinder being less than its diameter. In principle, however, any other conceivable spatial shape is possible, which is forced onto the premix due to an outer container. It is also possible to achieve the desired spatial shape by slightly pre-compressing the premix under low pressure and then irradiating the compact, which is not mechanically loadable.

In a preferred embodiment, the shaped bodies used according to the invention have a spherical shape, the diameter of the sphere being between 0.3 and 10 cm, preferably between 1.0 and 3 cm.

The moldings used in the process according to the invention have a compressive strength of at least 20 N / cm. In order to divide them if necessary, they can be provided with a break edge or one or more break grooves.

The moldings used in the process according to the invention have a fragrance content of 8 to 40% by weight, preferably 10 to 25% by weight, based on the total weight of the molded body. The perfume preparations, which are solid but preferably liquid, are in some cases complex mixtures of various individual chemical compounds, the so-called fragrances. The fragrances can be selected from a wide variety of chemical classes. The type of fragrance has practically no influence on the physical properties of the molded body. Of course, the present invention also includes shaped articles which contain only a single fragrance.

One can distinguish between alkali-stable and less alkali-stable fragrances. Alkali-stable odoriferous substances are, for example, linalool, geraniol, acetophenone, lilial, geranonitrile, dihydromyrcenol, o-tert-butylcyclohexyl acetate, anisaldehyde, tetrahydrolinalool, citronellol, cyclohexylsalicylate, phenylethyl alcohol, benzophenone, rose oxide, methylbenzylate; to the less alkali-stable fragrances include Vetivery1acetat, δ ^{'-Dodecalacton,} allyl amyl, HydroxyCitronellal benzyl acetate, amyl butyrate. When using less alkali-stable fragrances, it must be ensured that the carrier used does not have too high an alkalinity. If necessary, the pH can also be lowered with weakly acidic additives, e.g. NaHSÜ4, Na2HPÜ4, NaH £ P04 or citric acid.

In order to be subject to as few restrictions as possible when selecting the odoriferous substances, the pH value of a 1% by weight aqueous solution of the finished shaped bodies used according to the invention should ideally be 3 to 12, preferably 5.5 to 8.5 lie.

The fragrance bodies used according to the invention can furthermore contain surfactants in amounts of up to 40% by weight, preferably from 0.5 to 15% by weight, based on the total weight of the shaped body. This results in better wetting of the textile goods to be scented.

Suitable surfactants are anionic, cationic, amphoteric or zwitterionic, but above all nonionic surfactants, as are disclosed in WO 94/25563; preferred are nonionic surfactants, such as, for example, ethoxylated fatty alcohols which differ from primary alcohols preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide, in which the alcohol radical can be linear or methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, linear residues from alcohols of native origin with 12 to 18 carbon atoms are preferred, such as from coconut, tallow or oleyl alcohol.

In addition to fragrances, fabric softening substances can also be applied to textile goods using the method according to the invention. In a further embodiment, the fragrance-containing molded articles used according to the invention therefore contain textile-softening substances, preferably in amounts of 10 to 40% by weight, based on the total weight of the molded article. In addition to the usual softening substances, such as quaternary ammonium compounds, preferably natural or synthetic layered silicates, such as, for example, crystalline layered silicates of the hectorite and kenyaite type, which are sold under the brand names SKS-21 or SKS-1 by, are used as textile-softening substances Hoechst company.

In addition, the moldings used according to the invention can optionally also contain disinfectants, bleaches and activators, foam inhibitors, enzymes and emulsifiers and dyes.

Examples

22 g of a premix of fragrances and carriers and / or fillers (Table I, recipes 1 to 5) were placed in a microwave-suitable container (eg glass, polypropylene, Teflon) with a diameter of 4 cm and in a microwave device MLS 1200 the company MLS irradiated with a frequency of 2450 MHz. The set power was 250 watts. The recipe-specific high-frequency power was 190 W / kg ^« h.

For the production of moldings with a soft-care effect, the formulations 6 to 9 listed in Table II were processed according to the method described above in a suitable microwave-suitable form into spheres with a diameter of 1.9 cm and a weight of approximately 3.5 g.

In the recipes:

Porti1 A soda water glass (Henkel) (19% water by weight)

Portil A, over-dried soda water glass (Henkel) (13 wt.% Water)

Dehydol LT7 C ^ -Ciss fatty alcohol x 7 E0 (Henkel)

SKS-1 crystal layer silicate of the Kenyaite type (Fa. Hoechst)

SKS-21 Crystalline layered silicate of the hectorite type (from Hoechst) Table I

(Figures in% by weight)

Soda-10 H2O 10 20 _ 32.2

Soda anhydrous 6 23 - 36.8

Portile A 23 33 40.1 -

NaHS04 x H2O 48 - - -

Dehydol LT7 5 2 1 -

Perfume oil 8 22 19.1 12

Citric acid - - 30.7 -

Strength - - - 19

H ₂ 0 - - 9.1 -

Table II

(Figures in wt.

8th

Citric acid 32.8 39 20 26.5

Portil A, over-dried 25.2 41 - 20.5

SKS-21 32.0 - 39 32.0

SKS-1 - 10 - -

Perfume oil 10.0 10 10 21.0

Soda-10 H ₂ 0 - - 31 -

Abrasion-resistant, unbreakable, rapidly cold water-soluble tablets or balls with a compressive strength of at least 20 N / cm ^{3 were} obtained (measured with a SCHLEUNIGER tablet hardness tester, model 6D).

In the production of the fragrance bodies used according to the invention, there is a slight increase in the percentage by weight of the components used in the premix without water, since water is evaporated during the irradiation process.

Claims

claims

1. A process for applying fragrances to textile goods in a washing machine by adding a solid, fragrance-containing molded article in the rinse cycle, characterized in that porous, at least predominantly water-soluble carriers are mixed with hydrated substances and at least partially liquid perfume preparations in such a way that the Perfume preparation is at least predominantly sucked up in the pores of the mixture and the externally dry powder thus obtained is subjected to a sintering process by microwave radiation until a break-resistant molded body has formed, which is wholly or in divided form in the rinse cycle of a machine washing process for wet washing is given.

2. The method according to claim 1, characterized in that the porous carriers are selected from the group consisting of starches, silicas and silicates, preferably water glasses and in particular over-dried water glasses.

3. The method according to any one of claims 1 or 2, characterized in that the proportion of porous carriers is 10 to 80 wt .-%, based on the total weight of the molded body.

4. The method according to any one of claims 1 to 3, characterized in that the hydrated substances are selected from the group of salts containing water of crystallization, preferably alkali metal carbonates and bicarbonates, alkali metal sulfates and hydrogen sulfates as well as acetates and citrates.

5. The method according to any one of claims 1 to 4, characterized in that the mixture of porous carriers, hydrated substances and a perfume preparation 2 to 20 and preferably 6 to 12 wt .-% bound water, based on the total weight of the mixture, ent ent.

6. The method according to any one of claims 1 to 5, characterized in that the shaped body has a fragrance content of 8 to 40 wt .-%, preferably from 10 to 25 wt .-%, based on the total weight of the shaped body.

7. The method according to any one of claims 1 to 6, characterized in that the molded body surfactants in amounts of up to 40 wt .-%, preferably from 0.5 to 15 wt .-%, based on the total weight of the Form¬ body, contains.

8. The method according to any one of claims 1 to 7, characterized in that the molded body contains fabric softening substances in amounts of 10 to 40 wt .-%, based on the total weight of the molded body.

9. The method according to claim 8, characterized in that the textile-softening substances are selected from the group of natural or synthetic phyllosilicates.

10. The method according to any one of claims 1 to 9, characterized in that the shaped body has a spherical shape, the ball having a diameter between 0.3 and 10 cm, preferably between 1.0 and 3 cm.