DE102019123275A1 - Cleaning articles with dirt-repellent properties - Google Patents

Abstract

The present invention relates to a cleaning article which is at least partially finished with a polyester, a method for producing a cleaning article and the use of the cleaning article.

Description

BACKGROUND OF THE INVENTION

The present invention relates to a cleaning article which is at least partially finished with a polyester, a method for producing a cleaning article and the use of the cleaning article.

STATE OF THE ART

Various types of cleaning cloths are known in the household and in professional cleaning, which are used for cleaning the floor or other surfaces. The cleaning wipes can have a simple structure in that they are formed, for example, from a single-layer textile base body. It is important for the cleaning cloth that it absorbs the dirt from the surface to be cleaned well and releases it as completely as possible during the wringing process. In addition, the water absorption and release of the cloth is important. On the one hand, water is required to loosen adhering dirt, on the other hand, it binds the loosened dirt or loose dirt particles such as dust etc. and removes it from the surface to be cleaned with the cloth. Furthermore, the sliding properties of the cloth are important for the user. It has been shown here that when cleaning large surfaces (e.g. windows, school boards, large tables, walls, car bodies), the cleaning cloth should glide rather easily in order to achieve good ergonomics and less effort when wiping. In the case of smaller or heavily soiled surfaces, on the other hand, users often prefer cleaning cloths with a higher level of friction so that adhering dirt can be removed more easily or the cleaning process can also be detected haptically.

To increase the cleaning performance, it is known to provide textile carrier materials with a coating or impregnation. For example, textile materials can be provided with a polyurethane (PU) coating or impregnation. The application of the PU coating or impregnation compound is carried out according to current practice such that the substrate is immersed in a solution of PU and dimethylformamide (DMF). This is used in US 4201824 or US 20120015574 described.

Another known method is the coating or impregnation of a textile carrier material consisting of PVA (polyvinyl alcohol) fibers with a PVF microfoam (polyvinyl formal microfoam). With this method, the surface of the fibers is partially dissolved in the aqueous medium during the coating / impregnation process and a permanent and wash-stable chemical-physical surface connection between the carrier and coating material is achieved. DE 102013008985 and EP 3004452 describe a textile carrier material that is at least partially coated with PVF microfoam.

Another possibility is the coating or impregnation of textile materials with polyester-containing compositions.

US 5234753 describes a dirt-repellent composition that is used for application to or finishing of polyester textiles. The soil-repellent composition comprises a non-fiber-forming polyester-polyether copolymer and an antioxidatively effective amount of a sterically hindered phenol antioxidant material. The dirt-repellent composition is heat-set to the polyester textiles at a temperature of at least 191 ° C.

US 4045172 also describes a soil-repellent composition for textiles made from polyester-containing cellulose fibers, the compositions comprising partial alkyl and alkoxyalkyl esters and mixed esters of interpolymers of maleic anhydride with unsaturated compounds, such as styrene and ethylene, and with polyvinyl alkyl ethers, in which the proportion by weight of the esterified interpolymer is decisive.

US 3674548 describes textile materials containing natural fibers which can be obtained by treating a composition consisting of a textile resin, a pigment and a hydrophobic film-forming polymer binder. If additional dirt-repellent properties are desired for the textile material, dirt-repellent polymers such as synthetic acid polymers and low molecular weight polyesters of polycarboxylic acids and polyalkylene oxides are applied to the fabric in addition to the materials mentioned above.

US 6770581 describes fabrics, particularly absorbent knitted polyester fabrics, and methods of making such fabrics. In order to make the yarn / fabric hydrophilic, it can be advantageous that the yarn / fabric is chemically treated with an anionically ethoxylated sulfonated polyester (AESP, surfactant / stabilizer) and a high molecular weight ethoxylated polyester (HMWEP, lubricant / plasticizer). This treatment should enable the polyester fabric to quickly absorb water and promote moisture transport. Such chemical treatment is also said to help prevent stains in the fabric.

The treatment methods known from the prior art lead to textiles which have good cleaning properties. However, these are still in need of improvement.

It is therefore the object of the invention to provide a cleaning article which has an advantageous profile of properties and especially good cleaning properties. In particular, a cleaning article is to be provided which has both good dirt absorption properties (dirt binding properties) and good protective release properties when rinsed out. Textile cleaning articles should have good water absorption and sliding properties.

It has surprisingly been found that this object is achieved by the cleaning article according to the invention, the method for producing the cleaning article and its use.

• - Es können Reinigungsartikel zur mehrfachen Verwendung bei der Reinigung von Oberflächen mit wenigstens einem Polyester ausgerüstet werden.
• - Die Reinigungstextilien lassen sich über eine lange Zeit nutzen, wobei der Verbraucher den Eindruck hat, dass der benutzte Reinigungsartikel selbst nicht verschmutzt.
• - Die erfindungsgemäßen Reinigungsartikel weisen sowohl gute Schmutzaufnahmeeigenschaften (Schmutzbindungseigenschaften) als auch beim Ausspülen gute Schutzablöseeigenschaften auf.
• - Die Ausrüstung mit wenigstens einem Polyester kann erfolgen, ohne dass ein zusätzliches Bindemittel, z. B. ein Polyurethan-Kunstharz, nötig ist.
• - Eine zusätzliche Ausrüstung der Reinigungsartikel mit wenigstens einem Polyvinylformal führt nicht zu einer Anbindung des Polyesters an die Fasern des Reinigungsartikels über das Polyvinylformal.
• - Die angestrebte Wirkung lässt sich mit einer geringen Einsatzmenge an Polyestern erzielen.
• - Die Griffeigenschaften der Reinigungsartikel werden durch die vorgenommene Ausrüstung verbessert.

The cleaning article according to the invention has the following advantages:

• Cleaning articles for multiple use when cleaning surfaces can be equipped with at least one polyester.
• The cleaning textiles can be used over a long period of time, with the consumer having the impression that the cleaning article used does not itself become soiled.
• The cleaning articles according to the invention have both good dirt absorption properties (dirt binding properties) and good protective release properties when rinsed out.
• - Finishing with at least one polyester can be done without an additional binder, e.g. B. a polyurethane resin is necessary.
• Additional finishing of the cleaning article with at least one polyvinyl formal does not lead to a binding of the polyester to the fibers of the cleaning article via the polyvinyl formal.
• - The desired effect can be achieved with a small amount of polyesters.
• - The grip properties of the cleaning articles are improved by the equipment made.

SUMMARY OF THE INVENTION

A first object of the invention is a cleaning article, comprising at least one textile and / or sponge-like material, which has a finish that comprises at least one polyester.

A second subject matter of the invention is a method for producing a cleaning article, the cleaning article being at least partially upgraded with an aqueous dispersion containing at least one polyester.

Another object of the invention is the use of the cleaning article according to the invention for cleaning various surfaces, in particular non-textile surfaces.

DESCRIPTION OF THE INVENTION

The cleaning article according to the invention is advantageously suitable for wet and dry cleaning of various surfaces, especially non-textile surfaces, such as floors and stairs, furniture, kitchen surfaces, windows and doors, mirrors and other glass surfaces, ceramic, wood and metal surfaces, surfaces In other words, the cleaning article according to the invention has an increased cleaning performance. The increased cleaning performance is reflected in the fact that the cleaning article according to the invention has very good water absorption and very good rinsing behavior with respect to dirt. The dirt is very well absorbed by the cleaning article during cleaning. The absorbed dirt particles can very easily be rinsed out with water, causing pollution of the cleaning article is reduced. In addition, the increased cleaning performance is also maintained by machine cleaning of the cleaning article itself.

The cleaning article according to the invention exhibits improved dirt and dirt deposition behavior and / or improved rinsability of the dirt picked up when repeatedly cleaned in aqueous detergent solutions or dry cleaning solvents.

In the context of the invention, the cleaning article according to the invention comprises at least one textile and / or sponge-like material.

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

The fibers can be characterized by their fineness, i. H. the weight related to 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 fibers in the form of microfibers. In the context of the invention, “microfibers” are fibers that 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 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 therefore 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 deposited into a fleece, in particular in the form of at least partially split composite filaments. Composite filaments consist of at least two elementary filaments and can be split into elementary filaments and consolidated using 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 which 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, polyvinyl alcohol, polyacrylonitrile, 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, within the meaning of the invention, materials are regarded as hydrophobic in which water on the surface of a compact body formed from them has a contact angle of greater than or equal to 90 °. The contact angle can e.g. B. be determined with a contact angle measuring device 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 °.

The cleaning article according to the invention particularly preferably comprises fibers which contain or consist of the following materials: polyamides, polyester, viscose, polyvinyl alcohol, polyacrylonitrile, triacetate, acetate, polyolefins, polyvinyl chloride and / or mixtures thereof. Suitable polyamides are PA 6, PA 66, PA 46, PA610, PA612, PA10, PA810, 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. Specifically, the cleaning article of the invention comprises composite filaments comprising at least two incompatible polymers. Incompatible polymers are to be understood as meaning those polymers which, in combination, do not give rise to pairings that adhere only to a limited extent or that are difficult to adhere. 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 pairings is easier than with a composite filament that consists only of one of the polymers used.

The incompatible polymer pairs used are preferably polyolefins, polyesters, polyamides and / or polyurethanes in such a combination that pairings that are not, or only partially, or 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, polyamide / polypropylene or polyethylene terephthalate / polypropylene.

The cleaning articles according to the invention comprise at least one textile material, which is preferably selected from nonwovens, knitted fabrics, woven fabrics and combinations thereof. In the context of the invention, nonwovens are understood to be textile fabrics 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 way, 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 one 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 the case of woven fabrics, 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 e.g. B. be designed as a sponge or as a sponge cloth. The sponge-like material can be open-cell or closed-cell. Open-cell sponge-like materials can generally absorb larger amounts of liquid from a surface to be cleaned, whereas closed-cell sponge-like materials because of their ability to absorb 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 embodiment, 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 a further suitable embodiment, the sponge consists of a viscose sponge. One possible embodiment of a cleaning article according to the invention is, for. B. a scouring pad. 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 are suitable, which are prepared in a known manner, e.g. B. by the viscose process can be produced.

The polyesters according to the invention are polymers whose repeating units are predominantly linked to one another by ester groups. The polyester according to the invention does not contain any ethylenically unsaturated double bonds. The polyester according to the invention does not contain any urethane or urea groups.

In the context of the invention, the term aliphatic polyester also encompasses 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 present 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 C ₁ -C ₄ -alkyl esters, in particular the methyl esters or ethyl esters.

• A) aliphatischen, cycloaliphatischen und aromatischen Dicarbonsäuren,
• B) aliphatischen und cycloaliphatischen Diolen,
• C) niedermolekularen aliphatischen und cycloaliphatischen Glycolen,
• D) polymeren aliphatischen und cycloaliphatischen Diolen,
• E) aliphatischen, cycloaliphatischen und aromatischen Monocarbonsäuren,
• F) aliphatischen und cycloaliphatischen Monoalkoholen,
• G) aliphatischen und cycloaliphatischen Polycarbonsäuren mit drei oder mehr als drei Carbonsäuregruppen,
• H) mindestens dreiwertigen aliphatischen und cycloaliphatischen Alkoholen,
• I) Lactonen,
• K) von A) bis I) verschiedenen, damit cokondensierbaren Verbindungen.

The components used to produce the polyesters 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,
• H) 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, pimelic acid, suberic acid, azelaic acid, Sebacic acid, undecane-α, ω-dicarboxylic acid, dodecane-α, ω-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, naphthalenedicarboxylic 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) C ₁ -C ₄ -alkyl radical. In particular, substituted aromatic dicarboxylic acids A) have 1 or 2 C ₁ -C ₄ -alkyl radicals. These are preferably selected from 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.

The aromatic dicarboxylic acid A) used is particularly preferably 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 compounds which have a molecular weight of 60 to less than 500 g / mol. The low molecular weight compounds C) are particularly preferably 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. The compounds D) are particularly preferably 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 HO (CH ₂ CH ₂ O) _n —H, polypropylene glycols HO (CH [CH _3] CH ₂ O) _n —H, where n is an integer and n 4, polyethylene polypropylene glycols, where the sequence 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 of the hydroxyl groups in the above-mentioned diols 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, to starting components with reactive hydrogen atoms, 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. 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 dihydric carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof for the preparation of the polyester diols D). The polycarboxylic acids can be aliphatic or be 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- (CH ₂ ) _y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, e.g. B. succinic acid, 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 reacting phosgene with an excess of the low molecular weight alcohols mentioned as structural components for the polyester polyols.

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, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, pivalanic 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, flaxseed, 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 end-cap 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 isobutanol, in each case the iomeric pentanols, hexanols, heptanols, octanols, nonanols, decanols, cyclopentanol, cyclohexanol and mixtures thereof.

The aliphatic and cycloaliphatic polycarboxylic acids with 3 or more than 3 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, trimethylolmethane, trimethylolethane, trimethylolpropane, 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 HO- (CH ₂ ) _z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit is also represented by a C ₁ - to C ₄ -Alkyl radical can be substituted. Examples are ε-caprolactone, β-propiolactone, γ-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 homopolymers 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 diols B) mentioned above as a structural component for the polyester polyols. The corresponding polymers of ε-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 ω-aminocarboxylic acids, ω-aminocarboxylic acid amides, ω-aminocarboxylic acid salts, ω-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 °.

The invention further provides a method for producing a cleaning article, the cleaning article being at least partially finished with an aqueous solution or dispersion containing at least one polyester, as defined above.

To finish the cleaning article, an unfinished cleaning article, comprising textile material and / or sponge-like material, is treated with an aqueous solution or dispersion containing at least one polyester, as defined above.

Finishing the cleaning article is at least partial coating of the surface of the cleaning article and / or at least partial impregnation, d. H. Soaking the cleaning article with an aqueous solution or dispersion containing at least one polyester, as defined above.

The finishing is done according to the usual application methods, such as a padding process, a doctor blade process, a spray application or a padding process.

In the padding process, the cleaning article is passed through a padding tank (immersion tank) and then squeezed off to the desired application quantity of polyester via a pressure and, if necessary, gap-adjustable roller pair.

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 wipe off the excess dispersion, containing 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 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 horizontally running 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 a polyester or an aqueous dispersion containing a polyester. Excess polyester can be squeezed off, doctored off, vacuumed or removed in another 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 concentration of the polyester in the aqueous solution is preferably 20 g / L to 60 g / L, more preferably 30 g / L to 50 g / L.

The temperature in the finishing process is preferably between 60.degree. C. and 200.degree. C., preferably between 80.degree. C. and 180.degree.

The solution or dispersion used for finishing can additionally contain at least one additive. Suitable additives are e.g. B. preservatives, rheology modifiers, solubilizers, electrolytes, antioxidants, UV absorbers and mixtures thereof.

In a further embodiment, the solution or the dispersion, comprising at least one polyester, contains at least one preservative in order to prevent microbial contamination. The preservative can be dissolved or dispersed in the composition used for finishing. In particular, the preservative is contained in the aqueous medium of the solution or dispersion used for finishing.

Suitable preservatives include quaternary compounds, biguanide compounds, ethylhexyl glycerine, caprylyl glycol, phenethyl alcohol, propanediol, undecyl alcohol, tocopherol, and mixtures thereof. Examples of quaternary compounds are benzalkonium chlorides and / or substituted benzalkonium chlorides, di (C ₆ -C ₁₄ ) alkyl-di- (C _1-4 ) alkylammonium chlorides, N- (3-chloroallyl) hexamine chloride, benzethonium chloride, methylbenzethonium chloride, cetylpyridinium chloride, diester Quaternary ammonium compounds and mixtures thereof.

The finishing process for the cleaning article according to the invention can optionally be followed by a drying step. Drying takes place at a temperature of 15 to 120.degree. C., preferably at 20 to 90.degree.

The finishing of the textile and / or the sponge-like material is preferably carried out physically. This means that water and easily evaporable substances are released into the environment. According to the invention, the polyester adheres to the textile material and to the sponge-like material. According to the invention, the textile material and / or the sponge-like material are enveloped by the polyester. No covalent bonds are made between the polyester and the textile material and the sponge-like material. The textile and / or the sponge-like material are not chemically changed during the finishing process.

In particular, the cleaning article has areas that are finished with the polyester and areas that are not finished with the polyester. Advantageously, the areas not provided with a polyester are unequipped, i. E. H. uncoated or not impregnated.

The cleaning article according to the invention preferably contains the polyester, as defined above, in an amount of 2 to 25% by weight, in particular 3 to 10% by weight, based on the total weight of the cleaning textile.

The invention also relates to a method in which at least part of the cleaning article equipped according to the invention 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 polyester and one polyvinyl formal foam, hereinafter referred to as (PVF) foam.

In particular, the textile and / or sponge-like material has a finish that has at least one polyester and one PVF microfoam. The pore sizes of the PVF foam are preferably below 100 μm.

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 water solubility at 100 ° C. of less than 5% by weight.

In a suitable embodiment for equipping a cleaning article with a (PVF) foam and a polyester, polyvinyl alcohol is first applied to the cleaning article and converted into (PVF) foam. The finishing with the polyester is then carried out in a separate step.

The finish can contain a polyethylene glycol mono (tristyrylphenyl) ether as a further additive. These compounds are commercially available as nonionic surfactants.

Another object of the invention is the use of the cleaning article according to the invention, as defined above, for cleaning various surfaces, especially non-textile surfaces, especially floors and stairs, furniture, kitchen surfaces, windows and doors, mirrors and others Glass, ceramic, wood and metal surfaces. The cleaning article is preferably used in the form of a wipe, cleaning cloth, floor mop, dust cloth, sponge, sponge cloth or mop.

Another object of the invention is the use of at least one polyester, as defined above, for finishing cleaning articles to reduce soiling during use and / or to improve the rinsability of the dirt that has been picked up.

Figure list

• 1 : Effect visualization after using the cleaning article according to the invention made of 85% polyester, 15% polyamide, equipped with a PET; Type of dirt: 80% coffee extract, 10% coffee powder, 10% common household kitchen soiling.

Implementation: normal household use over a period of 14 days, with daily rinsing of the cleaning item; final thorough rinsing process under running water.

Left: cleaning article equipped with PET (according to the invention) Right: cleaning article not equipped (comparative example)

EXAMPLES

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

The following test is carried out to assess the washability of various types of stains after several household washes.

• - Mayonnaise,
• - Senf,
• - Tomatenmark,
• - heißer Kaffee,
• - schwarzer Tee,
• - Kondensmilch,

From the cleaning article made of 60% viscose, 25% polyester and 15% polypropylene, equipped with PET, one test item is washed 1 x 40 ° C, 5 x 40 ° C and 10 x 40 ° C (main wash cycle with a commercially available color detergent The three test items now available are with the following food products:

• - mayonnaise,
• - mustard,
• - tomato paste,
• - hot coffee,
• - black tea,
• - condensed milk,

approx. 2 cm in size wetted. Before wetting, the test specimens are dried on the uncoated side with the iron. The stain is acted on for 30 minutes. Afterwards, the protruding remnants of the respective stains are roughly removed with a clean cloth, after which the test objects are left for a further 24 hours. The spots are marked with a real pen. This is followed by washing once at 40 ° C. and drying the uncoated side with the iron. The stains marked with a washable pen are now assessed. The experimental data are summarized in Table 1. Table 1: 1 x 40 ° C washed + ironing • • 5 x 40 ° C washed + ironing • • 10 x 40 ° C washed + ironing • • mayonnaise 1 1 1 mustard 1 1 1 Tomato paste 1 1 1 hot coffee 1 1 1 black tea 2 2 2 Condensed milk 1 1 1 Grading: 1 = completely removed 2 = still visible 3 = visible 4 = strongly visible

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• US 4201824 [0003]
• US 20120015574 [0003]
• DE 102013008985 [0004]
• EP 3004452 [0004]
• US 5234753 [0006]
• US 4045172 [0007]
• US 3674548 [0008]
• US 6770581 [0009]

Claims (14)

Cleaning article comprising at least one textile and / or sponge-like material having a finish comprising at least one polyester. Cleaning articles after Claim 1 , the components used to produce the polyesters being 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 and cycloaliphatic diols aromatic monocarboxylic acids, F) aliphatic and cycloaliphatic monoalcohols, G) aliphatic and cycloaliphatic polycarboxylic acids with three or more than three carboxylic acid groups, H) at least trihydric aliphatic and cycloaliphatic alcohols, I) lactones, K) compounds different from A) to I) co-condensable therewith . Cleaning article according to one of the preceding claims, wherein the polyester is selected from condensation products - At least one aromatic dicarboxylic acid and at least one aliphatic glycol. A cleaning article according to any preceding claim, wherein the polyester is hydrophilic. A cleaning article according to any one of the preceding claims, wherein the finish is physically bound to the textile or sponge-like material. Cleaning article according to one of the preceding claims, 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. Cleaning article according to one of the preceding claims, wherein the fibers are selected from polyamide, polyester, viscose, polyvinyl alcohol, polyacrylonitrile, triacetate, acetate, polycarbonate, polyolefins, glass fibers, cotton, linen, wool, polylactide and mixtures thereof. Cleaning article according to one of the preceding claims, which comprises a textile material or consists of a material which comprises fibers in the form of staple fibers, filaments or combinations thereof. Cleaning articles after Claim 8 , wherein the fibers comprise at least two polymers, preferably comprise at least one polyester and at least one polyamide. Cleaning articles according to one of the Claim 1 to 6th , the sponge-like material being selected from polyester-polyurethanes, polyether-polyurethanes and viscose. A method for producing a cleaning article, wherein the cleaning article with an aqueous solution or dispersion containing a polyester, as in one of the Claims 1 to 10 is defined, at least partially equipped. Procedure according to Claim 11 , wherein a) 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, b) the cleaning article obtained in step a) with at least one polyester as in the Claims 1 to 10 is equipped in a defined manner. Use of a cleaning article, as in one of the Claims 1 to 10 defined, for wet and dry cleaning of various surfaces, especially non-textile surfaces, especially floors and stairs, furniture, kitchen surfaces, windows and doors, mirrors and other glass surfaces, ceramic, wood and metal surfaces. Use of at least one polyester, as in one of the Claims 1 to 10 defined, for equipping cleaning articles to reduce soiling during use and / or to improve the rinsability of the dirt picked up.

Images