EP0803012B1 - Process for producing tissue paper by using a treating agent - Google Patents

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

The present invention relates to a method for Manufacture of tissue paper and products made from it using a treatment agent as well as use a treatment agent.

Softness is an important characteristic of tissue products such as Handkerchiefs, facial tissues, toilet paper, napkins and also hand or kitchen towels and describes the feeling which the tissue paper produces when it touches the skin.

As in the weekly paper for paper manufacture issue 11/12, 1988 Page 435 ff. In the article ,, Softness and Softening of Hygiene Tissue ", the term softness is indeed generally understandable, but extremely difficult to define, since no physical method of determination and therefore also not a recognized industry standard as the standard for classification different degrees of softness is present.

In order to really grasp the softness, it has to go through a subjective method is determined, d. H. it is through a so-called panel test, in which several trained test subjects make a comparative judgment.

Softness can be characterized by its main characteristics: Surface softness and softness, break down:

Surface softness describes the feeling which one feels when you move your fingertips lightly over the Surface of the tissue sheet moves.

Under softness is meant the sensory impression, a tissue squeezed by hand during the Squeeze process created.

1. Auswahl der Rohstoffe, insbesondere der Zellstoffe,

2. maschinentechnische Maßnahmen ( z. B. Mahlung, Blattbildung, Trocknung und Kreppung, Glättung) und

3. chemische Zusatz- und Hilfsstoffe.

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.

Depending on the intended use, tissue papers require different properties. So are kitchen towels and to an even greater extent with towels strength, in particular Strength when wet and high suction power required to meet the needs of the consumer. For other products, such as handkerchiefs or facial tissues are softness of the surface and very smooth outstanding properties that in addition to strength Determine the utility value of these products. With toilet paper determines a combination of dry strength in addition to good Softness and good thickness appearance, suitability for use and Consumer acceptance.

It is a special challenge for the paper makers different, often contradicting influencing factors in to bring a special balance, from which the Optimal combinations of properties demanded by consumers to present the desired end products.

It is a sign of the times today that across everyone Product areas for hygiene articles an improvement of Softness is one of the most important requirements for the papermaker is. Properties like softness of a tissue product in their basic training through the manufacturing process and Selection of raw and auxiliary materials determines, as before discussed.

The tissue making process includes regardless of its different variants the following procedural Steps:

Suspend the fiber in water, possibly adding chemical aids for the targeted influencing of Product properties and process flow, activation of Fiber surfaces to develop 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 confusion on one or between two endless revolving seven of the paper machine under simultaneous Removal of the bulk of the dilution water up to Dryness between 12 and 35%, drying the formed primary nonwoven in one or more steps mechanical and thermal path to a final dry content from around 93 to 97%. Among those for tissue production The most relevant steps still include the creping process, the in the conventional process, the properties of the finished tissue product. Mostly today applied creping occurs on the creping a drying cylinder, usually 4.5 to 6 m Diameter, the so-called Yankee cylinder, with the help of a Crepe doctor at the aforementioned final dry content of Tissue paper. In older procedures with fewer That will also make demands on tissue quality Wet crepe process applied, similar to that Dry crepe process, but at lower dry contents below 80%, usually around 55 to 65% dryness expires, with subsequent drying on subsequent Drying cylinders of a dryer section up to the final dry content. The creped, finally dry raw tissue paper (raw tissue) is in a subsequent step on a core to one so-called drum or cut lengthways on sleeves Mother rolls wound up and stands in the form for the further Processing to finished products available.

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

The processing process, for example, to folding products such as Handkerchiefs or facial tissues are made in downstream, separate operations in special, for the task constructed processing machines, the processes like smoothing the tissue again, edge embossing, partially combined with flat and / or selective gluing to create layer adhesion of the composite individual layers (raw tissue) as well as longitudinal section, folding, Cross-section, storage and merging of several individual tissues and their packaging in so-called cloth bags or special jewelry boxes and their merging contain larger packaging or containers. Instead of Edge generation can also be achieved by layer adhesion Knurling are generated, as z. B. in cosmetic wipes is common.

In addition to the described, conventional Tissue manufacturing processes are particularly common in the United States, today increasingly also in Europe, modified Process technologies in use, where a special Type of drying inside the tissue machine Improvement of specific volume and in this way a Improvement of the softness of the tissue produced in this way is achieved. These exist in different subspecies Procedures are called TAD (Through Air Drying) procedures (Throughflow drying). Its characteristic is that the "primary" nonwoven leaving the sheet formation before final contact drying on the Yankee cylinder a dry content of about 80% is pre-dried by Hot air is blown through the nonwoven. The nonwoven is supported by an air-permeable sieve or belt and led over the surface of one during its transport air-permeable, rotating cylinder drum. By The support sieve or belt can be structured any pattern of compressed and by deformation in the damp state are generated on loosened zones that too increased, medium, specific volume and related thus lead to an increase in softness without the Strength of the nonwoven below that for use necessary measure drops. Another possibility to influence the Raw tissue production for softness and firmness consists in the Applying a stratification in which the primary to be formed Nonwoven fabric through a specially designed headbox in Form of different material layers is fed to the sheet formation together as a material jet become. When using layering, nonwovens include consisting of two, three or more layers to the state of the Technology, for example DE-C 43 47 499. By suitable Selection of raw materials in the stratification channels Headbox exit nozzle, for example the use of Eucalyptus fibers on the surface of the Yankee cylinder facing fleece side can be the surface softness be significantly increased, which is the result of the raw tissue production manufactured products.

In addition, the use of chemicals is in the form of a Lotion order on the raw tissue during the raw tissue production process, the duplication or the subsequent one Processing known to improve softness. The term "Lotion" encompasses in general cosmetic usage Understanding aqueous or aqueous-alcoholic preparations emulsifying agents. In particular, the use aqueous solutions or emulsions of polyhydroxy compounds such as glycol or polyethylene glycol or the use of Polysiloxanes to improve tissue softness described. So far it is not known that a significant increase in softness as a synergy effect Mixture of a polysiloxane with a polyethylene glycol in aqueous emulsion can be achieved.

The use of polysiloxanes as a treatment agent Softness improvement of tissue in the patent literature described. So far it is not known that a significant increase in softness as a synergy effect Use of a mixture of a polysiloxane with a Polyhydroxy compound, such as. B. polyethylene glycol or Glycerin in aqueous emulsion as a treatment agent for tissue can be achieved. For example, WO 90/09807 relates to Tissue product containing at least one layer of tissue, this tissue product being 0.1 to 5 percent by weight Contains solids of a silicone compound. This is what it is about preferably an aqueous emulsion and / or solution of these silicone compounds. From this patent application it is U.S. Patent 4,950,545 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 which results from this 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 being 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 being 0.004% to 2% of polysiloxane, based on the dry (fiber) weight of the tissue paper, which polysiloxane has a viscosity of 25 centistokes and has more and has a wetting time of not 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 production process for soft tissue paper with the step sequence of forming a sheet from aqueous suspension (wet laying) of cellulose fibers with formation of a nonwoven fabric (nonwoven fabric), drying the nonwoven fabric while increasing the temperature of the nonwoven fabric to at least 43 ° C., and creping the nonwoven fabric a temperature of at least 43 ° C, treating 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 in this nonwoven fabric remain, this tissue paper has a basis weight of 10 to 65 g / m ² and a density of less than 0.6 g / m ³ . According to 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), whereby this method is characterized in that it follows Steps includes:

Providing a dry tissue paper nonwoven, the dilution of a chemical papermaking additive with a suitable solvent to form a dilute chemical solution, the application of this dilute chemical Solution on a heated transfer surface, partially Evaporation of the solvent through the transfer surface below Formation of one containing this papermaking additive Films and the transfer of the film from the heated Transfer surface to the surface of the tissue nonwoven, that a sufficient amount of the chemical Papermaking additive is made in such a way that 0.004 to 2% of this chemical paper making additive based on the dry (fiber) weight of this tissue nonwoven in it Tissue nonwoven remains. Preferably one understands this papermaking additive plasticizers and their Mixtures, preferably plasticizers, selected are made of lubricants, plasticizers and their Mixtures, these lubricants being polysiloxanes. Provided a chemical softener, which is primarily used as Plasticizer should serve, is desired, it can be made selected from a group of chemicals, for which purpose other polyethylene glycol, for example polyethylene glycol a molecular weight of 400 counts. From this U.S. Patent No. 5,246,545 has been filed.

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 represents a boundary of the low density wiping zone that Wipe zone low density is permeable to dirt and a Plenty of cavities in and under the surface and wherein the low density wiping zone is about 10 up to 150% lipophilic cleaning enamel, based on the Weight of the fleece, is treated. Under the concept of Lipophilic cleaning moles also fall, among other things Silicone oils and non-ionic surfactants.

DE-C 34 20 940 relates to an agent for cleaning and Wiping the circuminal area comprising at least one Oil selected from the group of vegetable oils, animal oils and synthetic oils, characterized in that it is considered another Component comprises a silicone oil.

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

Furthermore, patents are known that use a Mixture of polyethylene glycol with quaternary amines Describe (cationic surfactants) as a treatment agent for example, US-A-5312522.

So 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 at least from a moisture regulator, preferably Polyethylene glycol and at least one other liquid substance consists.

It is also known as a plasticizer in the manufacture of soft tissue paper an anionic surfactant, non-ionic Use surfactant or mixtures thereof.

EP-A-03 47 177 relates to a process for the production of Soft tissue paper, which has 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 an organosilicon compound containing nonwovens, the improvement being that the organosilicon compound contains 45 to 98 wt .-% of a water soluble or water dispersible Polyether polysiloxane, the polyether groups being 30 to 100 mol% of oxyethylene units and oxypropylene units as the rest exist and the polysiloxane block 10 to 100 siloxane units comprises 1 to 20% by weight of a water-soluble or water-dispersible organopolysiloxane with at least one Ammonium group attached to the carbon atom and 1 to 20% by weight of water or a water-soluble alkylene glycol.

The pre-filed post-published EP-A-0688901 relates a tissue paper containing 3 to 30% by weight of an aqueous softness mediating composition have been added, wherein said softening composition 20 to 98 wt .-% glycerol and 0.2 to 5% by weight of at least one quaternary Contains ammonium compound, which is, among others a special one containing a quaternary ammonium compound Polysiloxane compound of the general formula (6), such as defined below, can act. Next is there described, instead of glycerol in amounts of 0.5 to 50 % By weight either 0.5 to 50% by weight, based on the Main component, propylene glycol and / or polyethylene glycol to use.

The present invention is based on the object Process for the production of tissue paper products under Use of a polysiloxane-containing treatment agent Provide improvement in softness, being it it is irrelevant which of the prescribed raw tissue production and processing methods the tissue product produces has been. Such a treatment agent is obtained from a mixture of special amounts of at least one polyhydroxy compound, except natural or chemically modified natural polymers especially one at room temperature, i.e. at 20 ° C, liquid polyethylene glycol and / or glycerin as further component, a portion of a polysiloxane and optionally up to 25 weight percent water. The Application of such a mixture surprisingly leads to a significantly improved softness of tissue products compared to a pure polysiloxane application as well as a pure polyethylene glycol or glycerin application (Synergy effect).

   wobei

und
R₁₉ eine langkettige C₁₂ - C₁₈-Alkylgruppe ist, auf das Faservlies oder die "Tissuebahn" innerhalb der Sieb/Pressenpartie und/oder Trockenpartie, also bei einer Faserstoffdichte von 20 bis 97 %, bezogen auf das Trockenfasergewicht der Bahn, in einer Menge von 0,01 bis 15 % appliziert und das Faservlies nach der Applikation einer Nachglättung unterzieht sowie ein Verfahren zur Herstellung von Tissuepapierprodukten, dadurch gekennzeichnet, daß man ein polysiloxanhaltiges Behandlungsmittel, welches 25 bis 95 Gewichtsteile, vorzugsweise 30 bis 90 Gewichtsteile wenigstens einer Polyhydroxy-Verbindung, insbesondere wenigstens eines bei Raumtemperatur flüssigen Polyethylenglykols und/oder Glyzerin, 5 bis 75 Gewichtsteile, vorzugsweise 10 bis 70 Gewichtsteile Polysiloxan sowie, bezogen auf 100 Gewichtsteile dieser Mischung, 0 bis 35 Gewichtsteile, vorzugsweise 1 bis 30 Gewichtsteile Wasser enthält, ausgenommen ein Behandlungsmittel, enthaltend 5 Gew.-% eines quaternäre Ammoniumgruppen enthaltenden Polysiloxans der allgemeinen Formel

   wobei

und
R₁₉ eine langkettige C₁₂ - C₁₈-Alkylqruppe ist, auf das Faservlies oder die Tissuebahn nach der Trockenpartie in der Tissuepapiermaschine und besonders bevorzugt innerhalb der Doubliermaschine bzw. innerhalb der Verarbeitungsmaschine in einer Menge von 0,01 bis 15 % auf die Bahn appliziert und die Bahn nach der Applikation einer Nachglättung unterzieht.The present invention thus relates to a process for the production of tissue paper products, characterized in that a treatment agent containing polysiloxane, which comprises 25 to 95 parts by weight, preferably 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 , 5 to 75 parts by weight, preferably 10 to 70 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 0 to 35 parts by weight, preferably 1 to 30 parts by weight of water, with the exception of a treatment agent containing 5% by weight of a quaternary ammonium group-containing polysiloxane general formula

in which

and
R _{19 is} a long-chain C ₁₂ - C ₁₈ alkyl group, onto the nonwoven or the "tissue web" within the wire / press section and / or dryer section, that is to say with a fiber density of 20 to 97%, based on the dry fiber weight of the web, in one Applied amount of 0.01 to 15% and subjected to post-smoothing after application and a process for the production of tissue paper products, characterized in that a polysiloxane-containing treatment agent containing 25 to 95 parts by weight, preferably 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, 5 to 75 parts by weight, preferably 10 to 70 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 0 to 35 parts by weight, preferably 1 to 30 parts by weight of water, with the exception of a treatment agent containing 5% by weight of a quaternary ammonium group containing polysiloxane of the general formula

in which

and
R _{19 is} a long-chain C ₁₂ - C ₁₈ alkyl group, applied to the nonwoven fabric or the tissue web after the drying section in the tissue paper machine and particularly preferably within the doubling machine or within the processing machine in an amount of 0.01 to 15% on the web and post-smoothing the web after application.

Preferred embodiments of the invention Manufacturing processes are explained below.

Under the polyhydroxy compound in the sense of Method used according to the invention is understood to be a low and macromolecular organic compound, the two or contain more hydroxy groups in the molecule. To these too Polyols called polyols belong by definition, especially polyhydric alcohols such as for example glycerol, polyethylene glycols, pentaerythritol, Sugar alcohols, such as B. tetrides, pentites, hexites etc., especially threit, 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.

Any water-soluble component can be used as the polysiloxane component and / or water-dispersible compound which at Room temperature (20 ° C) liquid, pasty or waxy is present. This polysiloxane component includes polymers, oligomers, copolymers and others polymonomeric siloxanes. In the following one should under the Term polysiloxane any polymeric, oligomeric or understand other multi-monomeric siloxane material. Farther can the polysiloxane material both a linear structure, a have a branched structure or a cyclic structure.

auf, wobei R₁ und R₂ für jede monomere Siloxaneinheit gleich oder verschieden sind und jeweils eine Alkyl-, Aryl-, Alkenyl-, Alkylaryl-, Arylalkyl-, Cycloalkyl-, halogenierte Kohlenwasserstoff- oder andere Gruppe ist. Jede dieser Gruppen kann substituiert oder unsubstituiert sein. R₁ und R₂-Gruppen von jeder speziellen monomeren Einheit können sich von den entsprechenden funktionellen Gruppen der nächsten anhängenden monomeren Einheit unterscheiden. Weiterhin können diese Gruppen sowohl geradkettig wie auch verzweigt sein oder eine cyclische Struktur aufweisen. Die Gruppen R₁ und R₂ können weiterhin und unabhängig voneinander andere Silikongruppen sein, aber sind nicht auf Siloxane, Polysiloxane und Polysilane beschränkt. Die Gruppen R₁ und R₂ können weiterhin eine große Anzahl von organischen funktionellen Gruppen enthalten, beispielsweise Alkohol, Carbonsäure und aminofunktionelle Gruppen.According to a preferred embodiment, the polysiloxane component has monomeric siloxane units of the following structure:

where R ₁ and R _{2 are the} same or different for each monomeric siloxane unit and each is an alkyl, aryl, alkenyl, alkylaryl, arylalkyl, cycloalkyl, halogenated hydrocarbon or other group. Each of these groups can be substituted or unsubstituted. R ₁ 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 limited to siloxanes, polysiloxanes and polysilanes. The groups R ₁ and R ₂ can furthermore contain a large number of organic functional groups, for example alcohol, carboxylic acid and amino-functional groups.

The degree of substitution and the type of substitution effect that relative degree of softness, silky feel and Hydrophilicity imparted to the tissue paper structure. in the generally the degree of softness and silky increases Griffs, which is caused, among other things, by the polysiloxane, provided the hydrophilicity of the substituted Polysiloxane component decreases. Amino functional polysiloxanes and Polyetherpolysiloxane are as polysiloxane component in Treatment agent particularly preferred.

wobei jeweils die R₁ bis R₉-Gruppen unabhängig voneinander C₁ bis C₁₀ unsubstituierte Alkyl- oder Arylgruppen sind und R₁₀ ein beliebig substituiertes C₁ bis C₁₀-Alkyl- oder Arylradikal ist. Vorzugsweise ist jede R₁ bis R₉-Gruppe unabhängig voneinander eine C₁ bis C₁₀ unsubstituierte Alkylgruppe. Dem Fachmann auf diesem Gebiete ist es bekannt, daß es keinen großen Unterschied ausmacht, ob beispielsweise R₉ oder R₁₀ die substituierte Gruppe ist. Vorzugsweise beträgt das Molverhältnis von b zu (a+b) zwischen 0 und 20 %, vorzugsweise zwischen 0 und 10 % und insbesondere zwischen 1 und 5 %.Preferred polysiloxanes include linear organopolysiloxane compounds of the following general formula,

where in each case the R ₁ to R ₉ groups are, independently of one another, C ₁ to C ₁₀ unsubstituted alkyl or aryl groups and R _{10 is} any substituted C ₁ to C ₁₀ alkyl or aryl radical. Preferably each R ₁ to R ₉ group is independently a C ₁ to C ₁₀ unsubstituted alkyl group. It is known to those skilled in the art that it makes little difference whether, for example, R ₉ or R _{10 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 R ₁₀ is a substituted or unsubstituted alkyl, aryl or alkenyl group. Such materials are generally referred to here as polydimethylsiloxanes, 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 an R ₁₀ alkyl hydrocarbon group and a polydimethylsiloxane with one or more amino, carboxyl, hydroxyl Polyether, aldehyde, ketone, amide, ester, thiol and / or other R ₁₀ functional groups, including alkyl and alkenyl analogs of such functional groups. For example, an amino functional alkyl group such as R ₁₀ 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 process 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 ^-6 m ² / s are preferred here. Highly viscous polysiloxanes that are not themselves flowable can be applied as an ingredient of the treatment agent to tissue paper in an effective manner, for example by emulsifying the polysiloxane component 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 hexane. Special methods for applying the polysiloxane component to tissue paper are discussed below.

The aforementioned polysiloxane components are, 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 described. The monograph "Silicon Compounds ", pages 181 - 217, edited by Petrarch Systems, 1984, a detailed listing and description such polysiloxanes.

in denen R₁₂ in dem Molekül gleich oder verschieden sind und eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen oder eine Polyethergruppe- (C_nH_2nO)_x R₁₃, wobei R₁₃ Wasserstoff, Hydroxyl, Alkyl oder eine Acylgruppe ist und n einen Zahlenwert von 2 bis 2,7 aufweist und x einen numerischen Wert von 2 bis 200 besitzt, mit der Maßgabe, daß wenigstens eine der R₁₂-Gruppen im Durchschnittsmolekül eine Polyethergruppe ist; a einen numerischen Wert von 0 bis 98 hat, b einen numerischen Wert von 0 bis 98 hat und a+b 8 bis 98 ist. R₁₂ kann eine Alkylgruppe mit 1 bis 12 Kohlenstoffatomen oder eine Polyethergruppe sein. Allerdings muß die Bedingung erfüllt sein, daß wenigstens ein R₁₂ im durchschnittlichen Molekül eine Polyethergruppe ist. Vorzugsweise sind 2 bis 5 der R₁₂-Gruppen Polyethergruppen, und die verbleibenden R₁₂-Gruppen haben dann die Bedeutung einer Alkylgruppe, wobei die Methylgruppe besonders bevorzugt ist. Die Alkylgruppe kann aber auch bis zu 12 Kohlenstoffatomen aufweisen. Auf diese Weise ist es möglich, die Eigenschaften des Behandlungsmittels zu variieren und auf diese Weise die Handhabung auf Tissuepapierprodukten zu verbessern. Die Polyethergruppen entsprechen der Formel (C_nH_2nO)_xR₁₃. Der Index n hat einen Zahlenwert von 2 bis 2,7. Im allgemeinen besteht die Ethergruppe aus einer Mehrzahl von Oxyethylenen und gegebenenfalls Oxypropylengruppen. Wenn der Index n 2 ist, besteht die Polyethergruppe ausschließlich aus Oxyethyleneinheiten. Sofern der Zahlenwert von n ansteigt, steigt ebenfalls der Anteil der Oxypropylengruppen an. Der numerische Wert von n = 2,7 bedeutet, daß 70 % der Polyethergruppen Oxypropylengruppen sind.According to a further preferred embodiment, polyethersiloxanes of the general average formula can be used as polysiloxane component in the treatment agents,

in which R ₁₂ in the molecule are the same or different and are an alkyl group having 1 to 12 carbon atoms or a polyether group - (C _n H _2n O) _x R ₁₃ , where R _{13 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 ₁₂ 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 R ₁₂ groups are polyether groups and the remaining R ₁₂ 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 R ₁₃ . 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 R ₁₂ 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 ₁₂ side chains. Siloxanes in which the R ₁₂ groups are arranged in the side chain are preferred. The R ₁₃ group can be hydrogen, hydroxyl, alkyl or also acyl. R ₁₃ is preferably a hydrogen atom. If R _{13 is} an alkyl group, lower alkyl groups with 1 to 4 carbon atoms are preferred. The acetyl group is the preferred acyl group.

wobei R₁₄ eine Gruppe der Formel und

in denen R₁₅ eine divalente Kohlenwasserstoffgruppe ist, deren Kohlenstoffkette durch ein Sauerstoffatom unterbrochen ist, R₁₆, R₁₇, R₁₈ gleich oder unterschiedlich sind und Alkylgruppen mit 1 bis 18 Kohlenstoffatomen darstellen, von denen eine der Gruppen R₁₆, R₁₇, R₁₈ eine -(CH₂)₃ NHCOR₁₉-Gruppe ist, bei denen R₁₉ eine Alkylgruppe mit 7 bis 17 Kohlenstoffatomen und X- ein einwertiges Anion und c einen Zahlenwert von 5 bis 100 aufweist. R₁₅ ist eine divalente Kohlenwasserstoffgruppe, beispielsweise die Gruppe der Formel -CH₂-C(OH)H-CH₂-O-(CH₂)₃-. Die R₁₆-, R₁₇-, R₁₈-Gruppen können gleich oder verschieden sein und sind Alkylgruppen mit 1 bis 18 Kohlenstoffatomen. Allerdings kann eine der vorgenannten Gruppen R₁₆, R₁₇, R₁₈ auch die Bedeutung einer (CH₂)₃ NHCOR₁₉-Gruppe haben.According to a particularly preferred embodiment, the polysiloxane component has the following formula:

where R _{14 is} a group of the formula and

in which R _{15 is} a divalent hydrocarbon group whose carbon chain is interrupted by an oxygen atom, R ₁₆ , R ₁₇ , R _{18 are the} same or different and represent alkyl groups with 1 to 18 carbon atoms, one of the groups R ₁₆ , R ₁₇ , R _{18 is} a - (CH ₂ ) ₃ NHCOR ₁₉ 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 -O- (CH ₂ ) ₃ -. The R ₁₆ , R ₁₇ , R ₁₈ groups can be the same or different and are alkyl groups with 1 to 18 carbon atoms. However, one of the aforementioned groups R ₁₆ , R ₁₇ , R _{18 can} also have the meaning of a (CH ₂ ) ₃ NHCOR ₁₉ group.

If R ₁₆ , R ₁₇ , R ₁₈ groups are alkyl groups, these have 1 to 18 carbon atoms. R ₁₄ groups are particularly preferred in which two of the aforementioned R ₁₆ , R ₁₇ and R ₁₈ groups have 1 to 4 carbon atoms and the third group has up to 18 carbon atoms. If one of the R ₁₆ , R ₁₇ and R ₁₈ groups is a (CH ₂ ) ₃ NHCOR ₁₉ group, the R ₁₉ 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 Cl ^- .

The index "c" indicates the number of dimethylsiloxy units in the linear siloxane and has a numerical value from 5 to 100 and preferably 10 to 80. Particularly preferred of the aforementioned siloxanes are such polydimethylsiloxanes as well for example polyether, alkyl, and with quaternary or betainic groups, especially nitrogen groups modified polydimethylsiloxanes.

Particularly preferred polysiloxanes are those under Designation Tegopren® distributed by Th. Goldschmidt AG organo-modified siloxanes with pronounced surface and Interface activity in aqueous and organic systems.

These are polyether siloxanes, as described in the company publication "Tegopren® Informative", undated, from Th. Goldschmidt AG at 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 mean cloud points in the range below 25 ° C to 71 ° C and modified siloxanes in the form of Teopren silicone quats and betaines, such as those among the Designations Tegopren® 6920, Tegopren® 6922 and Tegopren® 6950 to be expelled.

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 regardless of the fiber raw material to be used, in particular regardless of whether the fiber raw material is produced exclusively or predominantly from native pulps by the sulfate or sulfite process, or is used in a mixture with chemo-thermomechanical wood pulps (CTMP), or whether the fiber raw material used originates from a secondary fiber preparation process and accordingly the fiber raw material required for tissue production consists entirely or partially of "recycled fibers". To differentiate it from so-called nonwovens (nonwovens), it should be noted that although the predominant use of pulp-open, natural, i.e. 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 one Use of plastic fibers suitable for papermaking in a proportion of 10 to 30% falls under the aforementioned definition of tissue. An application of the treatment agent is possible beyond the area of tissue production to corresponding areas of the non-woven area and the textile area in analog transmission.

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

According to a further preferred embodiment of the The present invention is what is used in the method Treatment agent from 5 to 75 parts by weight (or% by weight) at least one polysiloxane and 25 to 95 parts by weight (or% by weight) glycerin. In this case, too, is preferred Treatment agent with 10 to 70 parts by weight, preferably 40 up 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 Glycerin.

Polyethylene glycol and glycerin can be used in the treatment agent can be exchanged in any quantity. But also mixtures of polyethylene glycol and glycerin can in particular under Economic aspects are used, whereby preferably the mixing ratios 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% by weight or Parts by weight, preferably 30 to 70 wt .-% glycerol turn off.

According to a preferred embodiment of the present Invention contains the treatment agent 30 to 90 parts by weight at least one polyhydroxy compound, i.e. at 20 ° C, in particular at least one liquid at room temperature Polyethylene glycol and / or glycerin, 10 to 70 parts by weight Polysiloxane and, based on 100 parts by weight of this Mixture, 1 to 30 parts by weight of water.

It is particularly preferred that such a ternary Treatment mixture 20 to 70 parts by weight of at least one Polyhydroxy compound, in particular at least one Polyethylene glycol and / or glycerin 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 of water contains.

According to a preferred embodiment lies next to the two organic components water as an additional component. The treatment agents then consist of 5 to 75 parts by weight at least one polysiloxane, 25 to 95 parts by weight at least one polyhydroxy compound, especially the aforementioned polyethylene glycol and, based on 100 1 to 30 parts by weight of the above mixture Parts by weight of water.

In this ternary blend with polyethylene glycol as one the components are preferred, 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 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 are used.

It is also particularly preferred per 100 parts by weight Polyethylene glycol 15 to 24, preferably 17 to 22 Parts by weight of water.

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

In addition to these components mentioned above Treatment agent as a further agent with cosmetic agents special properties as well as other usual auxiliary substances contain. For example, skin active ingredients are to be mentioned here based on vitamins or plant extracts, such as for example extracts of horse chestnut seeds, birch, arnica, Chamomile or bisabolol itself, St. John's wort, cucumber, aloe vera or witch hazel, which is partly due to their astringent and healing effects are known.

Other active ingredients here are skin care products, for example sorbitan fatty acid esters and oxyethylated, homologous compounds of glycerin, esters of oxethylated Fatty alcohols, fatty alcohol alkanolamides, oxetylated Fatty alcohols, ethoxylated wool fatty alcohols, Glycerol monostearate, stearic acid, cetylstearyl alcohol, To name Vaseline and Lanolin. In addition to lanolin itself lanolin derivatives are also used, for example Lanolin alcohols or wool wax alcohols, which under the Designation Amerchol® from Union Carbide Inc. in conjunction are sold with mineral oils. Are known here for example the 400, BL, C, CAB, U9, L99, L111, L500 series and RC. Other lanolin derivatives are the acetylated lanolins, and hydrophilic lanolin derivatives, for example lanolin-polyoxyethylene compounds. The invention Treatment agents can also be used as other additives hydrotropic solubilizers for fatty substances, such as Polyalcohol ethers and ethoxylated fatty alcohols are used become.

Another group that is used as an additional component in the treatment agents according to the invention can be used are quaternary ammonium compounds, but especially quaternary ammonium salts, as described, for example, in the US patents 5312522, 5397435, 5405501, 5427696 and the international patent applications WO 95/11344, WO95 / 11343, WO 95/01478, WO 95/01479, WO94 / 29521, WO94 / 29520, WO94 / 16143 and WO94 / 19381 are described.

In addition, fragrances of the usual type can also be added that are selected from natural, nature-identical or artificial fragrances, the corresponding Fragrances are preferred. For example, here Agricultural oils such as lemon oil, bergamot oil, orange oil, Petitgrain oil, softwood oils, foin-coupe fragrance compositions or flower oils such as B. Rose, Jasmine, lilac, lavender, as well as synthetic fragrances based on menthol etc. An overview is provided by Ullmanns Encyclopedia of Technical Chemistry, 4th ed. 1981, volume 20, p. 199-285.

In addition, together with the im Treatment agents used method according to the invention corresponding inorganic pigment or organic dyes can be added, as is usually the case with Tissue paper production can be used. Here are, not finally also for ecological reasons, physiologically safe and non-irritating dyes, especially the corresponding natural dyes, preferred. All of the aforementioned additives and auxiliaries in Treatment agents used method according to the invention can be contained individually or as a combination.

The treatment agent for Tissue paper products come in an order quantity 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. 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 safe wet strength agents, such as Epichlorohydrin resins, urea-formaldehyde resins, melamine-formaldehyde resins as well as cross-linked cationic polyalkylene amines be used.

The treatment agent, which in a preferred Embodiment is in the form of an emulsion, can be used with any any roller and spray application process or in one Impregnation process can be applied to the carrier material. It is always important to ensure that it does not become a Segregation of the emulsion can occur, d. that is, during the Applying the components of the treatment agent well must be mixed to prevent segregation. This happens, for example, by high shear forces for example due to high-speed stirrers, frequent pumping or by ultrasonic mixing.

The treatment agent, which to a noticeably improved Softness of tissue products can be used in can be used in a wide variety of product areas. As Its use, for example, has proven to be particularly advantageous on napkins, toilet paper and hand and kitchen towels, Handkerchiefs, facial tissues and facial tissues.

The above composition of the treatment solution is sized so that it can be used during the period at the consumer at the usually annual average prevailing air humidity due to the water content Long-term use does not cause skin irritation (drying out due to the hygroscopic properties of polyethylene glycol or Glycerin) can come. Also a water vapor proof, reclosable packaging is no longer necessary.

The treatment solution can both in the wet part Tissue paper machine (cotton machine), at the end of the wire section, in front of or within the press section (mechanical Drainage), d. H. with solids contents between 20 and 50% just as in the one arranged after the press section Dryer section with solids contents from 40 to 97% Dry fiber weight can be added. State of the art Dispatch locations on the transfer screen / belt, e.g. B. before Fleece transfer with a TAD arrangement and the feed on the moist nonwoven fabric after its transfer to the transport (Dry) felt in a conventional one- or two-felt tissue production machine. Furthermore, the prior art is Treatment chemicals are sprayed onto the Yankee cylinder.

An addition of the treatment agent is preferred in the Tissue production machine by spraying on the Pope-Roller producing a treatment agent film and its then transfer to the tissue web during the Roll-up process - usually the already creped one "Tissue web" as a result of the previous drying process a residual temperature between 20 ° C on the Yankee cylinder and about 70 ° C, which for the distribution of Treatment agent and its penetration into the raw tissue is favorable - on the contact surface of the single-layer Tissue web with the surface of the drum of the Pope-Roller. In addition to a spray application via a nozzle bar, the Use of centrifugal rotors or brushing plants as well as the indirect transmission of a treatment agent film via Roller applicators come into question. The job can also directly on the tissue paper web. Particularly preferred is an addition of the treatment agent within the Duplicating machine or within the processing machine the outer layers of the multilayered web before or during calibration / smoothing. The order is most preferred of the treatment agent within the processing machine the single or multi-layer web.

According to a preferred embodiment, the Get tissue paper products in such a way that one polysiloxane-containing treatment agent of the above type the tissue web or the nonwoven fabric after the dryer section in the tissue paper machine and particularly preferably within the Doubling machine or within the processing machine in an amount of 0.01 to 15% applied to the web and that Subsequent smoothing of fiber fleece after application. However, it is particularly preferred if you do this The aforementioned, polysiloxane-containing treatment agents at one Fiber density from 35 to 97%, based on the Dry fiber weight of the single-ply web, in an amount of 0.5 up to 10% applied to the single-layer web. Particularly preferred is to use a multi-layer web as a tissue web and that Treatment agent with a fiber density of more than 90%, based on the dry fiber weight, on at least one of the The outer layers of the multilayered web amount to 1 to 7% apply. It is very particularly preferred that Treatments on the multi-layer tissue web on both Apply outer layers in an amount of 3 to 6%.

In the context of the aforementioned method, it is preferred that the Smoothing through at least one pass of the tissue web through a nip of a pair of rollers, in which one Roll with a steel surface of a counter roll with a Steel, plastic, paper or rubber surface, preferably but is assigned to a plastic surface.

This is preferably carried out in such a way that the Smoothing through a double pass of the tissue web through a nip of a pair of rollers, in the first a roll with a steel surface of a counter roll with a Plastic surface and then a mirror with a roller a plastic surface of a counter roll with a Steel surface is assigned.

The smoothing of the tissue web after application of the treatment agent is therefore usually carried out in the manner that the tissue webs sprayed on both sides by a smoothing unit be performed. This calender generally consists of two smooth rollers with steel surfaces (steel rollers) whose Surfaces are usually hard chrome-plated. These reels will be hydraulically or pneumatically compressed or for Calibration run on gap. That is, one of the two Rolling is firmly positioned. The second or counter roll will pressed against a stop, so that the two Can not touch steel rollers, but in a certain, measurable and reproducible distance from each other. The tissue webs guided through this gap are opened Gap width compressed and smoothed. Here, the Structural structure of the surface unified, d. H. a uniform thickness. The result is smoothing by leveling the surface in connection with a Uniformity of the thickness profile under the premise of a as little volume loss as possible.

The usual influencing factors on smoothing are the line force, the surface temperature of the partially heated rollers, the Nip width and the number of nips (number of smoothing units). A The essays in "apr Europe", 3 (1991), pages 121 to 123 and "J.J.A. Rodal Tappi Journal", Volume 76, No. 12, pages 63 to 74 and 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, you can a so-called soft smoothing unit can also be used. Here a steel roller with a plastic surface against a smooth steel roller pressed. Such a smoothing will for example supplied by Küsters Maschinen GmbH. This Soft smoothing calenders include MAT-ON-Line smoothing units known. Another soft smoothing unit with a steel roller and counter roll 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 in DE 3445890 and in EP 0273185 described in more detail.

Furthermore, instead of the two steel rollers that the Form a calender, a calender can also be used, whereby together with a steel roller or steel counter roller a roller or counter roll is used, which is a rubber or Has paper surface.

The provides an overview of common post-smoothing processes German patent DE-A-1804418, the German DE-A-2455895, the German patent specification DE-A-2528803, EP-A-0033559, US patent US-A-2179057, US patent US-A-3337388, British patent GB-A-827735, and the German Patents DE-C-822228 and DE-B-1045783.

Finally, the present invention relates to the use of the aforementioned polysiloxane-containing treatment agent for Softening tissue paper products, in particular Handkerchiefs, facial tissues, facial tissues, napkins, Toilet paper, hand and kitchen towels.

The present invention is described below Exemplary embodiments explained in more detail.

Example 1:

A treatment solution of 32% by weight polyethylene glycol, molecular weight 200, 60% by weight of the polysiloxane Tegopren® 3021, was placed 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% fiber dry weight in the laboratory. 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 procedure according to Example 1 was repeated, however, instead of a ternary mix, it became a binary one Mixture of 50 percent by weight polyethylene glycol, Molecular weight 200 and 50 percent by weight of the polysiloxane used according to Example 1. The sample thus obtained was called B designated.

Comparative experiment 1:

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

Comparative experiment 2:

The procedure of Example 1 was repeated, however instead of the ternary mixture according to the invention, a pure one Polyethylene glycol with a molecular weight of 200 in one amount applied by 6%. The product obtained in this way was treated with D designated. All wipes of Examples 1 and 2 and the Comparative tests 1 and 2 were carried out in a 2-roll (steel / plastic) smoothing unit under identical conditions (Speed, temperature, contact pressure) reproducible smoothed.

The haptic properties of the products A and B were compared with the corresponding haptic results of the Comparative products C (pure polysiloxane) and D (pure Polyethylene glycol) (PEG) compared and these products in As part of a so-called panel test (based on "Manual on Sensory Testing Methods, ASTM, Special Technical Publication 434, p. 22; Test form D-Ranking Methods-Rank Order, Elevents Printings February 1993) was evaluated. Here, the increasing softness, defined here as the sum of Surface softness and softness of one Group of 9 people according to the following procedure rated:

The paper tissues to be checked were two halves folded so that the sample identifier is not for the test subject is recognizable and in any case the same outside of the Evaluation is presented. The cloths folded in this way were given to the test subjects with the instruction that folded towels between thumb, ball of thumb and finger rubbing and crumpling with regard to their softness and Check the surface softness and then the cloths to put increasing, subjective feeling of quality in line. The patterns were ranked 1, i.e. H. best to 4, d. H. worst rated.

The test showed that products A and B according to the invention out of 7 of the 9 test subjects as very good in softness referred to and in relation to the comparative products C and D as were clearly labeled softer. In contrast felt only one of the 9 test subjects compared the product D as softer the product A according to the invention, and one of 9 test subjects the comparative product C softer than that of the invention Products A and B. The panel test also shows that the Products A and B according to the invention are significantly better in relation on crumple softness and surface softness are than that Comparative products C and D.

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

In addition to this first in-house panel test, it continued conducted a studio consumer test with 160 people. Here were samples with a lotion composition Polyethylene glycol / polysiloxane / water in a ratio of 72/10/18 with a 3% order quantity as significantly softer judged as a corresponding comparison pattern with pure Siloxane. Here again the polysiloxane used in Example 1 described polysiloxane and as polyethylene glycol in Example 1 described polyethylene glycol with a Molecular weight of 200 used.

Claims (22)

1. A process for manufacturing tissue paper products , characterised in that a treatment medium comprising polysiloxanes which comprises 25 to 95 parts by weight, preferably 30 to 90 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol that is fluid at room temperature and/or glycerine, 5 to 75 parts by weight, preferably 10 to 70 parts by weight polysiloxane, and 0 to 35 parts by weight, preferably 1 to 30 parts by weight water in relation to 100 parts by weight of this mixture not including a treatment medium comprising 5 % by weight of a polysiloxane comprising quaternary amines having the following general formula

   

   wherein

   

   and wherein R₁₉ is a long-chain alkyl group having between 12 and 18 carbons, is applied in a quantity of 0.01 to 15% to the fibrous web or the "tissue sheet" inside the wire/press section and/or drier section, that is, at a fibre density of 20 to 97% with regard to the dry fibre weight of the sheet, and after application, the fibrous web undergoes a re-smoothing.
2. A process for manufacturing tissue paper products, characterised in that a treatment medium comprising polysiloxanes which comprises 25 to 95 parts by weight, preferably 30 to 90 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol that is fluid at room temperature and/or glycerine, 5 to 75 parts by weight, preferably 10 to 70 parts by weight polysiloxane, and 0 to 35 parts by weight, preferably 1 to 30 parts by weight water in relation to 100 parts by weight of this mixture not including a treatment medium comprising 5 % by weight of a polysiloxane comprising quaternary amines having the following general formula

   

   wherein

   

   and wherein R₁₉ is a long-chain alkyl group having between 12 and 18 carbons, is applied in a quantity of 0.01 to 15% to the fibrous web or the tissue sheet after the drier section in the tissue paper machine and in a particularly preferred manner, inside the combiner or inside the processing machine, and after application, the sheet undergoes a re-smoothing.
3. The process according to claim 2, characterised in that the polysiloxane-containing treatment medium is applied in a quantity of 0.05 to 10% at a fibre density of 35 to 97% in relation to the dry fibre weight of the single-ply sheet.
4. The process according to any of claims 1 to 3, characterised in that the tissue sheet is a multi-ply sheet and the treatment medium is applied in a quantity of 1 to 7% to at least one of the outer plies of the multi-ply sheet at a fiber density of more than 90% in relation to the dry fibre weight.
5. The process according to claim 4, characterised in that the treatment medium is applied in a quantity of 3 to 6% to the multi-ply tissue sheet on both outer plies.
6. The process according to any of claims 1 or 2, characterised in that the depositing of the treatment medium takes place in the tissue making machine by means of spray application onto the pope reel winder in order to produce a film of the treatment medium and to subsequently transfer it to the tissue sheet during the roll-up process.
7. The process according to claims 1 and 2, characterised in that the re-smoothing is carried out by means of at least one pass of the tissue sheet through a gap of a roller pair in which one roller having a steel surface is associated with an opposing roller having a steel, plastic, paper, or rubber surface, preferably a plastic surface.
8. The process according to claims 1 and 2, characterised in that the re-smoothing is carried out by means of a double passage of the tissue sheet through a gap of a roller pair in which first, a roller having a steel surface is associated with an opposing roller having a plastic surface and then, in mirror image fashion, a roller having a plastic surface is associated with an opposing roller having a steel surface.
9. The process according to any of claims 1 to 8, characterised in that the depositing of the treatment medium onto the fibrous web is carried out within the framework of a conventional tissue manufacturing process.
10. The process according to any of claims 1 to 8, characterised in that the depositing of the treatment medium onto the fibrous web is carried out within the framework of a through flow drying process or a TAD process.
11. The process according to claims 1 to 5, characterised in that one uses a treatment medium, comprising 30 to 70 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol that is fluid at room temperature and/or a glycerine, 30 to 70 parts by weight polysiloxane, and 5 to 25 parts by weight water in relation to 100 parts by weight of this mixture.
12. The process according to any of claims 1 to 5, characterised in that one uses a treatment medium comprising 5 to 75 parts by weight of at least one polysiloxane and 25 to 95 parts by weight of a polyethylene glycol that is fluid at room temperature.
13. The process according to claim 12, characterised in that one uses a treatment medium, comprising 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.
14. The process according to any of claims 1 to 5, characterised in that one uses a treatment medium, comprising 5 to 75 parts by weight of at least one polysiloxane and 25 to 95 parts by weight glycerine.
15. The process according to claim 14, characterised in that one uses a treatment medium, comprising 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 glycerine.
16. The process according to any of claims 1 to 3 , characterised in that one uses a treatment medium, wherein the polyhydroxy-compound comprises 20 to 80, preferably 30 to 70 parts by weight of the above-mentioned polyethylene glycol and 20 to 80 parts by weight, preferably 30 to 70 parts by weight of the above-mentioned glycerine.
17. The process according to any of claims 1 to 5 or 13 to 16, characterised in that one uses a treatment medium, wherein the polysiloxane has a viscosity of 25 x 10^-6 m²/s to 20,000,000 x 10^-6 m²/s.
18. The process according to claim 17, characterised in that one uses a treatment medium, wherein the polysiloxane is a polydimethylsiloxane which if necessary, has at least one betaine group, in particular a tetraalkyl ammonium group, in its side chain.
19. The process according to claims 17 or 18, characterised in that one uses a treatment medium, wherein the polysiloxane is a polyethersiloxane, in particular having average cloud points in the range from below 25°C up to 71°C.
20. The process according to any of claims 11 to 19, characterised in that one uses a treatment medium, which furthermore contains cosmetic substances with special properties, for example skin care substances and/or active substances for the skin based on plant extracts and/or scents.
21. The Process according to any of claims 11 to 20, characterised in that one uses a treatment medium, which furthermore contains auxiliary substances such as quaternary ammonium compounds and/or solubilizers and/or wet strength agents.
22. The use of a treatment medium comprising polysiloxanes which comprises 25 to 95 parts by weight, preferably 30 to 90 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol that is fluid at room temperature and/or glycerine, 5 to 75 parts by weight, preferably 10 to 70 parts by weight polysiloxane, and 0 to 35 parts by weight, preferably 1 to 30 parts by weight water in relation to 100 parts by weight of this mixture not including a treatment medium comprising 5 % by weight of a polysiloxane comprising quaternary amines having the following general formula

    

    wherein

    

    and wherein R₁₉ is a long-chain alkyl group having between 12 and 18 carbons for the treatment of tissue paper products, in particular handkerchiefs, cosmetic towels, makeup removal towels, napkins, toilet paper, and kitchen towels.