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

Translation of description of equivalent WO 9608601 A1

Treating agent for tissue paper, process for the production of tissue paper using the Behandlungsinittels and its use

The present invention relates to a treating agent for enhancing the softness of tissue paper, a method for the production of tissue paper, and products produced therefrom by using this treating 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 towels or kitchen towels and describes the feeling which produced the tissue paper when touching the skin.

As described in the week Papermaking Bulletin 11/12, 1988, on page 435 et seq. in the article "softness and softening sanitary tissue", the exact definition of softness although generally understood, but extremely difficult because no physical method of determination and therefore no accepted industry standard exists as a standard for grading of various degrees of softness.

To truly capture the softness, it must be determined by a subjective method, ie it is a so-called panel test determines in which several trained test persons make a comparative judgment.

Softness can be divided over its main characteristics, surface softness and bulk softness:

Surface softness describes the feeling that one feels when one moves slightly with the fingertips over the surface of the tissue sheet.

Under bulk softness is defined as the sensory impression which generates a squeezed with hands tissue during the process of compression.

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

1. Selection of raw materials, especially the pulps

2. machine technical measures (eg. As grinding, sheet forming, drying and creping, smoothing) and

3. Chemical additives and excipients.

Tissue papers require, depending on the application, different properties. So are kitchen towels and even more so with towels strength, particularly strength when wet and high suction capacity required to meet the demands of the consumer. For other products, such as handkerchiefs or facial tissues softness of the surface and very good conformability are salient features that determine next resistance the shelf life of these products. With toilet paper determines a combination of dry strength results in good softness and good appearance Dick fitness for use and consumer acceptance. For papermakers it is a particular challenge to bring the various, often conflicting influence factors in a particular balance to therefrom represent consumer demand for optimal combinations of properties for the desired end products.

Today it is a sign of the times that all product areas in hygiene articles to improve the softness is transversely one of the main demands of the papermaker. Properties like softness of a tissue product are determined in their basic training through the production process and selection of raw and auxiliary materials, as discussed previously.

The tissue making process includes independent of its different variants the following procedural steps:

Suspending the fibers in water, possibly adding chemical products for the targeted control of product characteristics and process flow, activation of the fiber surfaces to develop the strength potential of the fibrous raw materials by mechanical treatment such as grinding in a refiner, sheet formation by depositing the fibers, oriented or in random orientation on or between two endlessly revolving screens of the paper machine while simultaneously removing the main quantity of dilution water to dry contents 12-35%, drying of the primary fiber web formed in one or more steps by mechanical and thermal means until a final dry matter content of around 93 to 97%. Among the most relevant for tissue production steps continues to be one of the creping operation, the dominant influence on the properties of the finished tissue product in conventional process. At today mainly applied dry crepe process crepe is done on a drying cylinder, with typically 4.5 to 6 m diameter, the so-called Yankee cylinder, by means of a Crepe doctor with the aforementioned final dry the Tissuerohpapiers. With older methods with lower demands on the tissue quality also Naßkreppverfahren is applied, the dry creping process, however, runs similar at lower dry contents below 80%, usually about 55 to 65% solids content, with a secondary drying at subsequent drying cylinders of a dryer section to the final dryness. The creped, final dryness raw tissue paper (raw tissue) is wound in a subsequent step to a supporting core to a so-called drum or slit sleeves on to master rolls and is in the form for further processing into finished products.

To produce multi-ply tissue papers, such. As handkerchiefs, toilet paper, towels or kitchen towels is done often an intermediate step with the so-called doubling in which usually the Rohwatte (raw tissue) handled in a desired number of layers of the finished product corresponding reel number and common to a multilayer parent roll is wound. In this processing step is included in two or Mehrwalzenglättwerken often a smoothing or calibration. However, the smoothing (calibration) can be performed directly before the reel in the tissue making machine after drying and creping.

The processing process, for example, to Faltprodukten as handkerchiefs or cosmetic wipes (facials) takes place in subsequent, separate operations in particular, designed for the task processing machines, the operations such as repeated smoothing of the tissue, edge embossing, partially combined with a scale and / or selective bonding to produce layer adhesion of each other in the composite to be placed on individual layers (base tissue) and longitudinal section, folding, cross-filing and merge multiple wipes and their packaging in bags or towels so-called special jewelry boxes and bringing them together to include larger outer packaging or containers. Instead of edge embossing the ply adhesion can also be produced by knurling as z. B. is common in Kosmetitktüchern.

In addition to the described conventional tissue making process in particular in the United States, today, increasingly, in Europe, modified techniques in use, where by a special kind of drying within the tissue machine, an improvement of specific volume and in this way an improvement in bulk softness of thus prepared tissue is achieved. These existing in different subspecies methods are called TAD (Through Air Drying) processes (through-air drying). It is characterized in that the sheet formation leaving the "primary" fibrous web is pre-dried on the Yankee cylinder before final contact drying to a dry content of about 80%, by blowing hot air through the nonwoven fabric. The fiber web is thereby supported by an air-permeable screen or belt and out during its transport over the surface of an air-permeable rotating cylinder drum. by structuring the support wire or the Beltes can any pattern of compressed and by deformation in the moist state are generated on loosened zones increased, medium, volume and related thus leading to an increase in bulk softness without the strength of the nonwoven fabric drops below that required for our use measure. another influence the process of accurately, raw tissue softness and strength is the application of a layering in which the to be formed primary fibrous web specifically by a constructed headbox in the form of material is built up of different fibrous layers, which are supplied as a stock jet common sheet formation. In the application of lamination include fibrous webs, consisting of two or three or more layers to the prior Art, for example DE-C 43 47 499. By appropriate selection of raw materials in the stratification determining channels of Stoffauflaufaustrittsdüse, for example, the use of eucalyptus fibers on the Yankee cylinder surface facing web page can be significantly increased the surface softness, what the hergestellen from accurately, raw tissue products benefits.

In addition, the use of chemicals in the form of a lotion contract on the raw tissue during Rohtissue- generation process, the doubling or the subsequent processing to the softness improvement is known. The term "lotion" comprises cosmetic usage generally understood aqueous or aqueous-alcoholic preparations with emulsifying agents. In particular, the use of aqueous solutions or emulsions of polyhydroxy compounds such as glycol or polyethylene glycol or the use of polysiloxanes to the softness improvement of tissue are described. So far not known however, that a significant increase in softness can be achieved as a synergistic effect of a mixture of a polysiloxane in an aqueous emulsion with a polyethylene glycol.

The use of polysiloxanes described as a treating agent for improving softness of tissue in the patent literature. Not yet known, however, that a significant softness improvement can be achieved as synergistic effects of using a mixture of a polysiloxane with a polyhydroxy compound, such as. For example, polyethylene glycol or glycerol as a treating agent for tissue in aqueous emulsion. As relates to the WO 90/09807 a tissue product comprising at least one tissue sheet, said tissue product contains from 0.1 to 5 percent 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, US Patent 49 50 545 emerged. EP-A-0,347,154 relates to a tissue paper having a basis weight of 10 to 65 g / m² and a density of not more than 0.6 g / ml, wherein this paper contains cellulosic fibers and a polysiloxane, wherein the amount of at least 0.004% polysiloxane based on the dry (fiber) weight of this non-woven fabric. Object of the emerged therefrom US patent 50 59 282 is accordingly reduced to a tissue paper having a basis weight of 10 to 65 g / m² and a density of not more than 0.6 g / ml, wherein this paper cellulosic fibers and an effective amount of a polysiloxane material, wherein said polysiloxane is uniformly applied to the outward-facing surfaces of the tissue paper, said effective level of the polysiloxane 0, 004 % to 2% polysiloxane based on the dry (fiber) weight of the tissue paper refers, said polysiloxane has a viscosity of 25 centistokes and more and after an aging time of two weeks after its manufacture, has a wetting time of not more than 2 minutes. A manufacturing method for such a paper is the subject of EP-A-347 153 and the corresponding US patent 52 15 626th

WO93 / 02252 relates to a manufacturing method. (Laying wet) for soft tissue paper with the step sequence of a sheet formation from an aqueous suspension of cellulose fibers to form a nonwoven fabric (nonwoven), drying of the nonwoven fabric while raising the temperature of the nonwoven fabric to at least 43 ° C, creping of 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 such that 0.004%, relative to 0.75% of said polysiloxane on the dry (fiber) weight of this tissue paper remain in this nonwoven fabric, said tissue paper has a basis weight from 10 to 65 g / m and a density of less than 0.6 g / m³ having. After a preferred embodiment, may be added simultaneously with the polysiloxane, inter alia, a water-soluble surfactant. This subject is also described in US-A-50 59 282nd

WO94 / 05857 relates to a process for applying a chemical papermaking additive to a dry tissue paper web (tissue paper non-woven fabric raw tissue), said method being characterized in that it comprises the following steps:

Providing a dry tissue paper non-woven fabric, the diluting a chemical papermaking additive with a suitable solvent to form a dilute chemical solution, the application of this diluted chemical solution to a heated transfer surface, the partial evaporation of the solvent through the transfer surface to form a this paper making additive containing film and the transmission of the film from the heated transfer surface to the surface of the tissue non-woven fabric, that a sufficient amount of the chemical papermaking additive is carried out in such a way that 0.004 to 2% of said chemical papermaking additive, based on the dry (fiber) weight of this tissue non-woven fabric in this tissue nonwoven fabric remains. Preferably, this is understood to mean papermaking additive fabric softeners and mixtures thereof, preferably softeners, which are selected from lubricants, plasticizers and mixtures thereof, where these lubricants are polysiloxanes. If a chemical softener that is to serve primarily as a plasticizer, is desired, it can be selected from a group of chemicals, including inter alia polyethylene glycol, such as polyethylene glycol having a molecular weight of 400 counts. From this patent application, US 5,256,546 has emerged.

The DE-A-28 00 132 relates to a soft, supple skin cleansing products with a fleece with a wiper surface and a wiping zone of low density, wherein the wiping surface is a boundary of the wiping zone of low density, the wiping zone of low density is soil permeable and comprises a plurality of lying in and under the surface cavities and the wiping zone of low density with about 10 to 150% lipophilic Reinigungse oliens is, based on the weight of the nonwoven fabric treated. The term lipophilic Reinigungsemoliens cover, inter alia, silicone oils and nonionic surfactants.

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

EP-A-0459501 relates to a process for the reduction of the static charge and the destruction during a Naßdruckverfahrens, which is characterized in that to the paper a silicone polymer emulsion having a particle size of less than 200 nm, a cationic surfactant and a nonionic surfactant is applied.

Further patents are known which describe the use of a mixture of polyethylene glycol with quaternary amines (cationic surfactants) as the treating agent, for example, US-A-5312522nd

As relates to the DE-C-34 47 499 a non-drying cleaning cloth, which is characterized in that on a support material, an emulsion is applied which consists of at least one moisture regulator, preferably polyethylene glycol and at least one additional liquid substance. Furthermore, it is known to use as a plasticizer in the manufacture of soft tissue paper, an anionic surfactant, nonionic surfactant or mixtures thereof.

EP-A-03 47 177 relates to a method for preparing soft tissue paper comprising the steps of:

Sheet formation from an aqueous suspension (wet laying) of cellulose fibers to form a nonwoven fabric, application of a sufficient amount of a water-soluble noncationic surfactant such that from 0.01 to 2% of said non-cationic surfactant, relative to the dry (fiber) weight of this tissue paper through the web are retained, said application is carried out at a fiber consistency of 10 to 80% as well as drying and creping of the web, wherein this tissue paper has a basis weight of 10 to 65 g / m² and a density of less than 0.6 g / m³ having.

EP-A-0607796 relates to a an organo-silicone compound-containing non-wovens, wherein the improvement consists in that the organo-silicone compound contains 95 to 98 wt .-% of a water soluble or water

Polyether polysiloxane, the polyether groups of 30 to 100 mol% of oxyethylene units and oxypropylene units exist as a radical, and the polysiloxane comprises 10 to 100 siloxane units, 1 to 20 wt .-% of a water-soluble or water-dispersible organo-polysiloxane having at least one ammonium group on the carbon atom mounted and 1 to 20 wt .-% of water or a water-soluble alkylene glycol.

The present invention has for its object to provide a polysiloxane treatment agent for tissue paper products to improve the softness, it is irrelevant, according to which the prescribed Rohtissueerzeugungs- and Processing tissue product of the invention was produced. Such a treatment agent is obtained by a mixture of special Amounts of at least one polyhydroxy compound, in particular a liquid at room temperature of polyethylene glycol and / or glycerol as a 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 over a pure Polysiloxanapplikation and compared with a pure polyethylene glycol or glycerol application (synergistic effect).

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

Of the polyhydroxy compound in the context of the present compound refers to a low and macromolecular organic compound containing two or more hydroxy groups in the molecule. These also polyols mentioned polyhydroxy compounds by definition includes, in particular polyhydric alcohols such as glycerin, polyethylene glycols, pentaerythritol, sugar alcohols such. B. Tetride, pentites, hexitols etc., especially threitol, erythritol, Adonit, arabitol, xylitol, dulcitol, mannitol and sorbitol, carbohydrates such as D (+) - glucose, D (+) - fructose, D (+) - galactose, D (+) - mannose, L-gulose, sucrose, galactose or maltose, and synthetic polymers such as polyvinyl alcohol. When at room temperature, ie 20 ° C liquid polyethylene glycols, are those designated with an average molecular weight of 200 to 600th As polysiloxane can be any water-soluble and / or water-dispersible compound, which is at room temperature (20 ° C) in liquid, paste or waxy, are used. The polysiloxane component used for the purposes of the present invention includes polymeric, oligomeric, copolymeric and other polymonomere siloxanes. In the following we to understand any, the term polysiloxane polymeric, oligomeric or else mehrfachmonomeres siloxane. Further, the polysiloxane material may comprise both a linear structure, a branched structure or a cyclic structure.

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

Ri

I (1) Si - 0

I

R₂

, where Ri and R₂ for each siloxane monomeric unit are the same or different and each is an alkyl, aryl, alkenyl, alkylaryl, arylalkyl, cycloalkyl, halogenated hydrocarbon or other group. Each of these groups may be substituted or unsubstituted. Ri and R₂Groups of any particular monomeric unit may differ from the corresponding functional groups of the next adjoining monomeric unit. Furthermore, these groups may be either straight-chain or branched or have a cyclic structure. Groups R i and R₂ can continue to be independently and other silicone groups, but are not limited to siloxanes, polysiloxanes, and polysilanes. Groups R i and R₂ can still a large number of containing organic functional groups, for example, alcohol, carboxylic acid and aminofunktioneile groups.

The number of substitution and the type of substitution determine the relative degree of softness, the velvety hand and hydrophilicity imparted to the tissue paper structure. In general, the degree of softness and the velvety hand, which is caused inter alia by the polysiloxane increases, provided that the hydrophilicity of the substituted polysiloxane component decreases. Amino-functional polysiloxanes and polyether polysiloxanes are polysiloxane as the treatment agents of the invention are particularly preferred.

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

(2: R₂ - Rs

<img id="imgf000015_0001" he="31" wi="101" file="imgf000015_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> in each case the R to Rc, groups C are independently to C unsubstituted alkyl or aryl and Rio an arbitrarily substituted Ci to Cio-alkyl or aryl radical. Preferably, each Ri to Rg group is independently a Ci to Cio substituted alkyl group. Those skilled in this field, it is known that it does not make much difference whether, for example, R₉ or Rio is the substituted group. the mole ratio of b to (a + b) between 0 and 20 is preferably, preferably between 0 and 10% and in particular between 1 and 5%.

According to a particularly preferred embodiment, Ri to R₉Methyl groups, and Rio is a substituted or unsubstituted alkyl, aryl or alkenyl group. Such materials are generally herein as polydimethylsiloxane denotes which have a special functionality as they are used in this case. Examples of such polydimethylsiloxanes may be:

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

Polydimethylsiloxane with an Rio-alkyl hydrocarbon group and a polydimethyl siloxane with one or more amino, carboxyl, hydroxyl, ether, polyether, aldehyde, ketone, A ID, ester, thiol and / or other functional groups Rio a, included alkyl and alkenyl analogs of such functional groups. For example, an amino functional alkyl group as Rio an amino-functional or an aminoalkyl-functional polydimethylsiloxane .His. The exemplary listing of these polydimethylsiloxanes does not mean that others are not specifically mentioned herein, excluded from it.

The viscosity of the polysiloxanes used as component in the treatment agent according to the invention may vary over a wide range, so 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. These are understood, for example, viscosities of 25 x 10^"6 m²/ S to 20,000,000 x 10^"6 m²/ S or even higher. Preferred here are viscosities of 15,000 x 10^{~ 6} m²/ S to 3,400,000 x 10^" m²/ S. High viscosity polysiloxanes which themselves are not capable of flowing, may be applied as a component of a treatment agent of the present invention to tissue paper in an effective manner by, for example, the polysiloxane component according to the invention emulsified in PEG or glycerin or water or dissolved in a mixture thereof together with a surfactant or the polysiloxane unless it in PEG or glycerin or water is releasable by means of a solvent, such as hexane, brings in solution. Special methods for applying the polysiloxane component onto tissue paper are discussed in the following.

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 849,433th Furthermore contains the monograph "Silicon Compounds", page 181-217, published by Petrarch Systems, 1984, a detailed list and description of such polysiloxanes.

According to a further preferred embodiment of the general average formula can be used as the polysiloxane component in the inventive treatment compositions polyether siloxanes.

(3)

R i2 - i2

<img id="imgf000017_0001" he="26" wi="77" file="imgf000017_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" />

where Rχ₂ in the molecule are identical or different and an alkyl group having 1 to 12 carbon atoms or a Polyethergruppe- (C_nH_2nO)_x Rι₃Wherein Rι₃ Hydrogen, hydroxyl, alkyl or acyl group and n has 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 Rι₂Groups in the average molecule is a polyether; 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.. R₁₂ may be an alkyl group having 1 to 12 carbon atoms or a polyether group. However, the condition must be met that at least one R₁₂ in the average molecule is a polyether group. Preferably, 2 to 5 of Ri₂~ Groups polyether, and the remaining Ri₂~ Groups then have the meaning of an alkyl group, where the methyl group is particularly preferable. but the alkyl group may also have up to 12 carbon atoms. In this way, it is possible to vary the properties of the treatment agent and thereby to improve the handling of tissue paper products. The polyether according to the formula (C_nH_2nO)_xRι₃, The index n has a numerical value of 2 to 2.7. In general, the ether group consists of several oxyethylenes and optionally oxypropylene groups. If the index n is 2, the polyether consists exclusively of oxyethylene units. If the numerical value of n increases, also increases the proportion of the oxypropylene groups. The numerical value of n = 2.7 means that 70% of the polyether groups are oxypropylene groups.

The subscript x denotes the number of oxyalkylene units. This value is a mean numerical value since a mixture of products of varying chain length is usually obtained in the synthesis of polyethers. The index x has a numerical value from 2 to 200 and is preferably from 10 to 50. polyether having an average molecular weight from 600 to 4000 are preferred. The index a means the number of methyl siloxane units, of which R₂~ Group are supported. The index b corresponds to the number of the dimethylsiloxane units. While a and b can assume a value from 0 to 98, the condition must be satisfied that the sum of a + b has a value of 8 to 98th When a = 0, then the polyether group or groups is terminally connected. The siloxanes with positive values ​​for a are the Rι₂- Modified side chains. Siloxanes in which the Ri₂~ Groups are arranged in the side chain, are preferred. The Rι₃- Group can be hydrogen, hydroxyl, alkyl or acyl. Preferably Rι₃ a hydrogen atom. Unless Rι₃ is an alkyl group, then low alkyl groups having 1 to 4 Carbon atoms are 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_l4 - - Rn

<img id="imgf000019_0001" he="29" wi="58" file="imgf000019_0001.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> wherein Rι a group of formula and

(5) - R₁₅ - <img id="imgf000019_0002" he="21" wi="33" file="imgf000019_0002.tif" img-format="tif" img-content="drawing" orientation="portrait" inline="no" /> RL7

where R ₅ a divalent hydrocarbon group whose carbon chain is interrupted by an oxygen atom, Ri₆ R₁₇, Rie are the same or different and represent alkyl groups having 1 to 18 carbon atoms, of which one of the groups Ri_ß, Rι, Rie a ~ (CH₂)₃ NHCORig group, in which R₁₉ an alkyl group having 7 to 17 carbon atoms and X- is a monovalent anion and c has a numerical value of from 5 to 100 bar. R₁₅ is a divalent hydrocarbon group, for example the group of formula -CH₂-C (OH) H-CH₂-0- (CH₂)₃~. The Ri₆-, R₁₇-, Ri_8thGroups may be the same or different and are alkyl groups having 1 to 18 carbon atoms. However, one of the aforementioned groups Ri_ß, Rι₇, Rie, the importance of (CH₂)₃ have NHCORig group.

If Ri_ß, R₁₇, Rιβ groups are alkyl groups, as these have 1 to 18 carbon atoms. More preferably, R₁₄- Groups, where two of the above R_ß-, R₁7-, 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 a (CH₂)₃ NHCORι₉Group is, the Rig-group is an alkyl group having 7 to 17 carbon atoms. X^~ is a monovalent anion, in general an acetate group. X, however, may also be an inorganic group such as CI^" be.

The subscript "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 foregoing siloxanes are those polydimethylsiloxanes as well as, for example, polyether, alkyl, and with quaternary or betainic groups, in particular nitrogen group-modified polydimethylsiloxanes.

Particularly preferred polysiloxanes are sold under the name Tegopren® ® from Th. Goldschmidt AG organo-modified siloxanes having been Präger surface and interface activity in aqueous and organic systems.

These are polyether, as described in the company publication "Tegopren® Informative", undated, of 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, 5884 and Tegopren® Tegopren® be 7006 sold and typically have average cloud points in the range of below 25 ° C to 71 ° C and have modified siloxanes in the form of Teopren silicone quat and -Betainen as among

designations Tegopren®^® 6920, 6922 and Tegopren® Tegopren® be 6950 sold. The term tissue paper or shortly tissue within the meaning of the present invention is meant all kinds of from aqueous dispersion produced creped paper having a basis weight between 10 and 65 g / m², The term tissue paper covers according to the invention both from, called both the full range of creped raw papers, also raw tissue, in particular the area of ​​trockengekreppten raw tissue, regardless of whether one or more layers, and all of these creped raw papers single- or multilayer end products, such as handkerchiefs , face and facial tissues, toilet paper, kitchen towels, hand towels and serviettes. The term tissue paper is also independent of the to use fiber raw material to see, in particular, whether the fiber raw material produced solely or primarily from natural pulps according to the sulphate or sulphite, or is used in admixture with chemi-thermomechanical pulps (CTMP) or whether the fiber raw material used a

Secondary fiber processing method recorded and therefore the need for tissue generation fiber raw material in whole or in part from "recycled fibers" is. In order to distinguish over so-called nonwovens (non-wovens) should be noted that although the predominant use papermaking receptive to the tissue paper production, natural, ie vegetable pulp is characteristic , a proportional use by refinement of modified cellulose fibers in a range of 10 to 50% or even use with papermaking suitable synthetic fibers in a proportion of 10 to 30% under the above definition of the term tissue falls. one application of the treatment agent of the invention throughout the range of tissue production also possible to appropriate areas of the non-woven region and the textile area in analog transmission.

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

According to another preferred embodiment of the present invention, the treating agent of 5 to 75 parts by weight (or wt .-%) consists of at least one polysiloxane and 25 to 95 parts by weight (or wt .-%) glycerol. It is also preferred in this case, a treating agent containing 10 to 70 parts by weight, preferably 40 to 60 parts by weight of at least one polysiloxane and 30-90 parts by weight, particularly 40 to 60 parts by weight glycerin.

Polyethylene glycol and glycerol can be exchanged in the treatment compositions of the invention in any amount. But also mixtures of polyethylene glycol and glycerol may be used in particular under cost-effectiveness point of view, preferably the mixing ratios of 20 to 80 wt .-% and parts by weight, preferably 30 to 70 wt .-% and parts by weight of the above-mentioned polyethylene glycol and 20 to 80 parts by weight % or parts by weight, preferably 30 to 70 wt .-% glycerol account.

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 room temperature liquid polyethylene glycol and / or glycerol, 10 to 70 parts by weight of polysiloxane as well as, based on 100 weight parts 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 room temperature liquid polyethylene glycol and / or glycerol, 30 to 70 parts by weight polysiloxane, and, based on 100 weight parts of this mixture, 5 to 25 parts by weight contains water.

According to a preferred embodiment, in addition to the two organic components of water as an additional component before. The treating 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 of the above-mentioned polyethylene glycol and, based on 100 parts by weight of the aforementioned mixture to from 1 to 30 parts by weight of water.

With this ternary blend with polyethylene glycol as one of the components is preferred, a mixture of 30 and 90, but especially 40 to 60 parts by weight of polyethylene glycol, 10 to 70 parts by weight, preferably 40-60 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 water is used.

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

According to a further preferred embodiment, with glycerol as one of the components is preferred, a first binary mixture of 30 to 90, but especially 40 to 60 parts by weight of glycerol, 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 used. Is furthermore particularly preferred, per 100 use parts by weight glycerine 23 to 32 parts by weight, preferably 25 to 30 parts by weight of water.

In addition to these aforementioned components treatment agent of the invention can be used as additional agents contain cosmetic products with special properties as well as other, customary auxiliaries. These include, for example, skin-based drugs of 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, which is known partly for its astringent and healing promoting activity are.

Further active ingredients here are skin care products, for example, sorbitan, and oxyethylated, homologous compounds of glycerin, esters of ethoxylated fatty alcohols, Fettalkoholalkanolamide, oxetylierte fatty alcohols, ethoxylated lanolin alcohols,

Glycerol monostearate, stearic acid, cetostearyl alcohol, to name Vaseline and lanolin. In addition to lanolin itself also lanolin derivatives may be used, such as lanolin or wool wax alcohols, under the

Designation Amerchol® by Union Carbide Inc. in conjunction with Mineralöen be ertrieben. here are known, for example, the 400 series, BL, C, CAB, U9, L99, llll, L500 and RC. Other lanolin derivatives are the acetylated lanolin, and hydrophilic lanolin derivatives, for example, lanolin polyoxyethylene compounds. The treatment compositions of the invention can be used as other additives hydrotrope solubilizer for fats such as polyalcohol ethers and ethoxylated fatty alcohols.

Another group that can be used as an additional component in the treatment compositions of the invention are quaternary ammonium compounds, but especially quaternary ammonium salts, as described for example in U.S. Patents 5312522, 5397435, 5405501, 5427696 and International Patent Applications WO 95/11344, W095 / 11343, WO 95/01478, WO 95/01479, are described W094 / 29521, WO94 / 29520, W094 / 16143 and W094 / 19,381th

In addition, fragrances usual type can be added, which are selected from natural, nature identical or artificial fragrances, the corresponding fragrances are preferred. For example, here are citrus oils such as lemon oil, bergamot oil, orange oil, petitgrain oil, Softwood oils Foin-coupe

. Fragrance compositions or blossom oils such as rose, jasmine, lilac, lavender, as well as synthetic fragrances based on menthol, etc. An overview is Ullmann's Encyclopedia of Industrial Chemistry, Vol 20, pp 190-185.

In addition, appropriate together with the treating agent of the present invention, inorganic pigment or organic dyes can be added, as are commonly used in the tissue paper production. Here are, not least for environmental reasons, physiologically acceptable and not skin irritating dyes, especially the corresponding natural dyes, preferred. All of the above additives and adjuvants in the treatment agent of the invention may be both included individually and in combination.

The treatment agent for tissue paper products described above is in a coverage in the range of 0.01 to 15 weight percent, preferably 0.5 to 10 weight percent, most preferably 2 to 6 weight percent, based on the dry weight of fiber, is applied.

As carrier material to which the treatment agent is to be applied, is preferably a mono- or multi-layer, preferably at least two-ply or four-ply, and more preferably three or unembossed embossed tissue paper used. The individual paper webs can be mechanically joined together by edge embossing or knurling over glued or points or connected in any way with each other. For the individual webs continue to have a basis weight range of 10 to 40 g / m², Preferably 14 to 30 g / m², Especially 15 to 25 g / m², Most preferably from 15.5 to 17.5 g / m² proved. For special applications, however, may also be heavier or lighter papers having basis weight ranges from 8 to 65 g / m² be useful.

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

Melamine-formaldehyde resins and crosslinked cationic polyalkylene used.

The treating agent which is present in a preferred embodiment in the form of an emulsion may be applied by any roller and spray application or in an impregnation on the carrier material. This is necessary to take care that it can, that is, during the application of the components of the treating agent must be mixed thoroughly to prevent segregation not lead to a separation of the emulsion. This is done for example by high shear forces, produced for example by high-speed stirrers, frequent UMPU pen or an ultrasonic mixing.

The treatment agent which can be used in a perceptibly improved softness of tissue products can be used in a variety of product areas. Be particularly advantageous, for example, be used on napkins, toilet paper and towels and kitchen towels, handkerchiefs, cosmetic wipes and Abschminktüchern proves. The above-mentioned composition of the treatment solution is such that it can not lead to skin irritation (dehydration due to the hygroscopic properties of polyethylene glycol or glycerol) during the period of use by the consumer at the usually prevailing annual average humidity by the water content even in continuous use. Also its water vapor resistant, reclosable package is no longer necessary.

The treatment solution can be used both in the wet section of a tissue paper machine (wadding machine), at the end of the wire section, before or inside the press section (mechanic drainage), ie with solids contents between 20 and 50% as well as in arranged after the press section drying section at solids contents 40-97 % fiber dry weight is added. State of the art object places on the Transfersieb / Belt, z. B. before yarn transfer in a TAD arrangement and the addition to the wet nonwoven fabric after its transfer to the transport (dry) felt in a conventional single- or Zweifilz- tissue making machine , Further prior art is the feed of treatment chemicals in the spray application to the Yankee cylinder.

Preference is given to the addition of the treatment agent in tissue making machine by spray application onto the Pope roller to form a treatment agent film and the subsequent transfer to the tissue web during the reeling up process - which usually already creped "tissue web" as a result of the previous drying process on the Yankee cylinder or a final 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 - one on the contact surface of the single-ply tissue web to the surface of the carrier drum of Pope scooter in addition to spray over. nozzle beam can also Use of centrifugal rotors or Bürstwerken and the indirect transmission of a treating agent film on roll applicators come in question. The order can also be made directly to the tissue paper web. Particularly preferred is an addition of the treatment agent within the doubling machine or inside the processing machine to the outer layers of the multiply doubled web before or during the calibration / smoothing. Most preferably, the order of the treatment agent within the processing machine on the single or multi-ply web is.

The present invention therefore relates to a method for preparing soft tissue paper products, which is characterized in that, on the tissue web within the Siebpressenpartie and / or dry end or outside of the tissue-forming machine in the Doublier- or the processing machine, therefore, at a fibrous material density of 20 to 97% has been applied or is applied based on the dry fiber weight of the web, a treatment agent of the aforementioned type in an amount of 0.01 to 15% and the nonwoven fabric undergoes a re-smoothing process after the application.

According to a preferred embodiment, the tissue paper products are obtained in such a manner that a polysiloxane-treating agent of the above type to the tissue web or the nonwoven fabric after the dryer section in the tissue paper machine, and particularly preferably within the doubling machine or inside the processing machine in an amount of 0.01 to 15% applied to the web and the nonwoven fabric undergoes a re-smoothing process after the application. It is particularly preferred, however, if one applies the aforementioned, polysiloxane-containing treating agent at a fibrous material density of 35 up to 97%, based on the dry fiber weight of the single-ply web in an amount of 0.5 to 10% on the single-ply web. It is particularly preferred to use a multi-ply web as a tissue web and the treating agent at a fibrous material density of more than 90%, is relative to apply to the dry fiber weight, to at least one of the outer layers of the multilayer web in a quantity of 1 to 7%. Very particularly preferably, the multi-ply tissue web to apply the treatment agent on both outer plies in an amount of 3 to 6%.

In the context of the aforementioned method, it is preferred that the re-smoothing is carried out by at least one pass of the tissue sheet through a gap of a roller pair in which one roller having a steel surface a counter roller having a steel, plastic, paper or rubber surface, preferably, however, a plastic surface is associated.

Preferably, this is carried out in such a manner that the re-smoothing is carried out by a two-time passage of the tissue sheet through a gap of a roller pair in which first, a roller having a steel surface a counter roller having a plastics surface and then in mirror image a roller having a plastic surface of a counter roller having a steel surface assigned.

The re-smoothing of the tissue web after the application of the treatment agent, therefore, is usually carried out in the manner that the sprayed on both sides tissue webs are passed through a calender. This polishing stack is generally composed of two smooth steel rollers with surfaces (steel rollers) whose surfaces are usually hard-chrome plated. These rollers are hydraulically or pneumatically compressed or moved on to calibrate gap. That is, one of the two rollers is firmly positioned. The second or counter roll is pressed against a stop, so that the two steel rollers can not touch, but are in a specific, measurable and reproducible spacing. The run through this gap tissue webs are compressed to gap width and smoothed thereby. Here, the microstructure of the surface is unified, ie a uniform thickness caused. Thus is smoothed by leveling the surface in conjunction with a more uniform thickness of the profile under the premise of a minimum volume of loss.

Usual influence factors on smoothing are the line force, the surface temperature of the partially heated rollers, the nip width and the Nipzahl (number of calenders). An overview of this pass the essays in "apr Europe", 3 (1991), page 121 to 123, and "JJA Rodal Tappi Journal", Volume 76, no. 12, page 63-74, and the overview of E. Weißhun and H. Holik, in "Das Papier", Vol 38, (1984) Nr. 10A.

Instead of the two steel rollers that make up the polishing stack, also a so-called soft-calender can be used. Here, a steel roller is pressed with a plastic surface against a smooth steel roller. Such smoothing is supplied for example by the Küsters GmbH. These soft smoothing calenders are known among other things as a MAT-ON-line calenders. Another soft calender with steel roller and counter-roller having a plastic surface is the NIPCO MAT smoothing of the Edmund Küsters Maschinenfabrik, Krefeld, see. Wochenblatt papermaking 13/91, S. 491 to 498. Such rolls are described in DE 3445890 and in EP 0273185 described.

Furthermore, instead of the two steel rollers that make up the calender, a calender also be used, in which together with a steel roll or steel counter-roll, a roller or counter-roller is used, which has a rubber or paper surface.

An overview of customary Nachglättungsverfahren are German Patent 1804418, German Patent Application 2455895, German Patent 2528803, EP-A-0033559, US Patent 2179057, US Patent 3337388, British Patent 827,735, as well as the German patents 822 228 and 1,045,783th The present invention relates to the use of the aforementioned polysiloxane-treating agent for softening tissue paper products, in particular handkerchiefs, cosmetic wipes, Abschminktüchern, napkins, toilet paper, hand and kitchen towels.

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

Example 1:

A paper handkerchief (finished product) having a basis weight of about 4 x 15.5 g / m³ was performed at a dry fiber content of 92 and 97% dry weight of fiber in the laboratory, a treatment solution of 32 weight percent polyethylene glycol, molecular weight 200, 60 percent by weight of

Polysiloxane Tegopren® 3021, a polyether siloxane having a cloud point of 38 ° C of Th. Goldschmidt AG and 8% water sprayed under good turbulence in an amount of 6% on the tissue and undergo post-smoothing. The order was carried out symmetrically on the outer surfaces of this finished cloth. The product thus obtained was referred to as A.

Example 2:

The method of application of Example 1 was repeated, but a binary mixture of 50 weight percent polyethylene glycol, molecular weight 200 was used and 50 weight percent of the polysiloxane of Example 1, instead of a ternary mixture. The sample thus obtained was designated as B. Comparative Experiment 1

The procedure of Example 1 was repeated, but the pure polysiloxane according to Example 1 is applied in an amount of 6%, and refers to the product thus obtained with C in place of the ternary mixture according to the invention.

Comparative Experiment 2:

The procedure of Example 1 was repeated, but applied instead of the ternary mixture according to a pure polyethylene glycol having the molecular weight of 200 in an amount of 6%. The product thus obtained was designated D. All covers of Examples 1 and 2 and the comparative tests 1 and 2. were in a 2-roll (Steel / plastic) smoothing nachgeglättet reproducible under identical conditions (speed, temperature, contact pressure).

The tactile properties of the products A and B according to the invention were compared with the corresponding haptic results of Comparative Products C (pure polysiloxane) and D (pure polyethylene glycol) (PEG) and these products as part of a so-called panel tests (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) evaluated. Here was the increasing softness, defined here as the sum of surface softness and bulk softness of a group of persons by 9 persons following procedure rated:

The test paper towels were folded in half twice so that the sample identification for the subject than they are, in any case, the same outside of the review is presented. The thus folded towels were the subjects passed with the statement that rubbing and knüllend check folded sheets between thumb thenar and fingers with regard to their bulk softness and surface softness and then lay the towels by increasing, subjective perception of quality in series. The patterns were best ie, to 4, ie, boring, ranked in order of precedence of 1.

In the test, it was found that the inventive products A and B of 7 of the 9 test people described as very good in the softness and with respect to the comparison products C and D were called clearly softer. In contrast, only one of the 9 test subjects felt the product D as soft towards the product A of the invention, and of 9 subjects the comparison product C softer than the inventive products A and B. The panel test also shows that the inventive products A and D in relation to bulk softness and surface softness are significantly better than the comparison products C and D.

The results of this panel test are reported in the following table:

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

composition

parts by weight

PEG water Sil¬ Auftrags¬ Rang¬ Rangfo Ige dioxane quantity (%) total

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

# Identification of subjects

In addition to this first in-house panel test a studio consumer test still was conducted with 160 people. This pattern with a lotion composition of polyethylene glycol / polysiloxane / water in a ratio of 72/10/18 strength at a 3% application amount were a lot softer judged as an appropriate reference sample with pure siloxane. Here again, the polyethylene glycol described in Example 1 was used having a molecular weight of 200 as polysiloxane, the polysiloxane described in Example 1 and as a polyethylene glycol.