WO1996008601A1

WO1996008601A1 - Tissue paper treating agent, process for producing tissue paper by using said treating agent and its use

Info

Publication number: WO1996008601A1
Application number: PCT/EP1995/003588
Authority: WO
Inventors: Harald Elstner; Peter Von Paleske; Walter Hill
Original assignee: Sca Hygiene-Paper Gmbh
Priority date: 1994-09-16
Filing date: 1995-09-12
Publication date: 1996-03-21
Also published as: PL183481B1; EP0803012A1; DE59506319D1; EP0803012B1; CZ77897A3; NO971198L; FI971103A; AU3566295A; GR3031031T3; PL319139A1; SK32497A3; HU220737B1; ES2136307T3; CA2200049A1; NO971198D0; HUT77476A; FI971103A0; ATE181754T1

Abstract

A polysiloxane-containing treating agent for tissue paper products contains 25 to 95 parts by weight of polyethylene glycol and/or glycerine liquid at room temperature, 5 to 75 parts by weight polysiloxane and 0 to 25 parts by weight water with respect to 100 parts by weight of said mixture. Also disclosed is a process for applying said medium on a tissue paper web and its use.

Description

Tissue treating agent, method of making tissue paper using the treating agent and its use

The present invention relates to a treatment agent for increasing the softness of tissue paper, a method for producing tissue paper and products made therefrom using this treatment agent, and the use of the treatment agent.

Softness is an important property of tissue products such as handkerchiefs, facial tissues, toilet paper, napkins and also hand or kitchen towels and describes the feeling that the tissue paper creates when it touches the skin.

As described in the article "Softness and Softening of Hygiene Tissue" in the weekly paper for paper manufacture issue 11/12, 1988, on page 435 ff., The term softness is generally understandable, but extremely difficult to define, since no physical method of determination and therefore there is no recognized industrial standard as a standard for classifying different degrees of softness.

In order to really be able to grasp the softness, it has to be determined by a subjective method, ie it is determined by determined a so-called panel test, in which several trained test persons give a comparative judgment.

Softness can be broken down into its main characteristics, surface softness and softness:

Surface softness describes the feeling that you feel when you run your fingertips lightly over the surface of the tissue sheet.

Crumple softness is the sensory impression that a tissue squeezed with the hands creates during the process of squeezing.

The usual measures for producing or improving the softness of tissue paper can be divided into three main categories:

1. Selection of raw materials, especially pulp,

2. mechanical measures (e.g. grinding, sheet formation, drying and creping, smoothing) and

3. chemical additives.

Tissue papers require different properties depending on the intended use. For kitchen towels and even more so for towels, strength, in particular strength when wet and high suction power, are required in order to meet the demands of the consumer. With other products, such as handkerchiefs or facial tissues, the softness of the surface and very good suppleness are salient properties that determine the practical value of these products in addition to strength. In the case of toilet paper, a combination of dry strength in addition to good softness and good thickness perception determines suitability for use and consumer acceptance. It is a particular challenge for papermakers to bring the various, often contradicting, influencing factors into a special balance in order to present the optimal combinations of properties required by the consumer for the desired end products.

It is now a sign of the times that across all product areas of hygiene articles, improving softness is one of the most important requirements for the paper maker. Properties such as softness of a tissue product are determined in their basic formation by the manufacturing process and the selection of the raw and auxiliary materials, as previously discussed.

The tissue manufacturing process, regardless of its various variants, comprises the following procedural steps:

Suspending the fiber materials in water, possibly adding chemical aids to influence the product properties and process sequence, activating the fiber surfaces to unlock the strength potential of the fiber raw materials by mechanical treatment such as grinding in a refiner, sheet formation by laying down the fibers, oriented or in a tangled position on one or between two endlessly rotating sieves of the paper machine with simultaneous removal of the main amount of dilution water to a dry content between 12 and 35%, drying of the primary nonwoven formed in one or more steps by mechanical and thermal means to a final dry content of around 93 to 97%. One of the most relevant steps for tissue production is the creping process, which dominates the properties of the finished tissue product in the conventional process. In today's dry crepe process, the creping is done on a drying cylinder, usually 4.5 to 6 m in diameter, the so-called Yankee cylinder, with the help of a Crepe scraper at the aforementioned final dry content of the tissue paper. In older processes with lower demands on the tissue quality, the wet crepe process is also used, which is similar to the dry crepe process, but with lower dry contents below 80%, usually around 55 to 65% dry content, with subsequent drying on subsequent drying cylinders of a dryer section to the final dry content. In a subsequent step, the creped, end-dry raw tissue paper (raw tissue) is wound up on a supporting core to form a so-called drum or cut lengthways on sleeves to form mother rolls and is available in the form for further processing into finished products.

For the production of multi-layer tissue papers, such as. B. handkerchiefs, toilet paper, towels or kitchen towels, there is often an intermediate step with the so-called doubling, in which the raw cotton (raw tissue) is usually wound in a number of tambour corresponding to the desired number of layers of the finished product and wound up into a common, multi-layer mother roll. In this processing step, smoothing or calibration in two- or multi-roll smoothing plants is often included. However, the smoothing (calibration) can also be carried out in the tissue production machine after drying and creping directly before the reeling.

The processing process, for example into folded products such as handkerchiefs or facial tissues, takes place in downstream, separate work steps in special processing machines designed for the task, the processes such as smoothing the tissue again, embossing the edges, sometimes combined with a flat and / or selective gluing to produce Layer liability of the individual layers to be brought together (raw tissue) as well as longitudinal section, folding, cross-section, storage and merging of several individual tissues and their packaging in so-called tissue bags or special jewelery boxes and their combination into larger outer packaging or containers. Instead of the edge embossing, the layer adhesion generation can also be generated by knurling, as is the case, for example, with B. is common in cosmetic wipes.

In addition to the described, conventional tissue production process, modified process technologies are used in particular in the USA, today increasingly also in Europe, in which a special type of drying within the tissue machine improves the specific volume and in this way improves the softness of the tissue thus produced tissues is achieved. These processes, which exist in different subspecies, are referred to as TAD (Through Air Drying) processes. Their characteristic is that the "primary" nonwoven leaving the sheet formation is pre-dried to a dry matter content of about 80% on the Yankee cylinder before the final contact drying. Hot air is blown through the nonwoven. The nonwoven is supported by an air-permeable sieve or belt and guided during its transport over the surface of an air-permeable, rotating cylinder drum. By structuring the support sieve or the belt, any pattern of compacted and by deformation in the moist state on loosened zones can be generated, which are related to increased, medium, specific volumes This leads to an increase in softness of the crumple, without the strength of the nonwoven fabric dropping below the level required for use. A further possibility of influencing the soft tissue and strength in the production of raw tissue consists in the use of a layering in which d The primary nonwoven fabric to be formed is built up by a specially designed headbox in the form of different layers of fibrous material, which are fed together as a material jet to form the sheet. When using layering, nonwovens consisting of two, three or more layers belong to the state of the art Technology, for example DE-C 43 47 499. The surface softness can be significantly increased by a suitable selection of raw materials in the channels of the headbox exit nozzle which determine the stratification, for example the use of eucalyptus fibers on the nonwoven side facing the Yankee cylinder surface, which is the result of the products made from the raw tissue production benefits.

In addition, the use of chemicals in the form of a lotion application to the raw tissue during the raw tissue production process, the doubling or the subsequent processing for improving the softness is known. The term “lotion” in cosmetic parlance includes, as is generally understood, aqueous or aqueous-alcoholic preparations with emulsifying active ingredients. In particular, the use of aqueous solutions or emulsions of polyhydroxy compounds such as glycol or polyethylene glycol or the use of polysiloxanes to improve the softness of tissue are not described is, however, that a significant increase in softness can be achieved as a synergy effect of a mixture of a polysiloxane with a polyethylene glycol in an aqueous emulsion.

The use of polysiloxanes as a treatment agent for improving the softness of tissue is described in the patent literature. So far, however, it is not known that a significant increase in softness as a synergy effect of using a mixture of a polysiloxane with a polyhydroxy compound, such as. B. polyethylene glycol or glycerin in aqueous emulsion can be achieved as a treatment agent for tissue. For example, WO 90/09807 relates to a tissue product which contains at least one tissue layer, this tissue product containing 0.1 to 5% by weight of solids of a silicone compound. This is preferably an aqueous emulsion and / or solution of these silicone compounds. From this patent application the US patent 49 50 545 emerged. EP-A-0 347 154 relates to tissue paper with a basis weight of 10 to 65 g / m ² and a density of not more than 0.6 g / ml, this paper containing cellulosic fibers and a polysiloxane material, the amount at least 0.004% polysiloxane, based on the dry (fiber) weight of this nonwoven. The subject of US Patent 50 59 282 resulting therefrom is correspondingly restricted a tissue paper with a basis weight of 10 to 65 g / m ² and a density of not more than 0.6 g / ml, this paper cellulose fibers and an effective content of a polysiloxane material contains, said polysiloxane being applied uniformly to the outward-facing surfaces of the tissue paper, this effective content of the polysiloxane relating to 0.004% to 2% of the polysiloxane, based on the dry (fiber) weight of the tissue paper, this polysiloxane having a viscosity of Has 25 centistokes and more and has a wetting time of no more than 2 minutes after an aging time of two weeks after its production. A manufacturing process for such a paper is the subject of EP-A-347 153 or the corresponding US patent 52 15 626.

WO93 / 02252 relates to a manufacturing process. for soft tissue paper with the sequence of sheet formation from an aqueous suspension (wet laying) of cellulose fibers to form a nonwoven fabric, drying the nonwoven fabric while increasing the temperature of the nonwoven fabric to at least 43 ° C., creping the nonwoven fabric at a temperature of at least 43 ° C. Treatment of the nonwoven fabric at a temperature of at least 43 ° C with a sufficient amount of a polysiloxane so that 0.004% to 0.75% of this polysiloxane based on the dry (fiber) weight of this tissue paper remains in this nonwoven fabric, this tissue paper having a basis weight from 10 to 65 g / m and a density of less than 0.6 g / m ³ . After a In a preferred embodiment, a water-soluble surfactant can be added at the same time as the polysiloxane. This subject is also described in US-A-50 59 282.

WO94 / 05857 relates to a method for applying a chemical papermaking additive to a dry tissue paper fleece (tissue paper fleece, raw tissue), this method being characterized in that it contains the following steps:

To provide a dry tissue paper nonwoven, diluting a chemical paper making additive with a suitable solvent to form a dilute chemical solution, applying that diluted chemical solution to a heated transfer surface, partially evaporating the solvent through the transfer surface to form a film containing this paper making additive, and transferring the film from the heated transfer surface to the surface of the tissue nonwoven such that a sufficient amount of the chemical papermaking additive is made such that 0.004 to 2% of this chemical papermaking additive, based on the dry (fiber) weight of this tissue nonwoven, remains in this tissue nonwoven. This papermaking additive is preferably understood to mean plasticizers and mixtures thereof, preferably plasticizers selected from lubricants, plasticizers and mixtures thereof, these lubricants being polysiloxanes. If a chemical softening agent, which is primarily intended as a plasticizer, is desired, it can be selected from a group of chemicals, including polyethylene glycol, for example polyethylene glycol with a molecular weight of 400. From this patent application the US-5 256 546 emerged.

DE-A-28 00 132 relates to a soft, pliable skin cleaning article with a fleece with a wiping surface and a low density wiping zone, the wiping surface being a boundary of the low density wiping zone, the low density wiping zone permeable to dirt and having a plurality of cavities in and under the surface, and the low density wiping zone with about 10 to 150% lipophilic cleaning oils , is treated based on the weight of the fleece. The term lipophilic cleaning enamel also includes silicone oils and nonionic surfactants.

DE-C 34 20 940 relates to an agent for cleaning and wiping the circumental area, comprising at least one oil selected from the group of vegetable oils, animal oils and synthetic oils, characterized in that it comprises a silicone oil as a further component.

EP-A-0 459 501 relates to a process for reducing the static charge and the destruction during a wet printing process, which is characterized in that a silicone polymer emulsion having a particle size of less than 200 nm, a cationic surfactant and a nonionic surfactant is applied.

Furthermore, patents are known which describe the use of a mixture of polyethylene glycol with quaternary amines (cationic surfactants) as treatment agents, for example US Pat. No. 5,312,522.

For example, DE-C-34 47 499 relates to a non-drying cleaning cloth, which is characterized in that an emulsion is applied to a carrier material, which consists of at least one moisture regulator, preferably polyethylene glycol and at least one further liquid substance. It is also known to use an anionic surfactant, nonionic surfactant or mixtures thereof as plasticizers in the production of soft tissue paper.

EP-A-03 47 177 relates to a method for producing soft tissue paper, which comprises the following steps:

Sheet formation from an aqueous suspension (wet laying) of cellulose fibers to form a fleece, application of a sufficient amount of a water-soluble non-cationic surfactant in such a way that 0.01 to 2% of this non-cationic surfactant, based on the dry (fiber) weight of this tissue paper through the fleece are withheld, this application being carried out with a fiber consistency of 10 to 80% and drying and creping of the fleece, this tissue paper having a basis weight of 10 to 65 g / m ² and a density of less than 0.6 g / m ³ .

EP-A-0607796 relates to a non-woven fabric containing an organosilicon compound, the improvement being that the organosilicon compound contains 95 to 98% by weight of a water-soluble or water-dispersible

Polyether polysiloxane, the polyether groups consisting of 30 to 100 mol% of oxyethylene units and oxypropylene units as the remainder and the polysiloxane block comprising 10 to 100 siloxane units, 1 to 20% by weight of a water-soluble or water-dispersible organopolysiloxane having at least one ammonium group which is on the carbon atom is attached and 1 to 20 wt .-% water or a water-soluble alkylene glycol.

The present invention is based on the object of providing a polysiloxane-containing treatment agent for tissue paper products to improve the softness, it being irrelevant which of the prescribed raw tissue production and processing methods was used to produce the tissue product according to the invention. Such a treatment agent is obtained by a mixture of special ones Amounts of at least one polyhydroxy compound, in particular a polyethylene glycol and / or glycerol which is liquid at room temperature as a further component, a proportion of a polysiloxane and optionally up to 25% by weight of water.

The application of such a mixture surprisingly leads to a significantly improved softness of tissue products compared to a pure polysiloxane application and compared to a pure polyethylene glycol or glycerol application (synergy effect).

The present invention thus relates to a polysiloxane-containing treatment agent, in particular in the form of a lotion, for tissue paper products, which is characterized in that it contains 25 to 95 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol and / or glycerol which is liquid at room temperature, 5 to Contains 75 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 0 to 35 parts by weight of water.

For the purposes of the present compound, the polyhydroxy compound is understood to mean a low- and macromolecular organic compound which contain two or more hydroxyl groups in the molecule. These polyhydroxy compounds, which are also called polyols, by definition include, in particular, polyhydric alcohols, such as, for example, glycerol, polyethylene glycols, pentaerythritol, sugar alcohols, such as, for. B. tetrides, pentites, hexites etc., in particular threitol, erythritol, adonite, arabitol, xylitol, dulcitol, mannitol and sorbitol, carbohydrates, for example D (+) - glucose, D (+) - fructose, D (+) - galactose, D (+) - mannose, L-gulose, sucrose, galactose or maltose and synthetic polymers such as polyvinyl alcohol. Polyethylene glycols which are liquid at room temperature, ie 20 ° C., are those with an average molecular mass of 200 to 600. Any water-soluble and / or water-dispersible compound which is liquid, pasty or waxy at room temperature (20 ° C.) can be used as the polysiloxane component. The polysiloxane component used for the purposes of the present invention includes polymeric, oligomeric, copolymeric and other polymonomeric siloxanes. In the following, the term polysiloxane should be understood to mean any polymeric, oligomeric or other multi-monomeric siloxane material. Furthermore, the polysiloxane material can have both a linear structure, a branched structure or a cyclic structure.

According to a preferred embodiment, the polysiloxane component has monomeric siloxane units of the following structure:

Ri

I (1) Si - 0

I.

R ₂

where R 1 and R _{2 are the} same or different for each monomeric siloxane unit and are each an alkyl, aryl, alkenyl, alkylaryl, arylalkyl, cycloalkyl, halogenated hydrocarbon or other group. Each of these groups can be substituted or unsubstituted. Ri and R ₂ groups of each particular monomeric unit may differ from the corresponding functional groups of the next attached monomeric unit. Furthermore, these groups can be both straight-chain and branched or have a cyclic structure. The groups R 1 and R ₂ can furthermore and independently of one another be other silicone groups, but are not restricted to siloxanes, polysiloxanes and polysilanes. The groups Ri and R ₂ can continue to be a large number of contain organic functional groups, for example alcohol, carboxylic acid and amino functional groups.

The degree and type of substitution provide the relative degree of softness, silky feel, and hydrophilicity imparted to the tissue paper structure. In general, the degree of softness and silky feel caused by the polysiloxane, among others, increases as the hydrophilicity of the substituted polysiloxane component decreases. Amino-functional polysiloxanes and polyether polysiloxanes are particularly preferred as the polysiloxane component in the treatment agent according to the invention.

Preferred polysiloxanes include linear organo-polysiloxane compounds of the following general formula.

(2: R ₂ - Rs

where the R 1 to R c, groups are each independently Ci to Cio unsubstituted alkyl or aryl groups and Rio is any substituted Ci to Cio alkyl or aryl radical. Each Ri to Rg group is preferably, independently of one another, a Ci to Cio unsubstituted alkyl group. It is known to those skilled in the art that it makes little difference whether, for example, R ₉ or Rio is the substituted group. The molar ratio of b to (a + b) is preferably between 0 and 20, preferably between 0 and 10% and in particular between 1 and 5%.

In a particularly preferred embodiment, R 1 to R _{9 are} methyl groups, and Rio is a substituted or unsubstituted alkyl, aryl or alkenyl group. Such materials are commonly referred to here as polydimethylsiloxanes referred to, which have a special functionality, as used in the present case. Examples of such polydimethylsiloxanes can be:

Polydimethylsiloxanes such as Dow Corning ® 200 Fluid, polydimethylcyclosiloxanes such as Dow Corning ® 344 and 345,

Polydimethylsiloxane with a Rio alkyl hydrocarbon group and a polydimethylsiloxane with one or more amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, A id, ester, thiol and / or other Rio functional groups including alkyl and alkenyl analogs of such functional groups. For example, an amino functional alkyl group such as Rio can be an amino functional or an amino alkyl functional polydimethylsiloxane. The exemplary list of these polydimethylsiloxanes does not mean that others, not specifically mentioned here, are excluded from this.

The viscosity of the polysiloxanes used as a component in the treatment agent according to the invention can vary over a wide range, as long as the polysiloxane remains fluid and can be liquefied for use in the treatment agent according to the invention for application to the tissue paper. This includes, for example, viscosities from 25 x 10 ^"6 m ² / s to 20,000,000 x 10 ^{" 6} m ² / s or even higher. Viscosities of 15,000 x 10 ^{~ 6} m ² / s to 3,400,000 x 10 ^" m ² / s are preferred here. Highly viscous polysiloxanes, which are themselves not flowable, can be applied as an ingredient of a treatment agent according to the invention in an effective manner on tissue paper by for example, the polysiloxane component is emulsified according to the invention in PEG or glycerol or water or in a mixture thereof, together with a surfactant, or the polysiloxane, if it is not soluble in PEG or glycerol or water, by means of a solvent, such as, for example, hexane Brings solution. Special methods for applying the polysiloxane component to tissue paper are discussed below.

The aforementioned polysiloxane components are described, for example, in US-A-2826551, US-A-3964550, US-A-4364837, US-A-4395454, US-A-4950545, US-A-4921895 and British Patent 849433. Furthermore, the monograph "Silicon Compounds", pages 181-217, edited by Petrarch Systems, 1984, contains a detailed list and description of such polysiloxanes.

According to a further preferred embodiment, polyether siloxanes of the general average formula can be used as the polysiloxane component in the treatment agents according to the invention.

(3)

Ri2 - i2

in which Rχ ₂ in the molecule are the same or different and an alkyl group with 1 to 12 carbon atoms or a polyether group - (C _n H _2n O) _x Rι ₃ , where Rι _{3 is} hydrogen, hydroxyl, alkyl or an acyl group and n is a numerical value from 2 to 2.7 and x has a numerical value from 2 to 200, with the proviso that at least one of the R ₂ groups in the average molecule is a polyether group; a has a numerical value from 0 to 98, b has a numerical value from 0 to 98 and a + b is 8 to 98. R ₁₂ can be an alkyl group having 1 to 12 carbon atoms or a polyether group. However, the condition must be met that at least one R ₁₂ in the average molecule is a polyether group. Preferably 2 to 5 of the Ri ₂ ~ groups are polyether groups, and the remaining Ri ₂ ~ groups then have the meaning of an alkyl group, the methyl group being particularly preferred. The alkyl group can also have up to 12 carbon atoms. In this way it is possible to vary the properties of the treatment agent and in this way to improve the handling on tissue paper products. The polyether groups correspond to the formula (C _n H _2n O) _x Rι ₃ . The index n has a numerical value from 2 to 2.7. In general, the ether group consists of a plurality of oxyethylenes and optionally oxypropylene groups. If the index n is 2, the polyether group consists exclusively of oxyethylene units. If the numerical value of n increases, the proportion of oxypropylene groups also increases. The numerical value of n = 2.7 means that 70% of the polyether groups are oxypropylene groups.

The index x means the number of oxyalkylene units. This value is an average numerical value since a mixture of products of different chain lengths is usually obtained in the synthesis of polyethers. The index x has a numerical value of 2 to 200 and is preferably 10 to 50. Polyether groups with an average molecular weight of 600 to 4,000 are preferred. The index a means the number of methylsiloxane units carried by the Ri ₂ ~ group. The index b corresponds to the number of dimethylsiloxane units. While a and b can have a value from 0 to 98, the condition must be met that the sum of a + b has a value from 8 to 98. If a = 0, the polyether group or groups are terminally connected. The siloxanes with positive values for a are modified by the R ₂ side chains. Siloxanes in which the Ri ₂ ~ groups are arranged in the side chain are preferred. The R ₃ group can be hydrogen, hydroxyl, alkyl or acyl. R ₃ is preferably a hydrogen atom. If R _{3 is} an alkyl group, lower alkyl groups with 1 to 4 Carbon atoms preferred. The acetyl group is the preferred acyl group.

According to a particularly preferred embodiment, the polysiloxane component according to the invention has the following formula:

(4) R ₁₄ - - Rn

where Rι a group of the formula and

(5) - R ₁₅ -

Rl7

in which R _{5 is} a divalent hydrocarbon group, the carbon chain of which is interrupted by an oxygen atom, Ri ₆ R ₁₇ , Rie are identical or different and represent alkyl groups with 1 to 18 carbon atoms, of which one of the groups Ri _ß , Rι, Rie is a ~ ( Is CH ₂ ) ₃ NHCORig group, in which R _{19 has} an alkyl group with 7 to 17 carbon atoms and X- is a monovalent anion and c has a numerical value of 5 to 100. R ₁₅ is a divalent hydrocarbon group, for example the group of the formula -CH ₂ -C (OH) H-CH ₂ -0- (CH ₂ ) ₃ ~. The Ri ₆ -, R ₁₇ -, Ri ₈ groups can be the same or different and are alkyl groups with 1 to 18 carbon atoms. However, one of the aforementioned groups Ri _ß, Rι _7, Rie also have the meaning of (CH ₂₎ ₃ NHCORig group.

Provided that Ri _Q, R _17, Rιβ groups are alkyl groups, they have 1 to 18 carbon atoms. Especially preferred are R ₁₄ - groups, where two of the aforementioned Ri _ß -, R ₁ 7-, Riβ groups Have 1 to 4 carbon atoms and the third group has up to 18 carbon atoms. If one of the Ri6 ~, Ri7 ^_ * Riβ groups is a (CH ₂ ) ₃ NHCORι ₉ group, the rig group is an alkyl group with 7 to 17 carbon atoms. X ^~ is a monovalent anion, generally an acetate group. However, X can also be an inorganic group such as CI ^" .

The index “c” indicates the number of dimethylsiloxy units in the linear siloxane and has a numerical value of 5 to 100 and preferably 10 to 80. Particularly preferred of the abovementioned siloxanes are those polydimethylsiloxanes and, for example, polyether, alkyl and quaternary or betaine ones Groups, especially nitrogen groups, modified polydimethylsiloxanes.

Particularly preferred polysiloxanes are the organo-modified siloxanes sold under the name Tegopren® by Th. Goldschmidt AG with pronounced surface and interface activity in aqueous and organic systems.

These are polyether siloxanes, as undated in the company publication “Tegopren Informativ”, from Th. Goldschmidt AG under the trade name Tegopren 3012, Tegopren 3020, Tegopren

3021, Tegopren ^® 3022, Tegopren ^® 3070, Tegopren ^® 5830, Tegopren ^®

5840, Tegopren ^® 5842, Tegopren ^® 5843, Tegopren ^® 5847, Tegopren ^®

5851, Tegopren ^® 5852, Tegopren ^® 5863, Tegopren ^® 5873, Tegopren ^®

5878, Tegopren 5884 and Tegopren 7006 are sold and usually have medium cloud points in the range from below 25 ° C to 71 ° C as well as modified siloxanes in the form of teoprene silicone quats and betaines, such as those among the

Designations Tegopren ^® 6920, Tegopren 6922 and Tegopren 6950 are sold. The term tissue paper or tissue for short in the sense of the present invention is understood to mean all types of creped papers produced from aqueous dispersion with a basis weight range between 10 and 65 g / m ² . According to the invention, the term tissue paper covers both the entire area of creped base papers, also called raw tissue, in particular the area of dry creped base tissue papers, regardless of whether single-layer or multilayer, as well as all end products made from these creped base papers, such as handkerchiefs , Facial and facial tissues, toilet paper, kitchen towels, hand towels and serviettes. The term tissue paper is still to be seen independently of the fiber raw material to be used, in particular regardless of whether the fiber raw material is produced exclusively or predominantly from native cellulose by the sulfate or sulfite process, or is used in a mixture with chemo-thermomechanical wood materials (CTMP), or whether the fiber raw material used one

Secondary fiber preparation processes originate and therefore the fiber raw material required for tissue production consists wholly or partly of "recycled fibers". In order to differentiate them from so-called nonwovens, it should be noted that the predominant use of paper-based, natural, that is to say vegetable pulp fibers is characteristic for tissue paper production , a proportionate use by refinement of modified pulp fibers in a range of 10 to 50% or even a use of plastic fibers suitable for papermaking in a proportion of 10 to 30% falls under the aforementioned definition of tissue. One application of the treatment agent according to the invention is in the field of tissue production possible in corresponding areas of the non-woven area and the textile area in analog transmission.

According to a preferred embodiment of the present invention, the binary, polysiloxane-containing Treatment agent from 5 to 75 parts by weight (or wt .-%) of at least one of the aforementioned polysiloxane and 25 to 95 parts by weight (or wt .-%) of the aforementioned polyethylene glycol. However, 10 to 70 parts by weight of polysiloxane, in particular 40 to 60 parts by weight of polysiloxane and, as a further component, 30 to 90 parts by weight, but in particular 40 to 60 parts by weight of the aforementioned liquid polyethylene glycol are preferred in this treatment agent.

According to a further preferred embodiment of the present invention, the treatment agent consists of 5 to 75 parts by weight (or% by weight) of at least one polysiloxane and 25 to 95 parts by weight (or% by weight) glycerol. In this case too, a treatment agent with 10 to 70 parts by weight, preferably 40 to 60 parts by weight of at least one polysiloxane and 30 to 90 parts by weight, in particular 40 to 60 parts by weight of glycerol is preferred.

Polyethylene glycol and glycerol can be exchanged in any amount in the treatment agents according to the invention. However, mixtures of polyethylene glycol and glycerol can also be used in particular from an economic point of view, the mixing ratios preferably being 20 to 80% by weight or parts by weight, preferably 30 to 70% by weight or parts by weight of the aforementioned polyethylene glycol and 20 to 80 parts by weight. % or parts by weight, preferably 30 to 70 wt .-% glycerol.

According to a preferred embodiment of the present invention, the treatment agent according to the invention contains 30 to 90 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol and / or glycerol which is liquid at room temperature, 10 to 70 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 1 to 30 Parts by weight of water. It is particularly preferred here that such a ternary treatment mixture comprises 20 to 70 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol and / or glycerine which is liquid at room temperature, 30 to 70 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 5 to 25 parts by weight Contains water.

According to a preferred embodiment, water is present as an additional component in addition to the two organic components. The treatment agents according to the invention then consist of 5 to 75 parts by weight of at least one polysiloxane, 25 to 95 parts by weight of at least one polyhydroxy compound, in particular the aforementioned polyethylene glycol and, based on 100 parts by weight of the aforementioned mixture, 1 to 30 parts by weight of water.

In this ternary mixture with polyethylene glycol as one of the components, it is preferred to use a mixture of 30 to 90, but in particular 40 to 60 parts by weight of polyethylene glycol, 10 to 70 parts by weight, preferably 40 to 60 parts by weight of polysiloxane and, based on 100 parts by weight of the aforementioned two components, 1 to 30 parts by weight, preferably 5 to 25 parts by weight of water.

It is furthermore particularly preferred to use 15 to 24, preferably 17 to 22 parts by weight of water per 100 parts by weight of polyethylene glycol.

According to a further preferred embodiment with glycerol as one of the components, it is preferred to use an initially binary mixture of 30 to 90, but in particular 40 to 60 parts by weight of glycerol, 10 to 70 parts by weight, preferably 40 to 60 parts by weight of polysiloxane and, based on 100 parts by weight of the aforementioned two components, 1 to 30 parts by weight, preferably 5 to 25 parts by weight of water. It is furthermore particularly preferred per 100 Parts by weight of glycerin 23 to 32 parts by weight, preferably 25 to 30 parts by weight of water.

In addition to these aforementioned components, the treatment agent according to the invention may contain cosmetic agents with special properties and other customary auxiliaries as further agents. For example, skin active ingredients based on vitamins or plant extracts, such as extracts of horse chestnut seeds, birch, arnica, chamomile or bisabolol itself, St. John's wort, cucumber, aloe vera or witch hazel, are known in part because of their astringent and healing effects are.

Other active ingredients here are skin care products, for example sorbitan fatty acid esters and oxyethylated, homologous compounds of glycerol, esters of oxyethylated fatty alcohols, fatty alcohol alkanolamides, oxyethylated fatty alcohols, ethoxylated wool fatty alcohols,

Glycerol monostearate, stearic acid, cetylstearyl alcohol, petroleum jelly and lanolin are mentioned. In addition to lanolin itself, lanolin derivatives can also be used, such as, for example, lanolin alcohols or wool wax alcohols which are listed under the

Designation Amerchol® by Union Carbide Inc. in connection with mineral oils. The 400, BL, C, CAB, U9, L99, Llll, L500 and RC series are known here, for example. Other lanolin derivatives are the acetylated lanolins and hydrophilic lanolin derivatives, for example lanolin-polyoxyethylene compounds. Hydrotropic solubilizers for fatty substances, such as, for example, polyalcohol ethers and ethoxylated fatty alcohols, can also be used as other additives in the treatment agent according to the invention.

Another group that can be used as an additional component in the treatment agents according to the invention are quaternary ammonium compounds, but in particular quaternary ammonium salts, as described, for example, in US Pat. Patents 5312522, 5397435, 5405501, 5427696 and international patent applications WO 95/11344, W095 / 11343, WO 95/01478, WO 95/01479, W094 / 29521, WO94 / 29520, W094 / 16143 and W094 / 19381.

In addition, fragrances of a conventional type can also be added, which are selected from natural, nature-identical or artificial fragrances, the corresponding fragrances being preferred. For example, agricultural oils such as lemon oil, bergamot oil, orange oil, petitgrain oil, softwood oils, foin coupe

Fragrance compositions or floral oils such as B. rose, jasmine, lilac, lavender, as well as synthetic fragrances based on menthol etc. An overview is given by Ullmann Encyclopedia of Industrial Chemistry, Volume 20, pp. 190 - 185.

In addition, appropriate inorganic pigments or organic dyes, as are customarily used in tissue paper production, can also be added together with the treatment agent according to the invention. Here, not least for ecological reasons, physiologically harmless and non-irritating dyes, in particular the corresponding natural dyes, are preferred. All of the aforementioned additives and auxiliaries in the treatment agent according to the invention can be contained both individually and as a combination.

The treating agent for tissue paper products described above is applied in an application amount in the range of 0.01 to 15 percent by weight, preferably 0.5 to 10 percent by weight, most preferably 2 to 6 percent by weight, based on the dry weight of the fibers.

A single or multi-layer, preferably at least two-layer and particularly preferably three or four-layer, unembossed or embossed tissue paper is preferably used as the carrier material to which the treatment agent is to be applied used. The individual paper webs can be mechanically connected to one another by edge embossing or knurling, glued flat or punctually or else connected to one another in some other way. For the individual webs there is also a basis weight range of 10 to 40 g / m ² , preferably 14 to 30 g / m ² , in particular 15 to 25 g / m ² , most preferably 15.5 to 17.5 g / m ² ² proven. In special applications, however, heavier or lighter papers with basis weight ranges from 8 to 65 g / m ^{2 can also be} useful.

According to a further preferred embodiment, the carrier material can also be solidified wet, the usual health-friendly wet strength agents, such as epichlorohydrin resins, urea-formaldehyde resins

Melamine formaldehyde resins and crosslinked cationic polyalkylene amines can be used.

The treatment agent, which in a preferred embodiment is in the form of an emulsion, can be applied to the carrier material using any roller and spray application process or in an impregnation process. It is always important to ensure that the emulsion cannot separate, i. that is, the components of the treatment agent must be thoroughly mixed during application in order to prevent segregation. This is done, for example, by high shear forces, generated for example by high-speed stirrers, frequent pumping or by ultrasonic mixing.

The treatment agent, which can be used for a noticeably improved softness of tissue products, can be used in a wide variety of product areas. Its use, for example, on napkins, toilet paper and hand and kitchen towels, handkerchiefs, facial tissues and facial tissues has proven to be particularly advantageous. The above-mentioned composition of the treatment solution is dimensioned such that skin irritation (drying out due to the hygroscopic properties of polyethylene glycol or glycerol) cannot occur during the period of use by the consumer in the atmospheric humidities normally prevailing in the annual average due to the water content even when used continuously. Even water vapor-tight, resealable packaging is no longer necessary.

The treatment solution can be both in the wet part of a tissue paper machine (wadding machine), at the end of the wire section, in front of or within the press section (mechanical dewatering), i.e. H. with solids contents between 20 and 50% as well as in the drying section arranged after the press section with solids contents between 40 and 97% fiber dry weight. State of the art are task locations on the transfer sieve / belt, z. B. before the fleece transfer in a TAD arrangement and the feed to the moist nonwoven fabric after its transfer to the transport (dry) felt in a conventional one or two-felt tissue production machine. The state of the art is also the supply of treatment chemicals in a spray application onto the Yankee cylinder.

It is preferred to add the treatment agent in the tissue production machine by spraying it onto the Pope-Roller to produce a treatment agent film and then transfer it to the tissue web during the reeling process - usually the already creped "tissue web" as a result of the previous drying process on the Yankee cylinder has a residual temperature between 20 ° C and about 70 ° C, which is favorable for the distribution of the treatment agent and its penetration into the raw tissue - on the contact surface of the single-layer tissue web with the surface of the drum of the Pope-Roller The nozzle bar can also Use of centrifugal rotors or brushing units as well as the indirect transfer of a treatment agent film via roller application units are possible. The order can also be placed directly on the tissue paper web. It is particularly preferred to add the treatment agent within the doubling machine or within the processing machine to the outer layers of the multilayer doubled web before or during calibration / smoothing. Most preferred is the application of the treatment agent within the processing machine to the single or multi-layer web.

The present invention therefore relates to a method for producing soft tissue paper products, which is characterized in that on the tissue web inside the screen press section and / or dryer section or outside the tissue production machine in the doubling or processing machine, that is to say with a fiber density of 20 to 97%, based on the dry fiber weight of the web, a treatment agent of the aforementioned type has been applied or applied in an amount of 0.01 to 15% and the nonwoven undergoes a smoothing after application.

According to a preferred embodiment, the tissue paper products are obtained by applying a polysiloxane-containing treatment agent of the above type onto the tissue web or the nonwoven fabric after the dryer section in the tissue paper machine and particularly preferably inside the doubling machine or within the processing machine in an amount of 0.01 up to 15% applied to the web and after the application undergoes a smoothing. However, it is particularly preferred if the abovementioned polysiloxane-containing treatment agent is applied at a fiber density of 35 to 97%, based on the dry fiber weight of the single-layer web, in an amount of 0.5 to 10% to the single-layer web. It is particularly preferred to use a multi-layer web as the tissue web and the treatment agent with a fiber density of more than 90%, based on the dry fiber weight, to be applied to at least one of the outer layers of the multilayer web in an amount of 1 to 7%. It is very particularly preferred to apply the treatment agent to the multilayer tissue web on both outer layers in an amount of 3 to 6%.

In the context of the aforementioned method, it is preferred that the smoothing is carried out by at least one passage of the tissue web through a nip of a pair of rollers, in which a roller with a steel surface and a counter roller with a steel, plastic, paper or rubber surface, but preferably one Plastic surface.

This is preferably carried out in such a way that the smoothing is carried out by passing the tissue web twice through a nip of a pair of rollers, in which first a roller with a steel surface of a counter roller with a plastic surface and then a mirror image of a roller with a plastic surface of a counter roller with a steel surface assigned.

The smoothing of the tissue web after the application of the treatment agent is therefore usually carried out in such a way that the tissue webs sprayed on both sides are passed through a smoothing unit. This smoothing unit generally consists of two smooth rollers with steel surfaces (steel rollers), the surfaces of which are usually hard chrome-plated. These rollers are pressed together hydraulically or pneumatically or are moved to a gap for calibration. This means that one of the two rollers is firmly positioned. The second or counter roller is pressed against a stop, so that the two steel rollers cannot touch each other, but are at a certain, measurable and reproducible distance from one another. The tissue webs guided through this gap are compressed to the width of the gap and smoothed in the process. The structure of the surface is standardized, ie a uniform thickness is achieved. The result is smoothing by leveling the surface in connection with an equalization of the thickness profile under the premise of a minimal loss of volume.

The usual influencing factors on the smoothing are the line force, the surface temperature of the partially heated rollers, the nip width and the nip number (number of smoothing units). The articles in "apr Europe", 3 (1991), pages 121 to 123 and "JJA Rodal Tappi Journal", volume 76, no. 12, pages 63 to 74 provide an overview of this, as does the overview by E. Weißhun and H. Holik, in "Das Papier", Volume 38 (1984), No. 10A.

Instead of the two steel rollers that form the smoothing unit, a so-called soft smoothing unit can also be used. Here, a steel roller with a plastic surface is pressed against a smooth steel roller. Such a smoothing unit is supplied, for example, by Küsters Maschinen GmbH. These soft-smoothing calenders are known, among other things, as MAT-ON-Line smoothing units. Another soft smoothing unit with steel roller and counter roller with plastic surface is the NIPCO-MAT smoothing unit from Edmund Küsters Maschinenfabrik, Krefeld, cf. Wochenblatt der Papierfabrikation 13/91, pp. 491 to 498. Such rollers are described in more detail in DE 3445890 and in EP 0273185.

Furthermore, instead of the two steel rollers which form the smoothing unit, a smoothing unit can also be used, a roller or counter-roller having a rubber or paper surface being used together with a steel roller or steel counter-roller.

An overview of common post-smoothing processes is given in German patent 1804418, German patent application 2455895, German patent 2528803, EP-A-0033559, US patent 2179057, US patent 3337388, British patent 827735 and German patent 822228 and 1045783. Finally, the present invention relates to the use of the aforementioned polysiloxane-containing treatment agent for the softening of tissue paper products, in particular handkerchiefs, facial tissues, make-up wipes, serviettes, toilet paper, hand and kitchen towels.

The present invention is explained in more detail below by means of exemplary embodiments.

Example 1:

On a paper handkerchief (finished product) with a basis weight of about 4 x 15.5 g / m ³ with a fiber dry content of 92 to 97% dry fiber weight in the laboratory, a treatment solution of 32 weight percent polyethylene glycol, molecular weight 200, 60 weight percent of

Polysiloxane Tegopren 3021, a polyether siloxane with a cloud point of 38 ° C from Th. Goldschmidt AG and 8% water with good swirling in a quantity of 6% sprayed onto the tissue and subjected to a smoothing. The application was carried out symmetrically on the outer surfaces of this fabric. The product thus obtained was referred to as A.

Example 2:

The application process according to Example 1 was repeated, but instead of a ternary mixture, a binary mixture of 50 percent by weight polyethylene glycol, molecular weight 200 and 50 percent by weight of the polysiloxane according to Example 1 was used. The sample thus obtained was named B. Comparative experiment 1:

The process according to Example 1 was repeated, but instead of the ternary mixture according to the invention, the pure polysiloxane according to Example 1 was applied in an amount of 6% and the product thus obtained was designated C.

Comparative experiment 2:

The process according to Example 1 was repeated, but instead of the ternary mixture according to the invention, a pure polyethylene glycol with a molecular weight of 200 was applied in an amount of 6%. The product thus obtained was designated D. All of the cloths of Examples 1 and 2 and of Comparative Experiments 1 and 2 were reproducibly smoothed in a 2-roll (steel / plastic) smoothing unit under identical conditions (speed, temperature, contact pressure).

The haptic properties of the products A and B according to the invention were compared with the corresponding haptic results of the comparison products C (pure polysiloxane) and D (pure polyethylene glycol) (PEG) and these products were subjected to a so-called panel test (based on “Manual on Sensory Testing Methods, ASTM, Special Technical Publication 434, p. 22; Testform D-Ranking Methods-Rank Order, Elevents Printings February 1993). Here, the increasing softness, defined here as the sum of the surface softness and softness of a crotch of a group of 9 people, was assessed according to the following procedure:

The paper tissues to be tested were folded in half so that the test person could not recognize the sample identification and in any case the same outside of the evaluation was presented. The cloths folded in this way were given to the test subjects with the instruction that Check the folded cloths between the thumb, ball of the thumb and fingers rubbing and crumpling with regard to their softness and the softness of the surface and then placing the cloths in line according to increasing subjective quality perception. The samples were ranked from 1, the best, to 4, the worst.

The test showed that products A and B according to the invention were described by 7 of the 9 test persons as very good in softness and in relation to the comparison products C and D as clearly softer. In contrast, only one of the 9 test persons found product D to be softer than product A according to the invention, and one of 9 test persons found comparative product C to be softer than products A and B according to the invention. The panel test also shows that products A and D are significantly better in terms of softness and surface softness than the comparative products C and D.

The results of this panel test are shown in the table below:

Lotion 1 # 2 # 3 # 4 # 5 # 6 # 7 # 8 # 9 #

composition

Parts by weight

PEG Wasser Sil¬ order¬ Rang¬ Rangfo Ige oxan amount (%) sum

A PEG / water / 32 8 60 6 19.0 2 3 2 2 2 2 2 2 2 siloxane

B PEG / siloxane 50 - 50 6 11.0 1 1 3 1 1 1 1 1 1

C siloxane - - 100 6 30.0 4 4 1 4 3 3 4 3 4

D PEG 100 - - 6 30.0 3 2 4 3 4 4 3 4 3

# ID of the test subjects

In addition to this first in-house panel test, a studio consumer test was also carried out with 160 people. Samples with a lotion composition of polyethylene glycol / polysiloxane / water in a ratio of 72/10/18 with a 3% application quantity were judged to be significantly softer than a corresponding comparison sample with pure siloxane. Here again the polysiloxane described in Example 1 was used as the polysiloxane and the polyethylene glycol with a molecular weight of 200 described in Example 1 was used as the polyethylene glycol.

Claims

claims

Polysiloxane-containing treatment agent for tissue paper products, in particular in the form of a lotion, characterized in that it contains 25 to 95 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol and / or glycerine which is liquid at room temperature, 5 to 75 parts by weight of polysiloxane and, based on 100 parts by weight of these Mixture containing 0 to 35 parts by weight of water.

Treatment agent according to claim 1, characterized in that it contains 30 to 90 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol and / or glycerol which is liquid at room temperature, 10 to 70 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 1 to 30 parts by weight Contains water.

Treatment agent according to claims 1 or 2, characterized in that it contains 30 to 70 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol and / or glycerol which is liquid at room temperature, 30 to 70 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 5 to Contains 25 parts by weight of water.

Treatment agent according to the preceding claims, characterized in that it contains 5 to 75 parts by weight of at least one polysiloxane and 25 to 95 parts by weight of a polyethylene glycol which is liquid at room temperature.

5. Treatment agent according to claim 4, characterized in that it contains 10 to 70 parts by weight, in particular 40 to 60 parts by weight of at least one polysiloxane and 30 to 90 parts by weight, in particular 40 to 60 parts by weight of the polyethylene glycol.

6. Treatment agent according to claims 1 to 3, characterized in that it contains 5 to 75 parts by weight of at least one polysiloxane and 25 to 95 parts by weight of glycerol.

7. Treatment agent according to claim 6, characterized in that it contains 10 to 70 parts by weight, preferably 40 to 60 parts by weight of at least one polysiloxane and 30 to 90 parts by weight, in particular 40 to 60 parts by weight of glycerol.

8. Treatment agent according to the preceding claims, characterized in that the first component from 20 to 80, preferably 30 to 70 parts by weight of the aforementioned polyethylene glycol and 20 to 80 parts by weight, preferably 30 to 70 parts by weight of the aforementioned glycerol.

9. Treatment agent according to the preceding claims, characterized in that the polysiloxane has a viscosity of 25 x 10 ^"6 m ² / sec to 20,000,000 x 10 ^{" 6} m ² / sec.

10. Treatment agent according to the preceding claims, characterized in that the polysiloxane is a polydimethylsiloxane, which optionally has at least one betaine group, in particular a tetraalkylammonium group, in its side chain.

11. Treatment agent according to the preceding claims, characterized in that the polysiloxane is a polyether siloxane, in particular with average cloud points in the range from below 25 ° C to 71 ° C.

12. Treatment agent according to the preceding claims, characterized in that it also contains cosmetic agents with special properties, for example skin care agents and / or skin active ingredients based on plant extracts and / or fragrances.

13. Treatment agent according to the preceding claims, characterized in that it further contains auxiliaries such as quaternary ammonium compounds and / or solubilizers and / or wet strength agents.

14 A process for the production of tissue paper products, characterized in that a polysiloxane-containing treatment agent according to claims 1 to 13 is based on the nonwoven fabric or the "tissue web" within the wire / press section and / or dryer section, that is to say at a fiber density of 20 to 97% applied to the dry fiber weight of the web in an amount of 0.01 to 15% and subjected to post-smoothing after application.

15. A process for the production of tissue paper products, characterized in that a polysiloxane-containing treatment agent according to claims 1 to 13 on the nonwoven fabric or the tissue web after the dryer section in the tissue paper machine and particularly preferably within the doubling machine or within the

Processing machine applied in an amount of 0.01 to 15% on the web and subjected to a post-smoothing after application.

16. The method according to claim 15, characterized in that the polysiloxane-containing treatment agent is applied at a fiber density of 35 to 97%, based on the dry fiber weight of the single-ply web, in an amount of 0.5 to 10%.

17. The method according to claims 14 to 16, characterized in that the tissue web is a multi-layer web and the treatment agent at a fiber density of more than 90%, based on the dry fiber weight, on at least one of the outer layers of the multi-layer web in an amount of 1 to 7% is applied.

18. The method according to claim 17, characterized in that the treatment agent is applied to the multilayer tissue web on both outer layers in an amount of 3 to 6%.

19. The method according to claims 15 or 16, characterized in that the application of the treatment agent in the tissue production machine is carried out by spraying onto the Pope-Roller with the production of a treatment agent film and its subsequent transfer to the tissue web during the reeling process.

20. The method according to claims 14 and 15, characterized in that the smoothing is carried out by at least one passage of the tissue web through a gap of a pair of rollers, in which a roller with a steel surface of a counter-roller with a steel, plastic, paper or rubber surface, is preferably assigned to a plastic surface.

21. The method according to claims 14 and 15, characterized in that the smoothing is carried out by a double passage of the tissue web through a nip of a pair of rollers, in which first a roller with a steel surface of a counter-roller with a plastic surface and then a mirror image of a roller with a plastic surface Counter roll with a steel surface is assigned.

22. The method according to claims 14 to 21, characterized in that the application of the treatment agent to the nonwoven fabric takes place in the context of a conventional tissue manufacturing process.

23. The method according to claims 14 to 21, characterized in that the application of the treatment agent to the nonwoven fabric takes place in the context of a through-flow drying or a TAD process.

24. Use of the treatment agent according to claims 1 to 13 for the treatment of tissue paper products, in particular handkerchiefs, facial tissues, facial tissue, napkins, toilet paper and kitchen towels.