WO2021037487A1

WO2021037487A1 - Cleaning article which contains microcapsules

Info

Publication number: WO2021037487A1
Application number: PCT/EP2020/071786
Authority: WO
Inventors: Mauro Davanzo; Michael Greene; Christoph RIEGER; Diana THYSON
Original assignee: Carl Freudenberg Kg
Priority date: 2019-08-30
Filing date: 2020-08-03
Publication date: 2021-03-04
Also published as: EP4022123A1; DE102019123274A1

Abstract

The present invention relates to a cleaning article, e.g. in the form of a cleaning textile or sponge product, which has on at least part of its surface a finish which comprises microcapsules of which the core contains at least one fragrance. This cleaning article is distinguished by having a pleasant smell even when used for a relatively long period of time. Further finishes can serve to provide the cleaning article with good cleaning action both for hydrophilic dirt and for hydrophobic dirt, good dirt take-up properties (dirt-binding properties), good dirt-removal properties when the cleaning article is being rinsed out and/or reduction of soiling during use.

Description

Cleaning article that contains microcapsules

BACKGROUND OF THE INVENTION

The present invention relates to a cleaning article, e.g. B. in the form of a cleaning textile or sponge product that has a finish on at least part of its surface that includes microcapsules, the core of which contains at least one fragrance. These cleaning articles are characterized by a pleasant odor, even after prolonged use. Other finishes can be used to give the cleaning article a good cleaning effect for both hydrophilic and hydrophobic dirt, good dirt absorption properties (dirt binding properties), good protective release properties when rinsing out and / or a reduction in soiling during use.

STATE OF THE ART

Cleaning articles in their various designs, be it as cleaning textiles, as sponges, etc., are used in industrial and household cleaning to a large extent for wet and dry cleaning of various surfaces and especially non-textile surfaces such as floors and stairs, furniture, windows and doors , Mirrors and other glass surfaces, ceramic, wood and metal surfaces, etc. are used. The cleaning articles used can have a simple structure, where it then z. B. can be cleaning wipes made of a single-layer textile base body. Cleaning wipes based on nonwovens with a carrier layer made of a fiber web, which can be bound completely or in partial areas by means of a binding agent, are also widespread. The cleaning of surfaces with synthetic microfibers, which enable environmentally friendly, purely mechanical cleaning without the use of additional cleaning agents, is also very popular. An important property of cleaning articles is to absorb the dirt from the surface to be cleaned and to release it in a subsequent cleaning step. The ability to absorb and release water plays an important role here. In wet cleaning, water or a usually aqueous cleaning solution is used to loosen adhering dirt and to bind the loosened dirt or loose dirt particles such as dust etc. and to remove them from the surface to be cleaned with a cleaning article. Dirt-laden cleaning articles are again brought into contact with water or the cleaning solution for cleaning and should release the previously bound dirt as completely as possible during the wringing process. In addition, cleaning items are often machine washed on a regular basis. Another important property of cleaning articles is the sliding properties, whereby the cleaning article should slide rather easily, especially when cleaning large areas, in order to achieve good ergonomics and a low expenditure of force when wiping.

There is a need for cleaning articles that have good cleaning properties and that can be used for as long as possible. It is important that the consumer has the impression that the cleaning article used is fresh and clean.

It is known to use cleaning articles to modify their properties, e.g. B. to increase the cleaning performance, to be provided with a coating or impregnation.

WO 2014/191070 describes a cleaning cloth which contains a textile carrier material which comprises fibers made of a hydrophobic material and in particular micro-endless filaments, the textile carrier material having areas that are provided with a polyvinyl formal foam and areas that are not with a Polyvinyl formal foam are provided. The PVF foam can be present as a coating and / or impregnation. Due to the only partial coating or impregnation with the PVF foam, the water absorption is not or only insignificantly reduced. At the same time, the dirt picked up from the cloth can be easily rinsed out.

WO 2014/191070 describes a cleaning cloth which contains a textile carrier material which is at least partially provided with a PVF microfoam and which has no PVA fibers or PVA fibers in an amount of less than 50% by weight. The cloth is characterized by excellent wash resistance, despite the low proportion or absence of PVA fibers. It is known to equip cleaning articles with depot preparations for releasing fragrances. Thus, WO 01/73188 describes a disposable cleaning cloth made of a fiber fabric or nonwoven with microcapsules attached to the surface, which are filled with a liquid fragrance composition. When surfaces are wiped, the microcapsules are released and lead to a long-lasting release of active substances into the room air. The microcapsules can be attached to the cleaning cloth mechanically and / or electrostatically and / or via an odorless binder. The cleaning cloth can have polyolefin, polyester or cellulose fibers that can be used as microfibers. The microcapsules are made by coacervating gelatin with gum arabic on oil droplets.

For example, US Pat. No. 6,996,871 B1 describes a cleaning cloth for a mop which, among other things, contains a fragrance carrier, e.g. B. in the form of perfume-filled microcapsules. The use of special microcapsules that give the cleaning cloth a long-lasting fragrance is not described.

US 2006/0270586 describes a cleaning cloth for cleaning surfaces, e.g. B. with a mop that is equipped with drug-filled microcapsules.

The cleaning cloth comprises a cleaning substrate made of a nonwoven fabric or paper and is intended for single use or very limited multiple use.

Polyurethane is also mentioned as a possible polymeric shell material for the microcapsules, with only polyoxymethylene flarea capsules being used in the exemplary embodiments.

US 2013/0239344 A1 describes a cleaning cloth for dry cleaning, wel Ches comprises a nonwoven fabric equipped with microcapsules, the microcapsules comprising a shell made of a cross-linked polymer and a core that contains a scented oil. Preferably, polyurethane-flarea systems are used for encapsulation, the z. B. by reaction of a diisocyanate, such as flexamethylene diisocyanate, with a crosslinkable activator such as a polyethylene glycol or polyvinyl alcohol, he will be kept. A water-insoluble binder can be used to better bind the microcapsules, e.g. B. based on polyolefins or styrene block copolymers. Dry cleaning wipes equipped with these microcapsules only emit their odor when they are used.

DE 20311253 U1 describes a cleaning textile based on natural or synthetic fibers, whereby the individual filaments with fragrances or cleaning agents teln filled microcapsules are deposited and bound to them by a polyurethane synthetic resin. The cleaning textile is thus provided with a longer-lasting fragrance, the attractiveness of such textiles being improved by the addition of fragrances.

The present invention is based on the object of providing a cleaning article which is distinguished by a longer shelf life or a longer useful life. In particular, the cleaning article should have a pleasant smell for longer and can be kept clean and fresh for longer. In particular, the cleaning article should otherwise have good application properties, such as good cleaning performance. The rest of the property profile should not deteriorate as a result of the longer shelf life or longer service life.

Surprisingly, it has been found that this object is achieved by equipping a cleaning article with microcapsules, which are characterized by a particularly favorable release behavior, according to which the core material enclosed in the microcapsules, which contains at least one fragrance, under the conditions of use of the cleaning article is released in a noticeable amount for a prolonged period.

SUMMARY OF THE INVENTION

A first object of the invention is a cleaning article comprising at least one textile and / or sponge-like material that has a finish, the finish comprising microcapsules (especially multi-layer microcapsules) which have at least one core which contains at least one fragrance.

The cleaning article according to the invention is preferably in the form of a wipe, dust cloth, floor wiper, sponge or sponge cloth. In particular, the cleaning article according to the invention is a cleaning textile.

Another object of the invention is a method for producing a cleaning article, wherein at least part of the cleaning article is coated or impregnated (finished) with an aqueous dispersion containing multilayer microcapsules, as defined above and below.

Another object of the invention is the use of a cleaning article, as defined above and below, for cleaning various surfaces, especially special non-textile surfaces, such as floors and stairs, furniture, kitchen surfaces, windows and doors, mirrors and other glass surfaces, ceramic, wood and metal surfaces, etc.

Another object of the invention is the use of multi-layer microcapsules filled with at least one fragrance, as defined above and below, for equipping cleaning articles with a long-lasting fragrance.

DESCRIPTION OF THE INVENTION

The cleaning articles according to the invention have the following advantages:

Cleaning articles for multiple use when cleaning surfaces can be equipped with microcapsules. The cleaning articles can be used for a long time, giving the consumer the impression that the cleaning article used is fresh and clean.

Cleaning articles that contain microfibers can be equipped with microcapsules. In particular, cleaning textiles that contain microfibres can be equipped with microcapsules.

Finishing with microcapsules can take place without the microcapsules being replaced by an additional binder, e.g. B. a polyurethane resin, to the Rei nigungsartikel, especially the fibers of the cleaning article, are bound. Additional finishing of the cleaning article with at least one polyvinyl formal does not lead to a binding of the microcapsules to the cleaning article, especially the fibers of a cleaning article, via the polyvinyl formal.

The desired effect can be achieved with a small amount of microcapsules.

The cleaning articles according to the invention are especially suitable for cleaning hard surfaces. The term "hard surfaces" is understood broadly within the meaning of the invention and generally includes all in the household and commercial sector, the non-textile surfaces. These include floor and stair coverings, solid wall coverings, furniture, kitchen surfaces, doors, windows, mirrors and other glass surfaces, storage areas, etc. B. made of stone, ceramic, metal, wood, plastic, paint, etc. consist. Microcapsules

In the cleaning articles according to the invention, microcapsules are used which are distinguished by an advantageous release behavior. The fragrance enclosed in the microcapsules is then released in a perceptible amount over a longer period of time under the conditions in which the cleaning article is used. Furthermore, microcapsules are used, which remove the fragrances contained during storage of the cleaning article, i. H. before first use, enclose stably and only release at the moment of the desired fragrance development. This release under the conditions of use takes place with a delay in the sense of a “controlled release”, so that the cleaning articles according to the invention have a pleasant fragrance over a longer period of use, which can be perceived by the user.

In the cleaning articles according to the invention, microcapsules are used which adhere to the cleaning articles, especially to textile fibers, with sufficient stability. The use of an external binder can advantageously be dispensed with.

The microcapsules used according to the invention are preferably core-shell encapsulations in which at least one active substance (core) is encased with a shell material (shell) which comprises at least one film-forming polymer.

In a special embodiment, the cleaning articles according to the invention comprise multi-layer microcapsules, the shell of which has two, three or more than three layers. Multi-layer microcapsules and processes for their production are known in principle to the person skilled in the art. Thus, WO 2018/050248 describes microcapsules containing or consisting of a liquid core and at least one inner and one outer shell and a method for producing these microcapsules, comprising the following steps:

(a) providing an oil phase containing at least one lipophilic active ingredient and, if appropriate, at least one stabilizer;

(b) adding at least one polyisocyanate to the oil phase;

(c) providing an aqueous phase containing at least one film-forming polymer;

(d) emulsification of the oil phase from step (b) with the aqueous phase from step (c);

(e) adding a polyamine to the emulsion from step (d); (f) adding at least one aromatic alcohol and at least one aliphatic or aromatic aldehyde other than formaldehyde and optionally at least one film-forming polymer to the emulsion from step (e);

(g) optionally adding a crosslinking agent to the emulsion from step (f); and

(h) optionally separating and drying the optionally crosslinked capsules.

The cleaning articles according to the invention preferably comprise microcapsules, the shell of which has at least one layer which contains at least one polymer selected from polyurethanes, polyureas and mixtures thereof. In a special embodiment, all the shells of the microcapsules contain at least one polymer selected from polyurethanes, polyureas and mixtures thereof.

Single-core and multi-core microcapsules are suitable. Multi-core microcapsules (also called microspheres) contain two or more than two cores distributed in the continuous shell material. Both the single-core and the multi-core microcapsules can also be enclosed by a second, third, etc. shell. Multi-core microcapsules are z. B. in US 2005/0067726 A1. Mononuclear microcapsules with a continuous shell are preferred. This shell preferably has two, three or more than three layers. In a preferred embodiment, the shell of the microcapsules has three layers.

The microcapsules contain at least one solid or liquid core. The microcapsules used in the cleaning articles according to the invention preferably contain a liquid core. The liquid cores of the microcapsules can be in the form of solutions or emulsions or suspensions and contain at least one fragrance.

In a special embodiment, the core material is completely solubilized at 20 ° C. and 1013 mbar. I. E. the core material consists of a homogeneous liquid phase. In this embodiment, solid components of the core material may be present in dissolved form or in a microdispersed manner.

In a special embodiment, the core material comprises or consists of at least one lipophilic component. Lipophilic components in the sense of the invention have a water solubility of <10 mg / mL, preferably <5 mg / mL, in particular <3 mg / mL, at 20 ° C. and 1013 mbar. The core material preferably consists of at least 50% by weight, based on its total weight, particularly preferably at least 75% by weight, in particular at least 90% by weight, especially completely, of at least one lipophilic component.

The core material can additionally contain at least one solvent. In a special embodiment, the core material has no added solvent in addition to the fragrances and any other additives.

The fragrances contained in the microcapsules are in principle not critical and can be selected according to the desired odor. Lipophilic fragrances or sufficiently oil-soluble fragrances are used in particular. These are preferably selected from among fragrances from the following classes: natural fragrances, hydrocarbons, aliphatic alcohols, aliphatic aldehydes and their acetals, aliphatic ketones and their oximes, aliphatic sulfur-containing compounds, aliphatic nitriles, aliphatic carboxylic acids and their esters, acyclic terpene alcohols Terpene aldehydes, acyclic terpene ketones, cyclic terpene alcohols, cyclic terpene aldehydes, cyclic terpene ketones, various cyclic alcohols, cyclic ethers, cyclic aldehydes, cyclic ketones, esters of cyclic alcohols, esters of cyclic carboxylic acids, aromatic hydrocarbons, araliphatic alcohols, esters of araliphatics Carboxylic acids, araliphatic ethers, aromatic aldehydes, araliphatic alcohols, aromatic Ke tone, araliphatic ketones, aromatic carboxylic acids and their esters, araliphatic cal carboxylic acids and their esters, nitrogen-containing aromatic V compounds, phenols, phenol ethers, phenol esters, lactones and mixtures thereof. Specific fragrances from these classes are described in WO 2018/050248, to which reference is made here in its entirety.

The microcapsules can in principle have any shape, but they are preferably spherical or almost spherical, e.g. B. egg-shaped or ellipsoidal.

The microcapsules used in the cleaning articles according to the invention preferably have a volume-average particle diameter (D50) in the range from 100 nanometers to 10 millimeters, preferably 1 to 1000 micrometers, especially 10 to 500 micrometers. The volume-average D50 particle diameter is that point in the particle size distribution at which 50% by volume of the particles have a smaller diameter and 50% by volume of the particles have a larger diameter. The volume average particle diameter can be, for. B. be determined on a dilute microcapsule dispersion with the help of dynamic light scattering. Microcapsules with a volume average Ren particle diameter (D50) of at least 10 μm are generally characterized by a good brush effect of the fragrance contained.

For use in the cleaning articles according to the invention suitable microcapsules which contain at least one fragrance are commercially available, for. B. from Symrise AG, Holzminden, Germany.

The release of the active ingredient from the microcapsules takes place preferably through mechanical stress on the microcapsules during the cleaning process. Alternatively or additionally, a release of the active ingredient by dissolving the capsules on contact with an aqueous cleaning solution, changing the temperature (bringing in a warm cleaning solution), changing the pH value, changing the electrolyte content, etc. is also conceivable.

Cleaning items

The cleaning articles according to the invention comprise at least one textile material or at least one sponge-like material or a combination of at least one textile material and at least one sponge-like material.

Textile materials can contain fibers in the form of staple fibers, filaments or combinations thereof.

The fibers used can be characterized by their fineness, i. H. the weight based on a certain length. The so-called fineness of the fibers is specified in dtex (1 dtex = 0.1 tex or 1 gram per 10,000 meters). The cleaning articles according to the invention preferably comprise fibers which have a titer of 0.05 to 3 dtex, particularly preferably 0.1 to 2 dtex. In a special embodiment, the cleaning articles according to the invention consist only of fibers which have a titer of 0.05 to 3 dtex, particularly preferably 0.1 to 2 dtex.

In a preferred embodiment, the cleaning articles according to the invention comprise or consist of the cleaning articles according to the invention from fibers in the form of microfibers. In the context of the invention, “microfibers” are fibers which have a titer of at most 1 dtex. The term "microfiber" also includes finer fibers such as nanofibers. In particular, the cleaning articles according to the invention comprise or consist of the cleaning articles according to the invention of fibers which have a titer of 0.05 to 1 dtex, especially 0.1 to 0.7 dtex. The advantage of using microfibers is that they show good cleaning results, are very soft and thus offer a pleasant feel.

The term filaments is understood to mean fibers which, in contrast to staple fibers, have a theoretically unlimited length (also called continuous filaments). According to a preferred embodiment of the invention, the cleaning article comprises fibers in the form of filaments. Multi-component filaments are a special design. These have at least two different types of fiber, e.g. B. fibers made from two or more than two different polymers. The cleaning article according to the invention preferably has multicomponent continuous filaments, preferably bicomponent continuous filaments. Preferably, multicomponent continuous filaments used according to the invention, especially bicomponent continuous filaments, in the unsplit state have a titer of 1.5 to 3 dtex and are preferably at least partially, in particular at least 60%, split into micro-continuous filaments.

In a special embodiment, the cleaning articles according to the invention comprise microfibers in the form of melt-spun microfilaments laid down to form a fleece, in particular in the form of at least partially split composite filaments. Compound filaments consist of at least two elementary filaments and can be split and solidified into elementary filaments by common splitting processes, such as water jet needling.

The cleaning article according to the invention preferably comprises a textile material or consists of a textile material which contains fibers that can in principle be selected from natural plant and animal fibers, chemical fibers made from natural and synthetic polymers and combinations thereof.

The cleaning article according to the invention preferably comprises fibers selected from polyamide, polyester, viscose, polyacrylonitrile, polyvinyl alcohol, triacetate, acetate, polycarbonate, polyolefins, glass fibers, cotton, linen, wool, polylactide and mixtures thereof.

The cleaning article according to the invention preferably comprises fibers made of at least one hydrophobic material. According to the invention, the term “hydrophobic” is understood in the conventional sense. In particular, materials are regarded as hydrophobic in the context of the invention, in which water on the surface of a compact body formed from them has a contact angle of greater than or equal to 90 °. shows. The contact angle can e.g. B. be determined with a contact angle measuring system G 40 from Krüss.

The cleaning article according to the invention particularly preferably comprises fibers which contain the following materials or which consist of the following materials: polyamides, polyester, viscose, polyvinyl alcohol, polyacrylonitrile, triacetate, acetate, polyols fine, polyvinyl chloride and / or mixtures thereof. Suitable polyamides are PA 6, PA 66, PA 46, PA610, PA612, PA10, PA810, PA106, PA1010, PA11, PA12 and mixtures thereof. Preferred polyamides are PA 6, PA 66, PA 46 and mixtures thereof, particularly preferably PA 6 and / or PA 66. Preferred polyesters are polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and polylactide. A particularly preferred polyester is PET. Hydrophobized viscose is particularly suitable as viscose. Polyolefins are preferably selected from polyethylenes, polypropylenes and mixtures thereof. In a special embodiment, the cleaning article according to the invention comprises fibers which consist of at least one polyamide or at least one polyester or a mixture of at least one polyamide and at least one polyester. In a further special embodiment, the cleaning article according to the invention comprises fibers which consist of a mixture of two or three types of fibers, selected from polyamide, polyester and polyolefin. In particular, a mixture of PET and PA6 and / or PA66 is used.

The cleaning article according to the invention specifically comprises fibers which contain at least one polyester and at least one polyamide in a quantitative ratio of 90:10 to 10:90, preferably 80:20 to 20:80. More specifically, the cleaning article according to the invention comprises fibers which contain PET and at least one polyamide, selected from PA 6, PA66 and mixtures thereof, in a quantitative ratio of 90:10 to 10:90, preferably 80:20 to 20:80.

According to a further special embodiment, the cleaning article contains polyester, in particular PET and / or modified polyester. This can either be used as the exclusive raw material or mixed with other polymer fibers (e.g. polyamide fibers, especially PA6).

In a special embodiment, the cleaning article according to the invention comprises fibers which contain at least two thermoplastic polymers. In particular, the cleaning article of the invention comprises composite filaments which comprise at least two incompatible polymers. Incompatible polymers are to be understood as meaning those polymers which, in combination, do not, only to a limited extent, or difficultly adhesive pairings give. Such a composite filament has good cleavability into elementary filaments and produces a favorable ratio of strength to weight per unit area. Pairings that adhere only to a limited extent or that are difficult to stick are present when the splitting of the composite filaments having these pairs is easier than with a composite filament that consists only of one of the polymers used.

As incompatible polymer pairs, polyolefins, polyesters, polyamides and / or polyurethanes are preferably used in such a combination that pairings that are not, or only conditionally, difficult to adhere result.

The polymer pairs used are particularly preferably selected from polymer pairs with at least one polyolefin and / or at least one polyamide, preferably with polyethylene, such as polypropylene / polyethylene, polyamide 6 / polyethylene or polyethylene terephthalate / polyethylene, or with polypropylene, such as polypropylene / polyethylene, polyamides / Polypropylene or polyethylene terephthalate / polypropylene.

The cleaning articles according to the invention comprise at least one textile fabric, which is preferably selected from nonwovens, knitted fabrics, woven fabrics and combinations thereof. In the context of the invention, a nonwoven is understood to mean textile sheet-like structures which consist of fibers of limited length or continuous fibers (filaments) and optionally at least one bonding agent, and which have been joined to form a nonwoven (i.e. a fiber layer or a fiber pile) and connected to one another. The connection can be carried out in the usual manner, e.g. B. by needling, stitching, swirling by means of water jets, the action of heat and / or pressure or by adhesive and cohesive bonding with at least egg nem binder. Textile fabrics are referred to as knitted fabrics in which a loop formed by means of a thread is looped into another loop. Knitted goods are specifically available as knitted or knitted fabrics. In Ge weaving, the textile fabric is produced by crossing two thread systems, warp (warp threads) and weft (weft threads).

In a suitable embodiment, the cleaning article according to the invention comprises at least one sponge-like material. Suitable sponge-like materials can, for. B. be designed as a sponge or as a sponge cloth. The sponge-like material can be open-cell or closed-cell. Open-celled sponge-like materials can usually absorb large amounts of liquid from a surface to be cleaned, whereas closed-cell, sponge-like materials take up due to their porosity are highly elastic compressible, but can only absorb very little liquid and protect a surface to be cleaned from too much moisture.

Sponges are preferably made of polymer foams. In a suitable execution, the sponge consists of a polyurethane foam. Polyurethane foams can be produced in a known manner from polyisocyanates, polyols and, if appropriate, at least one further comonomer. Sponges made from polyester-polyurethanes and / or polyether-polyurethanes are preferred. In another suitable embodiment, the sponge consists of a viscose sponge. A mögli che embodiment of a cleaning article according to the invention is z. B. a scrub swam. This can, for example, comprise a handle part made of flexible polyurethane foam and, as a scouring part, a coarse nonwoven fabric which may contain abrasives.

For example, cellulose-based sponge cloths, which can be produced in a known manner by the viscose process, are suitable.

polyester

The finishing of the cleaning articles according to the invention can additionally comprise at least one polyester. Cleaning articles which are at least partially coated and / or impregnated with at least one polyester can be used for a long time, the consumer having the impression that the cleaning article used does not itself get dirty. The cleaning articles obtained in this way have both good dirt absorption properties (dirt binding properties) and good protective release properties when rinsing off. Finishing with at least one polyester can take place without an additional binder, e.g. B. a polyurethane resin is necessary.

The polyesters used to finish the cleaning articles according to the invention are specifically polymers whose repeat units are predominantly linked to one another by ester groups. The polyester specifically does not contain any ethylenically unsaturated double bonds. Specifically, the polyester does not contain any urethane or urea groups.

In the context of the invention, the term aliphatic polyester also includes compounds which contain built-in cycloaliphatic components. The polyesters used according to the invention preferably have a number average molecular weight M _n in the range from 400 to 500,000 g / mol, particularly preferably at least 500 to 200,000 g / mol, in particular 1000 to 100,000 g / mol.

The polydispersity of the polyesters used according to the invention is preferably 1 to 10, particularly preferably 1.1 to 6, in particular 1.2 to 5.

The number average and weight average molecular weights M _n and M _w and the polydispersity can be determined by gel permeation chromatographic measurements (GPC).

In the case of the dicarboxylic acids and monocarboxylic acids mentioned below, the carboxyl groups can each be in non-derivatized form or in the form of derivatives. In the case of dicarboxylic acids, none, one or both carboxyl group (s) can be present in the form of a derivative. Suitable derivatives are e.g. B. anhydrides, esters and acid chlorides. Preferred derivatives are anhydrides or esters. Anhydrides of dicarboxylic acids can be in monomeric or polymeric form. Preferred esters are alkyl esters and vinyl esters, particularly preferably Ci-C4-alkyl esters, in particular the methyl esters or ethyl esters.

The components used to make the polyester are preferably selected from

A) aliphatic, cycloaliphatic and aromatic dicarboxylic acids,

B) aliphatic and cycloaliphatic diols,

C) low molecular weight aliphatic and cycloaliphatic glycols,

D) polymeric aliphatic and cycloaliphatic diols,

E) aliphatic, cycloaliphatic and aromatic monocarboxylic acids,

F) aliphatic and cycloaliphatic monoalcohols,

G) aliphatic and cycloaliphatic polycarboxylic acids with three or more than three carboxylic acid groups,

Fl) at least trihydric aliphatic and cycloaliphatic alcohols,

I) lactones,

K) from A) to I) different, thus cocondensable compounds.

The aliphatic or cycloaliphatic dicarboxylic acids A) are preferably selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pelic acid, suberic acid, azelaic acid, sebacic acid, undecane-a, co-dicarboxylic acid, Dodecane-a, co-dicarboxylic acid, maleic acid, fumaric acid or itaconic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane-1,4 -dicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid, cis- and trans-cyclopentane-1,3-dicarboxylic acid and mixtures thereof.

The aromatic dicarboxylic acids A) are preferably selected from unsubstituted or substituted phthalic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids or diphenyldicarboxylic acids and the derivatives and mixtures of the aforementioned aromatic dicarboxylic acids.

Substituted aromatic dicarboxylic acids A) preferably have at least one (for example 1, 2, 3 or 4) Ci-C4-alkyl radical. In particular, substituted aromatic dicarboxylic acids A) have 1 or 2 C1-C4-alkyl radicals. These are preferably selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, particularly preferably methyl, ethyl and n-butyl, in particular methyl and ethyl and especially methyl.

Particularly preferred aromatic dicarboxylic acid A) is terephthalic acid.

The aliphatic or cycloaliphatic diols B) are preferably selected from ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane

1,4-diol, butane-2,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2,3- diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane-1,6-diol, Hexane-2,5-diol, heptane-1,2-diol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol , 1,2-dodecanediol, 1, 12-dodecanediol, 1,5-hexadiene-3,4-diol, 1,2- and 1,3-cyclopentanediol, 1, 2-, 1,3- and 1, 4-cyclohexanediol, 1, 1-, 1,2-, 1,3- and 1,4-bis (hydroxymethyl) cyclohexane, 1,1-, 1, 2-, 1,3- and 1,4-bis (Hydroxyethyl) cyclohexane, neopentyl glycol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5 -hexanediol,

2.2.4-Trimethyl-1,3-pentanediol, pinacol and mixtures thereof.

Ethylene glycol is particularly preferably used as the aliphatic diol B).

Preferred low molecular weight aliphatic and cycloaliphatic glycols C) are selected from among compounds which have a molecular weight of 60 to less than 500 g / mol. The low molecular weight compounds are particularly preferred C) selected from diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and mixtures thereof.

Preferred polymeric aliphatic and cycloaliphatic diols D) are selected from compounds which have a molecular weight of more than 500 g / mol. Particularly preferred are the compounds D) selected from polyether diols, polyester diols, polyether ester diols and polycarbonate diols. The compounds D) containing ester groups can have carbonate groups instead of or in addition to carboxylic acid ester groups.

Preferred polyether diols D) are polyethylene glycols H0 (CH CH ₂ 0) _n -H, polypropylene glycols H0 (CH [CH ₃ ] CH ₂ 0) _n -H, where n is an integer and n> 4, polyethylene poly propylene glycols, where the The sequence of the ethylene oxide and propylene oxide units can be block-wise or random, polytetramethylene glycols (polytetrahydrofurans), poly-1,3-propanediols or mixtures of two or more representatives of the above compounds. One or both hydroxyl groups in the diols mentioned above can be substituted by SH groups.

Suitable polyether diols D) are in particular by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran or epichlorohydrin with itself, for. B. in the presence of BF ₃ or by addition of these compounds, optionally in a mixture or in succession, atoms of starting components with reactive hydrogen, such as alcohols or amines, eg. B. water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-bis (4-hydroxyphenyl) propane or aniline. A particularly preferred polyether diol is polytetrahydrofuran. Suitable polytetrahydrofurans can be prepared by cationic polymerization of tetrahydrofuran in the presence of acidic catalysts, such as. B. sulfuric acid or fluorosulfuric acid, produced who the. Such manufacturing processes are known to the person skilled in the art.

Preferred polyester diols D) are those which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters of lower alcohols or mixtures thereof for preparing the polyester diols D). The polycarboxylic acids can be aliphatic or cycloaliphatic and optionally, e.g. B. substituted by halogen atoms and / or unsaturated. Examples include: suberic acid, azelaic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, and dimeric fatty acids. Preference is given to dicarboxylic acids of the general formula HOOC- (CH2) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, e.g. B. Bernsteinsäu re, adipic acid, sebacic acid and dodecanedicarboxylic acid.

Also suitable as component D) are polycarbonate diols, such as those used, for. B. can be obtained by implementing phosgene with an excess of the low molecular weight alcohols mentioned as structural components for the Po lyesterpolyols.

The polyesters can contain at least one aliphatic, cycloaliphatic or aromatic monocarboxylic acid E) in copolymerized form. The monocarboxylic acids E) serve to end-cap the polyesters used according to the invention. In principle, all monocarboxylic acids which are capable of reacting with at least some of the available alcohol groups under the reaction conditions of the polyester condensation are suitable. Suitable monocarboxylic acids E) are acetic acid, propionic acid, n-, iso- or tert-butyric acid, valeric acid, trimethyl acetic acid, capric acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, Cyclohexanecarboxylic acid, benzoic acid, methylbenzoic acids, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, phenylacetic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, fatty acids from soy, linseed, castor and sunflower, acrylic acid, methacrylic acid and mixtures thereof.

The polyesters can contain at least one aliphatic or cycloaliphatic monoalcohol F) in copolymerized form. The monoalcohols F) serve to endcap the polyesters used according to the invention. In principle, all monoalcohols which are capable of reacting with at least some of the available carboxylic acid groups under the reaction conditions of the polyamide condensation are suitable. Preferred monoalcohols F) are selected from methanol, ethanol, n-propanol, isopropanol, n-, sec-, tert- and iso-butanol, in each case the isomeric pentanols, hexanols, heptanols, octanols, nonanols, decanols, cyclopentanol, Cyclohexanol and mixtures thereof.

The aliphatic and cycloaliphatic polycarboxylic acids with three or more than three carboxylic acid groups G) are preferably selected from aconitic acid,

1, 3,5-cyclohexane tricarboxylic acid and derivatives and mixtures thereof.

The at least trihydric aliphatic and cycloaliphatic alcohols H) are preferably selected from glycerol, trimethylol methane, trimethylol ethane, trimethylol methane thylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol or higher condensation products of glycerol, di (trimethylolpropane), di (pentaerythritol), Inositols or sugars, such as. B. glucose, fructose or sucrose, sugar alcohols, such as. B. sorbitol, mannitol, threit, erythritol, adonitol (ribitol), arabitol (lyxitol), xylitol, dulcitol (galactitol), maltitol, isomalt, tri- or higher-functional polyetherols based on tri- or higher-functional alcohols and ethylene oxide, propylene oxide and / or butylene oxide.

The lactones I) are preferably derived by intramolecular esterification from compounds of the general formula FiO- (CFi2) _z -COOFI, where z is a number from 1 to 20 and an F1 atom of a methylene unit is also substituted by a C to C4 alkyl radical can be. Examples are e-caprolactone, β-propiolactone, g-butyrolactone and / or methyl-γ-caprolactone and mixtures thereof. The polyesters used according to the invention are then preferably lactone-based polyester diols, which are flomopolymers or copolymers of lactones, preferably addition products of lactones with suitable difunctional starter molecules containing terminal hydroxyl groups. Suitable starter components are, for. B. the vorste starting as a structural component for the polyester polyols mentioned diols B). The corresponding polymers of e-caprolactone are particularly preferred. Lower polyester diols or polyether diols can also be used as starters for the production of the lactone polymers. Instead of the polymers of lactones, it is also possible to use the corresponding, chemically equivalent polycondensates of the hydroxycarboxylic acids corresponding to the lactones.

Suitable compounds K) different from A) to I) and co-condensable therewith are selected from w-aminocarboxylic acids, w-aminocarboxylic acid amides, w-aminocarboxylic acid salts, w-aminocarboxylic acid esters, diamines and dicarboxylic acids, dicarboxylic acid / diamine salts, dinitriles and mixtures thereof .

The polyester is preferably selected from condensation products of an aromatic dicarboxylic acid and an aliphatic diol. In one embodiment, the polyester is polyethylene terephthalate.

Preferably the polyester is hydrophilic. The determination of whether a polyester is hydrophilic can be done by means of contact angle measurement, e.g. B. with a contact angle measuring system G 40 from Krüss. Hydrophilic means that a drop of a sample solution of the polyester on a glass plate has a contact angle of well below 90 °. Polyvinyl formal

The finishing of the cleaning articles according to the invention can additionally comprise at least one polyvinyl formal. To produce such cleaning articles, at least part of the cleaning article is coated or impregnated with at least one polyvinyl alcohol and the coating or impregnation is then subjected to at least partial acetalization with formaldehyde.

In a particular embodiment, the textile and / or sponge-like material has a finish which comprises at least one aliphatic polyester and a polyvinyl formal) foam, hereinafter referred to as (PVA) foam.

In particular, the textile and / or sponge-like material has a finish which comprises at least one aliphatic polyester and a PVF microfoam. The pore size of the PVF foam is preferably less than 100 mΐti.

As is known to the person skilled in the art, the (PVF) foam can be formed by reacting PVA (polyvinyl alcohol) with formaldehyde. This reduces the water solubility of the PVA. According to the invention, the (PVF) foam preferably has a solubility at 100 ° C. of less than 5% by weight.

The finish can contain a polyethylene glycol mono (tristyryl phenyl) ether as a further additive. These compounds are commercially available as nonionic surfactants and are used, among other things, for microencapsulations.

Application process

Finishing the cleaning article comprises at least partial coating of the surface of the cleaning article and / or at least partial impregnation, ie impregnation, of the cleaning article with a composition which contains microcapsules. To equip the cleaning article with microcapsules, an unfinished cleaning article, comprising at least one textile material and / or sponge-like material, is treated with a composition that contains microcapsules. The microcapsules are preferably used in the form of an aqueous dispersion. The finishing is done according to the common application methods, such as a padding process, a doctor blade process, a spray application or a padding process.

In the padder process, the cleaning item is passed through a padder (immersion tank) and then squeezed off to the required amount of aliphatic polyester using a pair of pressure and, if necessary, gap-adjustable rollers.

In the squeegee process, a distinction is made between gravure printing and screen printing. In gravure printing, for example, a knife-like ground steel strip with or without a supporting squeegee is used as the squeegee. It serves to strip the excess dispersion, containing aliphatic polyester, from the webs of the printing cylinder. This process is called doctoring. In screen printing, on the other hand, the squeegee is usually made of rubber or plastic with a sharp or rounded edge.

In the case of spray application, the solution or dispersion containing aliphatic polyester, as defined above, is applied to the cleaning article to be finished by means of a slot nozzle or a slot nozzle.

The kiss-roll process is used to coat the underside of the material of horizontally extending material webs and structured carrier materials. The coating medium can be applied to the web in opposite directions or in parallel. An indirect coating with small application quantities can be realized by means of transfer rollers.

It has proven particularly suitable to impregnate the cleaning article to be finished with an aqueous solution containing an aliphatic polyester or an aqueous dispersion containing an aliphatic polyester. Excess aliphatic polyester can be squeezed off, doctored off, sucked off or worn in some other way, depending on the desired coating or impregnation thickness.

In a particular embodiment, the padding process is used to finish the cleaning articles according to the invention.

The content of microcapsules in the dispersion used to finish the cleaning article is usually from 0.005 to 5.0% by weight, preferably from 0.01 to 3.0% by weight, based on the total weight of the dispersion. The temperature in the finishing process is preferably at most 90.degree. C., preferably at most 80.degree. The temperature in the finishing process is preferably in a range from 10 to 90.degree. C., particularly preferably from 20 to 80.degree.

In addition to water, the microcapsule composition used for finishing can contain at least one organic solvent other than water. The organic solvent is then selected, for example, from methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, ethylene glycol mono (Ci-C4-alkyl ) ethers, ethylene glycol di (Ci-C4-alkyl) ethers, 1,2-propylene glycol, 1,2-propylene glycol mono (Ci-C4-alkyl) ethers, 1,2-propylene glycol di (Ci-C ₄ -alkyl) ethers, Glycerine, polyglycerines, polyalkylene glycols and mixtures thereof. The microcapsule composition used for finishing preferably contains only water as a solvent.

The microcapsule composition used for finishing can additionally contain at least one additive. Suitable additives are, for example, preservatives, rheology modifiers, solubilizers, electrolytes, antioxidants, UV absorbers and mixtures thereof.

Suitable preservatives include quaternary compounds, biguanide compounds, ethylhexylglycerin, caprylylglycol, phenethyl alcohol, propanediol, undecyl alcohol, tocopherol and mixtures thereof. Examples of quaternary compounds are benzalkonium chlorides and / or substituted benzalkonium chlorides, di (C6-Ci4) alkyl-di- (Ci-4) alkyl-ammonium chlorides, N- (3-chloroallyl) -hexamine chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, Diester quaternary ammonium compounds and mixtures thereof.

If at least one additional component is used to finish the cleaning article, preferably selected from at least one aliphatic polyester and / or at least one polyvinyl formal, the finish with microcapsules and with the additional component (s) can be carried out in a single treatment step or in several separate treatment steps respectively.

If the cleaning article is finished with microcapsules and with at least one aliphatic polyester, the finish can be carried out in one step or in two separate steps. Finishing with microcapsules and with at least one aliphatic polyester is preferably carried out in a single treatment step. If the finishing with microcapsules and with at least one aliphatic polyester takes place in one step, an aqueous treatment medium is preferably used which contains the microcapsules in dispersed form and the aliphatic polyester as a solution. The concentration of the aliphatic polyester in the aqueous treatment medium is preferably 20 g / L to 60 g / L, particularly preferably 30 g / L to 50 g / L.

If the finishing with microcapsules and with at least one aliphatic polyester takes place in two separate steps, an aqueous microcapsule dispersion is preferably used for finishing with the microcapsules and an aqueous solution is used for finishing with the aliphatic polyester. The concentration of the aliphatic polyester in the aqueous solution is preferably 20 g / L to 60 g / L, particularly preferably 30 g / L to 50 g / L. The order of the equipment steps is then arbitrary.

If the cleaning article is equipped with microcapsules and with at least one polyvinyl formal, the finishing with the microcapsules and the first step of finishing with at least one polyvinyl formal, the treatment with at least one polyvinyl alcohol, can be carried out in one step or in two separate steps. Finishing with microcapsules and with at least one polyvinyl alcohol is preferably carried out in two separate treatment steps.

If the cleaning article is equipped with microcapsules and with at least one polyester, the finish with the microcapsules and the polyester can take place in one step or in two separate steps. Finishing with the microcapsules and the polyester is preferably carried out in a single treatment step.

In particular, the cleaning article has areas that are equipped with the polyester and areas that are not equipped with the polyester. Advantageously, the areas not provided with a polyester are unfinished; H. uncoated or not impregnated.

Another object of the invention is the use of the cleaning article according to the invention, as defined above, various surfaces, especially non-textile surfaces, in particular floors and stairs, furniture, kitchen surfaces, windows and doors, mirrors and other glass surfaces, ceramic, wood and metal surfaces . The cleaning article is preferably in the form of a wipe, cleaning cloth, floor mop, mop, dust cloth, sponge or sponge cloth. Another object of the invention is the use of multi-layer microcapsules filled with at least one fragrance, as defined above, for equipping cleaning articles with a long-lasting fragrance.

The following examples serve to illustrate the invention without restricting it in any way.

EXAMPLES

To test the smell, a textile made of 60% viscose, 25% polyester and 15% polypropylene is equipped with microcapsules. The 10 textile samples used for the odor test are washed in a conventional washing machine at 60 ° C without detergent to simulate usage cycles per cycle.

Claims

PATENT CLAIMS

1. Cleaning article, comprising at least one textile and / or sponge-like material which has a finish, the finish comprising microcapsules which have at least one core which contains at least one fragrance.

2. The cleaning article of claim 1, wherein the finish comprises two-ply, three-ply, or more than three-ply microcapsules.

3. Cleaning article according to one of the preceding claims, wherein the microcapsules comprise at least one shell which has at least one layer which contains at least one polymer selected from polyurethanes, polyureas and mixtures thereof.

4. Cleaning article according to one of the preceding claims, wherein the equipment additionally comprises at least one polyester.

5. Cleaning article according to claim 4, wherein the components used to produce the aliphatic polyester are selected from

A) aliphatic, cycloaliphatic and aromatic dicarboxylic acids,

B) aliphatic and cycloaliphatic diols,

C) low molecular weight aliphatic and cycloaliphatic glycols,

D) polymeric aliphatic and cycloaliphatic diols, selected from polyether diols, polyester diols, polyether ester diols and polycarbonate diols,

E) aliphatic, cycloaliphatic and aromatic monocarboxylic acids,

F) aliphatic and cycloaliphatic monoalcohols,

H) at least trihydric aliphatic and cycloaliphatic alcohols,

I) lactones,

K) from A) to I) different, thus cocondensable compounds.

6. Cleaning article according to one of claims 4 or 5, wherein the aliphatic polyester is selected from condensation products of at least one aromatic dicarboxylic acid and at least one aliphatic diol.

7. Cleaning article according to one of claims 4 to 6, wherein the polyester is hydrophilic.

8. Cleaning article according to one of claims 4 to 7, wherein the cleaning article contains the polyester in an amount of 2 to 25% by weight, in particular 3 to 10% by weight, based on the total weight of the cleaning article.

9. Cleaning article according to one of the preceding claims, wherein the micro-capsules are physically bound to the textile or sponge-like material.

10. Cleaning article according to one of the preceding claims, wherein the equipment additionally comprises at least one polyvinyl formal.

11. Cleaning article according to one of the preceding claims, which comprises a textile material or consists of a textile material which contains fibers selected from natural plant and animal fibers, chemical fibers made from natural and synthetic polymers and combinations thereof, preferably selected from fibers Polyamide, polyester, viscose, polyvinyl alcohol, polyacrylonitrile, triacetate, acetate, polycarbonate, polyolefins, glass fibers, cotton, linen, wool, polylactide and mixtures thereof.

12. Cleaning article according to one of the preceding claims, which comprises a textile material or consists of a textile material which contains fibers in the form of staple fibers, filaments or combinations thereof.

13. A method for producing a cleaning article, wherein at least part of the cleaning article is coated or impregnated with an aqueous dispersion which contains multilayer microcapsules as defined in one of claims 1 to 3.

14. The method according to claim 13, wherein at least part of the cleaning article with an aqueous solution or dispersion containing at least one polyester, as defined in one of claims 4 to 8, is.

15. The method according to claim 13 or 14, wherein at least part of the cleaning article is coated or impregnated with at least one polyvinyl alcohol and the coating or impregnation is then subjected to at least partial acetalization with formaldehyde.

16. Use of a cleaning article, as defined in one of claims 1 to 12, for cleaning various surfaces, especially non-textile surfaces, especially floors and stairs, furniture, kitchen surfaces, windows and doors, mirrors and other glass surfaces, ceramics , Wood and metal surfaces.

17. Use of microcapsules filled with at least one fragrance, as defined in one of claims 1 to 3, for equipping cleaning articles with a long-lasting fragrance.