SK32497A3 - Tissue paper treating agent containing polysiloxane, process for producing tissue paper by using said treating agent and its use - 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

A composition comprising polysiloxane for processing tissue paper, a method of making tissue paper using the composition and the use thereof.

Technical field

The present invention relates to a composition comprising polysiloxane for processing tissue paper that enhances its softness, to a method of making tissue paper and products made therefrom using the composition, as well as to a processing composition.

BACKGROUND OF THE INVENTION

Softness is an important property of silk products, such as handkerchiefs, cosmetic handkerchiefs, toilet paper, napkins, and towels and wipes, and describes the feel of tissue paper when it touches the skin.

As in Wochenblatt für Papierfabrikation Heft 11/12, 1988, on page 435 ff. In the article Weichheit und Weichmachen von Hygiene-Tissue, the concept of softness is generally understandable, but it is difficult to define because there is no industry recognized standard as a standard for grading different degrees of softness.

To be truly understood, softness must be determined by a subjective method, that is to say, by means of a so-called panel test, in which it is assessed by several trained persons by comparison.

-2 Softness can be classified by characteristics, surface softness, and fissure.

her main softness at

Surface softness describes the feeling that feels when it passes easily through the tissue paper surface with the fingertips.

The softness of the feathering is understood to be the sensory impression produced by the hand-flapping tissue paper process.

The measures usual in the production of tissue paper softness are in the main categories:

or improvement into three

1. Selection of raw material, in particular pulp,

2. mechanical engineering measures (for example, grinding, sheet production, drying and creping, smoothing); and

3. chemical additives and excipients.

Tissue papers require different properties, depending on the intended use. Thus, for towels and, to a greater extent, for towels, strength, especially wet strength and high absorbency, is necessary to meet consumer requirements. For products other than handkerchiefs or cosmetic handkerchiefs, surface softness and high adhesion are characteristics which, in addition to strength, determine the applicability of these products. For toilet paper, the suitability for use and user acceptability is determined by a combination of dry strength at a suitable softness and a suitable thickness.

In particular, it is a challenge for the paper manufacturer to balance the various, often contradictory influencing factors, in a special balance to create combinations of desired end products that are desired by consumers.

A symptom of the times today is that one of the most important requirements imposed on paper manufacturers is the requirement to improve softness in all areas of hygiene product manufacturing. Properties such as the softness of the silk product are determined in their basic design by the manufacturing process and the selection of raw materials and excipients, as already mentioned.

The process of producing silk products, independently of its various variants, includes the following technological steps:

Suspending pulp in water, or adding chemical auxiliaries to influence product properties and manufacturing progressively, activating fiber surfaces to achieve raw fiber strength potential by mechanical treatment such as refining by milling, sheet formation by fiber sweeping, oriented or disordered on or between two infinitely circulating by sieving the paper machine while removing the major amount of dilution water up to a dry matter content of between 12 to 33%, drying the formed primary fiber web in one or several steps by mechanical or thermal means to a final dry matter content of about 93 to 97%. Furthermore, the most relevant steps in the production of silk products include creping, which in a conventional process influences predominantly the properties of the finished silk product. In the currently used dry creping, the creping is carried out on a drying roller, usually 4.5 to 6 m in diameter, the so-called Yankee roller, using a creping scraper at the above-mentioned final dry tissue paper content. In the older processes with lower requirements for the quality of the silk product, wet creping was also used, which was similar to that of the dry creping process but with lower dry matter contents t. j. below 80%, usually at about 55 to 65% dry matter content, with additional drying on the attached drying rollers of the drying group up to the final dry matter content. In the next step, the creped-dried dry tissue paper is wound onto a carrier core to form a so-called tambour or cut longitudinally into a tube to form a parent roll, and in this form is available for further processing into finished products.

In the manufacture of multi-ply tissue paper, such as handkerchiefs, toilet paper, towels or wipes, an intermediate step is often performed with so-called doubling, which usually unwinds the raw cotton (tissue paper) in the required number of layers of finished product. together to form the parent wheel. In this processing step, smoothing or calibrating is often performed in two-roll or multi-roll stools. However, the smoothing (calibrating) can also be carried out in tissue paper machines after drying and creping directly before winding.

The processing process, for example, for folded silk products, such as handkerchiefs or facial tissues, is carried out in the following downstream, special work steps in special purpose-designed machine tools that include processes such as repeated tissue stroking, edge stamping, partially combined with surface and / or spot bonding to create the adhesion of the individual layers (raw tissue paper) to be bonded to the sandwich, as well as longitudinal cutting, folding, cross cutting, stacking and joint guidance of several individual scarves and wrapping them in so-called scarves and the like or special ornamental crabs, as well as joining in larger overpacks and binding. Instead of embossing the edges, the adhesion of the layers can also be achieved by scoring, as is usual with cosmetic handkerchiefs, for example.

According to the conventional process for the production of silk products, in particular in the US but increasingly in Europe, modified process techniques are used in which the specific volume of the tissue paper machine is improved by means of a special type of drying in this tissue paper. tissue paper products thus produced. These methods, existing in various variations, are referred to as TAD (Through Air Drying) methods. Their characteristic is that the primary fibrous web leaving the sheet formation is pre-dried to a dry matter content of about 80% before the final contact drying on a Yankee roll by blowing hot air through the fibrous web. The fibrous web is supported and guided through an air permeable screen or belt during this transport through the surface of an air permeable cylindrical drum 6. By structuring the backing screen or web, any pattern can be produced on densified and wet-formed zones that result in an increased, moderate, specific volume and, consequently, an increase in the softness of the shrinkage without compromising the fiber strength. fleece below the degree necessary for use. A further possibility of affecting the softness and strength in the production of raw tissue paper consists in the use of a layer in which the primary fibrous web is to be formed by a specially designed fabric inflow in the form of various fiber layers which are fed as a fabric stream together with sheet formation. . In the application of the lamination, fibrous webs consisting of two, three or more layers belong to the prior art, for example according to DE-C 43 47.499. By suitably selecting the raw materials in the inlet nozzle exit channels to determine the layering, for example by using eucalyptus fibers on the side of the web facing the surface of the Yankee roll, the surface softness can be significantly increased, which benefits the products made from the raw tissue paper.

In addition, the use of chemicals in the form of a wash solution coating on the raw fabric during the raw tissue paper production process, doubling or subsequent processing to improve softness is known. The term lotion (washing solution), when used in the cosmetic language, generally includes aqueous and water-alcohol preparations with emulsifying active substances. In particular, aqueous solutions or polyethylene glycol or the use of polysiloxanes are described to improve the softness of the silk products. So far it is not yet known to be significant

Softness enhancement can be achieved as a synergistic phenomenon of a mixture of polysiloxane with polyethylene glycol in an aqueous emulsion.

The use of polysiloxanes as a working agent to improve the softness of tissue paper is described in the patent literature. However, until now it is not known that a significant increase in softness can be achieved as a synergistic phenomenon by using a mixture of a polysiloxane with a polyhydroxy compound, such as polyethylene glycol or glycerin in an aqueous emulsion as a tissue processing agent. Thus, for example, WO 90/09807 relates to a tissue paper product comprising at least one tissue paper layer, wherein the tissue paper product comprises 0.1 to 5 wt. silicone solids. This is preferably an aqueous emulsion and / or a solution of these silicone compounds. U.S. Pat. 49 50 543

EP-A-0 347 154 relates to tissue paper having a basis weight of 10 to 65 g / m ² and a density of not more than 0.6 g / ml, the paper comprising cellulose fibers and polysiloxane material, the amount being at least 0.0004 % of polysiloxane based on the dry weight of the fibers of the fibrous web. The object of US patent 50 59 282 resulting from the previous patent is a reasonably limited tissue paper having a basis weight of 10 to 65 g / m ² and a density of not more than 0.6 g / ml, wherein the paper comprises cellulose fibers and an effective content The polysiloxane material is applied identically to the outwardly facing tissue paper surfaces, wherein the effective polysiloxane content is 0.004 to 2% polysiloxane based on the dry weight of the fibers, the polysiloxane having a viscosity of 25 centisks or more and over time

-8 aging two weeks after its production wettability not more than 2 minutes. A process for the production of such paper is the subject of EP-A-347 153 or corresponding US patent 52 15 626.

WO 93/02252 relates to a process for producing soft tissue paper with a sequence of steps of forming sheets from an aqueous slurry of cellulosic fibers to form a fibrous web (web), drying the web while increasing the web temperature to at least 43 ° C, creping the web at a temperature 43 ° C, treating the web at a temperature of at least 43 ° C with sufficient polysiloxane to provide 0.004% to 0.75% of the polysiloxane based on the dry weight of the tissue paper webs in said web, said tissue paper having 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 inter alia with the polysiloxane. This subject is also described in US-A-50 59 282.

WO 94/05857 relates to a method of applying a chemical additive added in the manufacture of paper to a dry tissue web of nonwoven webs for tissue paper, and the method is characterized in that it has the following steps:

Dry tissue nonwoven webs are available for tissue paper, diluting the chemical additive for paper making with a suitable solvent to form a dilute chemical solution, applying the diluted chemical solution to the heated transfer area, partially evaporating the solvent transfer area to form a film containing the additive and transferring the film from the heated transfer area to the surface of the tissue paper web so as to retain a sufficient amount of the chemical paper additive based on the dry fiber weight of the web paper in the web. nonwovens for the manufacture of tissue paper. Preferably, the paper-making additive refers to a plasticizer and mixtures thereof, preferably plasticizers selected from the group of lubricants, plasticizers and mixtures thereof, the lubricants being polysiloxanes. If a chemical emollient is desired to primarily serve as a plasticizer, it may be selected from the group of chemicals; which include, but are not limited to, polyethylene glycol, for example polyethylene glycol having a molecular weight of 400. U.S. Pat. No. 5,246,546 issued to this application.

DE-A-28 00 132 relates to a soft, skin-friendly skin-cleaning product having a non-woven surface and a lower density wiping area, the wiping surface being the limit of the lower density wiping area. The wiping area is impermeable and has a plurality of cavities in the surface and below the surface, with a lower density wiping zone being treated with about 10 to 150% lipophilic cleaning plasticizer based on the weight of the web. Lipophilic cleansing emollients include, but are not limited to, silicone oils as well as nonionic surfactants.

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

10EP-A-0 459 501 relates to a method for reducing static charge and disruption during a wet printing process, characterized in that a paper of a silicone polymer emulsion having a particle size of less than 200 nm, a cationic surfactant and a nonionic surfactant is applied to the paper. .

Furthermore, patents are known which disclose the use of a mixture of polyethylene glycol with quaternary amines (cationic surfactants) as a working agent, for example US-A-5312522.

Thus, DE-C-34 47 499 relates to a non-drying cleaning bag which is characterized in that an emulsion is applied to the carrier material, which consists of at least one moisture regulator, preferably polyethylene glycol and at least one other liquid substance.

It is further known that an anionic surfactant, a nonionic surfactant or mixtures thereof are used as a plasticizer in the manufacture of soft tissue paper.

EP-A-03 47 177 relates to a process for producing soft tissue paper having the following steps:

Formation of sheets from an aqueous slurry of cellulosic fibrous webs to form a web, applying a sufficient amount of a water-soluble non-cationic surfactant such that 0.01-2% of the non-cationic surfactant based on the dry fiber weight of the tissue paper is retained by the web the application is carried out at a fiber consistency of 10 to 80%, as well as drying and creping of the web,

- 11 tissue paper has a basis weight of 10 to 65 g / m ² and a density of less than 0.6 g / m ² .

EP-A-0607796 relates to a non-woven fabric containing an organosilicon compound, the improvement being that the organosiloxane compound contains 45 to 98 wt. water-soluble or water-dispersible polyetherpolysiloxane, wherein the polyether groups consist of 30 to 100 mol% of oxyethylene units and oxypropylene units as a residue and the polysiloxane block comprises 10 to 100 siloxane units, 1 to 20 wt. % water-soluble or water-dispersible organopolysiloxane having at least one ammonium group attached to a carbon atom and 1 to 20 wt. water or water-soluble alkylene glycol.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a working composition comprising polysiloxane for tissue paper products to improve softness, and it is immaterial according to which the tissue paper and processing methods described above have been made according to the invention . Such a working agent is obtained by a mixture of special amounts of at least one polyhydroxy compound selected from natural or chemically modified natural polymers, in particular at room temperature of liquid polyethylene glycol and / or glycerin as an additional component of one part of polysiloxane as well as optionally up to 25% by weight. water. Surprisingly, the application of such a mixture leads to a significantly improved softness of the products

- 12 from tissue paper versus pure application of polysiloxane as well as pure application of polyethylene glycol or glycerin (synergistic phenomenon).

Subject of the present. Accordingly, the present invention provides a polysiloxane-containing working composition, in particular in the form of a lotion for tissue paper products comprising 25 to 95 parts by weight of at least one polyhydroxy compound selected from natural polymers or chemically modified natural polymers, in particular at least one at room temperature of liquid polyethylene glycol and / or glycerin, 5 to 75 parts by weight of polysiloxane, as well as 0 to 35 parts by weight of water, based on 100 parts by weight of the mixture.

in the sense of me, except for cone

The polyhydroxy compound of the present compound means low and an organic compound containing two or more hydroxy groups. These also include polyols of the aforementioned polyhydroxy compounds by definition, in particular polyhydric alcohols such as glycerin, polyethylene glycols, pentaerythritol, sugar alcohols such as tetrides, pentites, hexites, etc. , in particular treite, erythrite, adonit, mannitol and sorbitol, hydrocarbons

D / + / - fructose, D / + / - galactose,

D / + / - mannose, L-cellulose, sucrose, galactose or maltose and synthetic polymers such as polyvinyl alcohol.

arabite, xylite, dulcite ,. e.g. D - / - glucose

Any water-soluble and / or water-dispersible compound which is liquid, pasty or waxy at room temperature (20 ° C) can be used as the polysiloxane component. The polysiloxane component used for the purposes of the present invention includes polymeric, oligomeric, copolymeric and other polymonomeric siloxanes. Polysiloxane is to be understood as meaning any polymer, oligomeric or other non-ammonomeric siloxane material. Further, the polysiloxane material may have both a linear structure and a branched structure or a cyclic structure.

According to a preferred embodiment, the polysiloxane component of the siloxane monomer unit has the following structures:

ri

- Si - 0 - (1),

R ₂ wherein R 1 and R ₂ are the same or different for each siloxane monomer unit and now represent an alkyl group, an aryl group, an alkenyl group, an alkylaryl group, an arylalkyl group, a cycloalkyl group, a halogenated hydrocarbon group or other group. Each of these groups may be substituted or unsubstituted. The R _x and R ₂ groups of each special monomer unit may be different from the corresponding groups of the next bound monomer unit. Further, these groups may be both linear and branched or may have a cyclic structure. The groups R ₂ and R ₂ may be further and independently of each other silicone groups, but are not limited to siloxanes, polysiloxanes and polysilanes. The groups R 1 and R ₂ may further contain a large number of organic functionalities

- 14 groups such as alcohol, carboxylic acid and amino-functional groups.

The degree of substitution and the type of substitution cause the relative degree of softness, silk touch and hydrophilicity that is imparted to the tissue paper structure. In general, the degree of softness and the silky feel that is caused inter alia by the polysiloxane increases as the hydrophilicity of the substituted polysiloxane component decreases. Amino-functional polysiloxanes and polyetherpolysiloxanes are particularly preferred as the polysiloxane component in the detergent composition of the invention.

Preferred polysiloxanes include the organopolysiloxane compounds of the following formula 2, linear of the general formula

ri

ra

R ₂ - Si - 0

Ra r ₃

- Are you

r ₄

Si - R ₃ (2),

Re wherein R ₂ and R _g groups are each independently _a Cl-Cio alkyl or unsubstituted aryl and R ₁₀ is an optionally substituted Ci to Cio alkyl or aryl radical. Each R 1 to R ₉ group which is independently C 1 to O _je unsubstituted alkyl is _preferred . It is known to the person skilled in the art that there is no large difference between whether R 8 or R 10 is a substituted group. Preferably, the molar ratio of b to (a + b) is between

150 to 20%, preferably between 0 to 10% and most preferably between 1 to 5%.

According to a particularly preferred embodiment the R and _Rg are methyl groups and R a substituted or unsubstituted alkyl., Aryl, or alkenyl group. Such materials are commonly referred to herein as polydimethylsiloxanes that have special functionality as those used in the present case. Examples of such polydimethylsiloxanes may be: polydimethylsiloxanes such as Dow Corning® 200 fluid, polydimethylcyclosiloxanes such as Dow Cornung® 344 and 345, polydimethylsiloxane with R 10 alkyl hydrocarbon group and polydimethylsiloxane with one or more carboxylic acid groups, ketone groups, ester groups, and / or other functional groups, including alkyl and alkenyl analogs of such functional groups. An example may be an amino-functional alkyl group such as R 10 amine-functional or aminoalkyl-functional polydimethylsiloxane. The exemplary calculation of these polydimethylsiloxanes does not mean that other, not specifically mentioned here, are excluded.

polyether groups, groups, thiol amide groups

The viscosity of the polysiloxanes used as a component in the fabric of the present invention can vary widely, as long as the polysiloxane remains liquid and can be liquefied for use on tissue paper for use in the fabric of the present invention. This means, for example, viscosities of 25 x 10 ⁶ m ² / s to 20,000,000 x 10 ⁶ m ² / s or even higher. Preferred here are viscosities from 15,000 x 10 ^-6 m ² / s to 3,400,000 x 10 ⁶ m ² / s.

Highly viscous polysiloxanes, which in themselves cannot be liquefied, can be applied effectively as a constituent of the working agent according to the invention to tissue paper by, for example, dissolving the polysiloxane component according to the invention in PEG or glycerin or in water or other mixture together with with a surfactant or polysiloxane, if it is not soluble in PEG or glycerin or water soluble, with a solvent such as hexane.

Special methods for applying the polysiloxane component to tissue paper are discussed.

The aforementioned polysiloxane components are described, for example, in US-A-2826551, US-A-3964550, US-A-4364837, US-A4395454, US-A-4950545, US-A-4921895 and British Patent Specification 849435. and a description of such polysiloxanes is contained in the monograph Silicon Compounds, pages 181-217, published by Petrarch systems, 1984.

According to a further preferred embodiment, the polyesiloxanes of general formula 3 can be used as the polysiloxane component in the working agents according to the invention:

ch ₃ : h ₃ You are about - and You are about - ch ₃ ch ₃

CH ₃

Si 'R12 ch ₃

A 17-average molecule of 2 to 5 R ₁₂ groups wherein R ₁₂ in the molecule are the same or different and represent an alkyl group having 1 to 12 carbon atoms or a polyether group, (C _n H _{2 n} O) _x R ₁₃ , wherein R ₁₃ is hydrogen, a hydroxyl or alkyl or aryl group having a numerical value of 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 is a number of 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 that at least one R ₁₂ group is a polyether group must be fulfilled. Preferred polyether groups and the remaining R ₂ groups are then defined alkyl group being particularly preferred methyl. However, the alkyl group may also have up to 12 carbon atoms. In this way, it is possible to vary the properties of the working agent and thus improve the handling of the tissue paper products. Polyether groups correspond to the formula (C _n H _2n O) _z 'R _3rd The index n has a numerical value of 2 to 2.7. Generally, the ether group consists of a plurality of oxyethylene units and optionally oxypropylene groups. When the index n is 2, the polyether group consists exclusively of oxyethylene units.

the value of n increases, increases the oxypropylene groups. The numerical value of n = 2.7 means that 70% of the polyether groups are oxypropylene groups.

number share

If so

The index z is the number of oxyalkylene units. This value is a mean numerical value since usually a mixture of products with different chain lengths is obtained in the synthesis of polyethers. The index x is a numerical value of 2 to 200, and is preferably about 10 to 50. Polyether groups having an average molecular weight of 500 to 4,000 are preferred. Index a represents the number of methylsiloxane

-18 units carried by the group R ₁₂ . Index b corresponds to the number of dimethylsiloxane units. While a and b can have a value of 0 to 98, the condition that the sum of (a + b) has a value of 8 to 98 must be satisfied. Siloxanes with positive values for and are modified by the side chains of R ₁₂ . Siloxanes in which the R ₁₂ groups are in the side chain are preferred. The group R ₁₃ can be hydrogen, hydroxyl, alkyl or acyl. Preferably, R ₁₃ is hydrogen. When R _{@ 3 is an} alkyl group, alkyl groups having 1 to 4 carbon atoms are preferred. A preferred acyl group is an acetyl group.

According to a particularly preferred embodiment, the polysiloxane components have the following formula:

CH,

SiO CH ₃

CH,

You are about

CH,

CH,

Si - R

CH,

4), wherein R 14 is a group of formula

R16 'Ris ~ N ⁺ - R _X g.

X '

rn

- 19v wherein _R15 is divalenčná hydrocarbon group whose carbon chain is interrupted by oxygen, R _6, R, R _{1 S} are the same or different and are alkyl radicals having 1 up to 18 carbon atoms, of which one group of R _6, R _i7 , Rig is CH _2/3 NNCOR ₁₉ groups where R ₁₉ is alkyl of 7-17 carbon atoms and X is a monovalent anion and c is the numerical value of 5 to 100. R ₅ is a hydrocarbon group divalenčná, e.g., a group of the formula - _CH2-C / OH / HCH ₂ -O-CH _2/3 -. The groups R ₁₆ , R ₁₇ , R ₁₈ may be the same or different and are alkyl groups having 1 to 18 carbon atoms. Of course, one of said groups R _i6, R _17, R ₁₈ may also represent a group / CH _2/3 NHCORic. .

When R ₁₆ , R ₁₇ , R ₁₈ are alkyl, they have 1 to 18 carbon atoms. Particular preference is given to R ₁₄ groups in which two of the above R ₁₆ , R ₁₇ , R ₁₈ groups have 1 to 4 carbon atoms and the third group has up to 14 carbon atoms. When one of R _15, R _17, R _i8 is the group / CH _2/3 NHCOR _4, and R ₁₉ is an alkyl group having 7 to 17 carbon atoms. X 1 is a monovalent anion, generally an acetate group. However, X may 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 of 5 to 100 and preferably 10 to 80. Particularly preferred of the abovementioned siloxanes are those polydimethylsiloxanes, as well as, for example, polyether alkyl as well as quaternary or betaine groups, in particular nitrogen modified groups. polydimethylsiloxane.

Particularly preferred polysiloxanes are those bearing the designation Tegopren ^R of Th, Goldschmiedt AG, which are

-20organomodified siloxanes with significant surface activity and ranges in aqueous and organic systems.

These are polyethersiloxanes, as in the corporate form Tegopren ^R Informativ ,. no date fa. Th. Goldschmidt AG, listed under the names TEGOPREN ^R 3012, TEGOPREN ^R 3020, TEGOPREN ^R 3021, TEGOPREN ^R 3022, TEGOPREN ^R 3070, TEGOPREN ^R 5823, TEGOPREN ^R 3840, TEGOPREN ^R 5842, TEGOPREN ^R 5843, TEGOPREN ^R 5847, TEGOPREN ^R 5851 , Tegopren ^R 5852, Tegopren ^R 5861, Tegopren ^R 5873, Tegopren ^R 5878, Tegopren ^R 5884 as well as Tegopren ^R 7006 and usually have a mean cloud point ranging from less than 25 ° C to 71 ° C as well as modified siloxanes in the form of teoprene-silicone-quats or teoprene-silicone-betaines, which are manufactured under the designations Tegopren ^R 6920, Tegopren ^R 6922 and Tegopren ^R 6950.

For the purposes of the present invention, tissue or short tissue is to be understood as meaning all types of creped paper made from an aqueous dispersion with a basis weight range of between 10 and 65 g / m ² . The term tissue paper according to the invention covers both, as a whole range of creped raw tissue paper, also called raw tissue, in particular ranges, dry tissue creped tissue, regardless of whether it is single or multi-layer, as well as all of these. creped base papers made with single or multi-layer finished products such as handkerchiefs, facial and cosmetic handkerchiefs, toilet paper, towels, towels and napkins. Furthermore, the term tissue paper should be seen irrespective of the fibrous raw material used, particularly whether the fibrous raw material is produced exclusively or

-2Ϊ predominantly from native pulps in a sulphate or sulphite (sulphate or sulphite) manner or used in admixture with chemothermomechanical pulp (CTMP) or whether the fibrous raw material used is derived from a secondary fiber treatment process and therefore fibrous raw material necessary for the production of tissue paper or consists in part of recycled fibers. As a limitation to the so-called Non-wovens, it should be noted that, while the production of tissue paper is characterized by a predominantly ground, natural, i.e. fiber, characteristic, the combined use of refined modified pulp fibers in the range of 10-50% or even use papermaking of suitable plastic fibers in a proportion of 10 to 30% falls under the above definition of tissue paper. The use of the working agent according to the invention can be carried out analogously over the entire tissue production range in the corresponding non-wowen and textile areas.

use of paper pulp plants

According to a preferred embodiment of the present invention, the polysiloxane-containing binary working agent may contain 5 to 75 parts by weight (or% by weight) of at least one of the above polysiloxane and 25 to 95 parts by weight (or% by weight) of the aforementioned polyethylene glycol. However, it is preferred that the detergent composition comprises 10 to 70 parts by weight of polysiloxane, in particular 40 to 60 parts by weight of polysiloxane and, as a further component, 30 to 90 parts by weight, in particular 40 to 60 parts by weight of the aforementioned liquid polyethylene glycol.

According to one further preferred embodiment of the present invention, the working agent comprises 5 to 75 parts by weight (or% by weight) of at least one polysiloxane and 25 to 95 parts by weight (or% by weight) of glycerin. Also preferred in this case is a working agent having 10 to 70 parts by weight, preferably 40 to 60 parts by weight of at least one polysiloxane and 30 to 00 parts, in particular 40 to 60 parts by weight of glycerin.

The polyethylene glycol and glycerin can be arbitrarily interchanged in the compositions according to the invention. However, mixtures of polyethylene glycol and glycerin can also be used, in particular according to economic considerations, preferably the mixing ratios are 20 to 80% by weight or parts by weight, preferably 30 to 70% by weight, of the aforementioned 20 to 80% by weight or parts of polyethylene glycol. and parts by weight, preferably 30 to 70 or parts by weight, of glycerin.

weight

According to a preferred embodiment of the present invention, the working agent according to the invention comprises 30 to 90 parts by weight of at least one polyhydroxy compound, in particular at least one at room temperature of liquid polyethylene glycol and / or glycerine, 10 to 70 parts by weight of polysiloxane and 1 to 30 parts by weight of water. per 100 parts by weight of the composition.

It is particularly preferred here that such a ternary working mixture comprises 20 to 70 parts by weight of at least one polyhydroxy compound, in particular at least one at room temperature of liquid polyethylene glycol and / or glycerin, 30 to 70 parts by weight of polysiloxane and 5 to 25 parts by weight of water. per 100 parts by weight of the composition.

According to one preferred embodiment, water is present as an additional component in addition to both organic components. The detergent composition according to the invention then consists of 5 to 75 parts by weight of at least one polysiloxane, 25 to 95 parts by weight of at least one polyhydroxy compound and up to 1 to 30 parts by weight of water, based on 100 parts by weight of the mixture.

by weight,

In this ternary mixture with polyethylene glycol as one of the components, it is preferred that when using a mixture consisting of 30 to 90, in particular 40 to 60 parts, polyethylene glycol, 10 to 70 parts, preferably 40 to 60 parts by weight of polysiloxane, 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.

Furthermore, it is particularly preferred that 15 to 24, preferably 17 to 22 parts by weight of water are used per 100 parts by weight of polyethylene glycol.

According to a further preferred embodiment with glycerine as one of the components, preferably a binary mixture consisting of 30 to 90, in particular 40 to 60 parts by weight of glycerol, 10 to 70 parts, is preferably used first.

24 wt.%, Preferably 40 to 60 parts by weight of polysiloxane, and, based on 100 parts by weight of the above two components, 1 to 30, preferably 5 to 25 parts by weight of water. It is particularly preferred to use 23 to 32 parts by weight, preferably 25 to 30 parts by weight of water, per 100 parts by weight of glycerol.

In addition to the aforementioned ingredients, the working agent according to the invention may contain, as an additional ingredient, a cosmetic composition having special properties, as well as other conventional adjuvants. Here, mention may be made of skin-acting substances based on vitamins or plant extracts such as extracts of seeds of horse chestnuts, birch, arnica, camomile or bisabololusamot, juniper, cucumber, aloe vera or hamamel, which are partly known for their astringency and healing-promoting effect.

Other active ingredients include skin care agents such as sorbitan acid ester and an oxyethylated glycerin homolog, esters of oxyethylated fatty alcohols, fatty alcohol alkanolamides, oxethylated sheep fat fats, glycerin monostearate, stearic acid, cetyl stearyl alcohol, petroleum jelly. In addition to lanolin alone, lanolin derivatives such as lanolin alcohols or sheep wool fat alcohols, which are available under the name Amerchol ^R Union Carbide Inc., can also be used. in conjunction with mineral oils. For example, the 400 series, BL, C, CAB, U9, L99, LII, L500 and RC are known. Other lanolin derivatives are acetylated lanolin as well as hydrophilic lanolin derivatives, for example lanolin polyoxyethylene compounds. Work equipment according to

Hydrotropic fat-dissolving aids such as polyalcohol ethers as well as oxethylated fatty alcohols can also be added as other additives.

Another group of substances which can be added as additives to the compositions according to the invention are quaternary ammonium salts, such as those described in US Patents 5312522, 5397435, 5405501, 5427696, as well as in international patent applications WO 95/11344 , WO 95/11342, WO 95/01478, WO 95/01479, WO 94/29521, WO 94/29520, WO 94/16143, as well as WO 94/19381.

In addition, conventional fragrances which are selected from natural fragrances, substances identical to natural fragrances or artificial fragrances may be added, with corresponding fragrances being preferred. For example, mention is made of agruman oils such as lemon oil, bergamot oil, orange oil, petitgrain oil, conifer oil, the composition of fragrance foin-coupé or flower oils such as roses, jasmine, lilac, lavender, and synthetic menthol-based fragrances, etc. The review is provided by Ullmann Enzyklopädie der technischen Chemie, Band 20, p. 190-195.

In addition, the corresponding inorganic pigments or organic dyes customarily used in the production of tissue paper can be added together with the working agent according to the invention. In this connection, not only for ecological reasons, non-toxic and non-irritating dyes are preferred, in particular the corresponding natural dyes.

All of the above ingredients and excipients may be included in the detergent as individually as combinations.

Above described working. The tissue paper composition is applied in an amount ranging from 0.01 to 15% by weight, preferably 0.5 to 10% by weight, most preferably 2 to 6% by weight, based on the dry weight of the fibers.

The carrier material to which the working agent is to be applied is preferably a single-layer or multi-layer, preferably at least two-layer and even more preferably a three-layer or four-layer uncoated or embossed tissue paper. The individual strips of paper may be joined to each other mechanically by crimping edges or crimping, glued flat or spot together, or otherwise joined together. For each strip was further proven range of basis weight 10-40 g / m ^2, preferably 14-30 g / m ^2, preferably 15-25 g / m ^2, and most preferably a total of from 15.5 to 17.5 g / m ² . However, heavier and lighter papers with a basis weight range of 8 to 65 g / m ² may also make sense in special applications.

According to another preferred embodiment, the carrier material can also be wet strengthened using non-toxic wet solids such as epichlorohydrin resins, urea-formaldehyde resins, melamine-formaldehyde resins as well as crosslinked cationic polyalkyleneamines.

The working agent, which is in the preferred embodiment in the form of an emulsion, can be applied by any desired method of roll and spray application. In doing so, care must always be taken to avoid separation of the emulsion, i.e., during application, the components of the working agent must be well mixed together in order to avoid separation. This is accomplished, for example, by means of large shear forces, produced, for example, by a high-speed stirrer, frequent pumping or ultrasonic mixing.

The detergent, which can be used to appreciably improve the softness of the tissue paper products, can be used in a wide variety of production areas. For example, it has proven to be particularly advantageous for use on napkins, toilet paper and towels and tea towels, handkerchiefs, cosmetic handkerchiefs and make-up wipes.

The abovementioned composition of the detergent is designed so that during the period during which these products are consumed by consumers, the skin irritations (hygroscopic drying out) cannot occur due to the water content or continuous use during the period of normal humidity during the year. properties of polyethylene glycol or glycerin). It is no longer necessary to use a vapor-tight package and a resealable package.

The working solution can be added as in the wet part of the tissue paper machine (cotton machine), at the end of the sieve part, before or during pressing (mechanical dewatering), i.e. for solids contents between 20 to 50% as well as in the dry part , ranked after

By compression, with solids contents of 40 to 97% by weight of the dry matter of the fibers. The state of the art is the feed sites on the conveyor belt / belt, for example, prior to transferring the web in a TAD arrangement as well as feeding onto a damp fiber web after transferring it to a conveying dry felt using a conventional single or felt tissue paper machine. Further, the state of the art is to supply working chemicals by spraying onto a Yankee cylinder.

Advantageously, the additive of the fabric in the tissue paper machine is carried out by spraying onto a reel to produce the fabric of the fabric and then transferring it to the fabric web during winding - usually having a creped fabric web as a result of the previous drying process on the Yankee roll. a temperature between 20 ° C and about 70 ° C, which is favorable to the distribution of the detergent and its penetration into the raw fabric, onto the contact surface of the single-layer fabric web with the surface of the Pope reel support drum. In addition to spraying with a spray nozzle, the use of spray rotors or brushes may also be envisaged, as well as indirect transfer of the working agent film by the application rollers. The application can also be carried out directly onto the tissue paper web. Particularly preferred is the addition of a working agent inside the double-acting machine or inside the working machine to the outer layers of the multi-layer double belt prior to or during calibration / smoothing. It is most preferred to apply the working agent inside the working machine to a single-layer or multi-layer belt.

The present invention therefore relates to a method for producing soft tissue paper, which is characterized in that it is applied or applied to the web of tissue within the sieve press and / or dry portion or outside the tissue paper machine in a double-action or working machine, that is, at a fiber density of 20 to 97% based on the dry weight of the web fibers, the working agent of the above type in an amount of 0.01 to 15% and the fibrous web is subjected to post-polishing after application.

According to one preferred embodiment, the tissue paper products are obtained by applying a polysiloxane-containing working agent of the above type to the web or web of dry tissue in a tissue paper machine, and particularly preferably inside a double-action machine or within the working machine in an amount of 0.01 to 15% per belt and the fibrous web is subjected to post-polishing after application. However, it is particularly preferred that the above-mentioned polysiloxane-containing working agent is applied at a fiber density of 35-97% based on the dry weight of the fibers of the monolayer web. It is particularly preferred that a multilayer belt is used as the web of fabric and the detergent is applied at at least one of the outer layers of the multilayer web in an amount of 1 to 7% at a fiber density of greater than 90% by weight of the fiber dry weight. Most preferably, the working agent is applied to the multilayer fabric web on both outer layers in an amount of 3 to 6%.

In the method, it is advantageous that the additional screening is carried out by means of at least one pass of the fabric web through a slot of a pair of rollers in which one roll with a steel surface is assigned to a counterpart to the surface

-30 of steel, plastic, paper or rubber, but preferably with a plastic surface.

Preferably, this is done by additionally polishing the fabric strip twice by passing through a slot of a pair of rollers in which the roller with the steel surface is firstly assigned to the plastic surface, and then, as a mirror image, the plastic surface roller is assigned to the steel surface.

Therefore, the post-wiping of the fabric web in connection with the application of the working agent is usually carried out in such a way that the double-sprayed fabric webs are guided through the polishing mill. This smoothing stand usually consists of two smooth rollers with steel surfaces (steel rollers), the surfaces of which are most often hard-chromed. These rollers are pressed together pneumatically or hydraulically, or come up to the slot for calibration. That is, one of the rollers is set to a fixed position. The other roller or counter-roller is pressed against the stop so that the two rollers cannot touch but are at a certain, measurable and reproducible distance from each other. The fabric webs guided through the slit are compressed to the width of the slit and are smoothed. In doing so, the surface structure is uniform, i.e. a uniform thickness is produced. Thus, the smoothing is performed by leveling the surface in conjunction with leveling the profile thickness by overlapping as little volume loss as possible.

The factors that usually affect the smoothing are the line force, the surface temperature of the partially heated rollers, the slot width as well as the number of slots (the number of stools). Articles in April,

-31 3 (1991), pp. 121-123, and J.J. Rodal Tappi Journal, Volume 76, no. 12, pp. 63-74, as well as a review by Weisshun and H. Holik in Das Papier, Vol. 38 (1984), no. 10A.

Instead of the two steel rollers that make up the smoothing stand, a so-called Softholding stand can also be used. In this case, the steel cylinder with the plastic surface is pressed against the smooth steel cylinder. Such a stool is supplied, for example, by fa. Kusters Maschinen GmbH. These soft-calendering calendars are known among others as MAT-ON-Line-smoothing stools. Another Softholding stool with a steel cylinder and a counterpart with a plastic surface is the NIPCO-MAT smoothing stool fa. Edmund Kusters Maschinenfabrik, Krefeld, comparison Wochenblatt der Papierfabrikation 13/91, p. 491 to 498. Such rollers are described in DE 3445890 as well as in EP 0273185.

Furthermore, instead of the two steel rollers forming the smoothing mill, a smoothing mill can also be used, where a roller or a counterpart having a rubber or paper surface is used together with the steel roller or steel counterpart.

For an overview of conventional methods of additional screening, see German Patent Specification 1804418, German Interpretation 2455895, German Patent Specification 2528803, EP-A-0033559, US Patent 2179057, US Patent 3337388, British Patent 827735, and German Patents 822228 and 1045783.

Finally, the present invention also relates to the use of the aforementioned working agent which comprises polysiloxane for softening tissue paper products,

-32 especially handkerchiefs, cosmetic handkerchiefs, make-up remover tissues, napkins, toilet paper, towels and tea towels.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is explained in more detail below with reference to exemplary embodiments.

Example 1

A working solution consisting of 32% by weight of polyethylene glycol of molecular weight was sprayed in the laboratory onto a paper towel (finished product) with a basis weight of about 4 x 15.5 g / m ³ at a fiber dry matter content of 92 to 97% by weight of fiber dry matter. 200, 60% by weight of polysiloxane Tegopren ^R 3021, polyethersiloxane with a turbidity temperature of 38 ° C Th. Godschmiedt AG as well as 8% water with good mixing of 6% per paper tissue and was subjected to post-polishing. The application was carried out symmetrically on the outer surfaces of this finished handkerchief. The product thus obtained was designated A.

Example 2

The deposition procedure according to the example was repeated, but in addition to the ternary mixture, a binary mixture consisting of 50% by weight polyethylene glycol with a molecular weight was used.

- by weight of 200 and 50% by weight of polysiloxane according to Example 1. The sample thus obtained was designated B.

Comparative experiment

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

Comparative experiment 2

The process of Example 1 was repeated, but instead of the ternary mixture of the invention pure polyethylene glycol with a molecular weight of 200 was applied in an amount of 6%. The product thus obtained was labeled D. All the handkerchieves of Examples 1 and 2 as well as Comparative Experiments 1 and 2 were additionally glazed in a two-roll (steel / plastic) stool under identical conditions (speed, temperature, pressure) and reproducible.

The haptic properties of the products A and B according to the invention were compared with the corresponding haptic results of the compared products C (pure polysiloxane) and D (pure polyethylene glycol) and these products were evaluated in the so-called panel test (based on Manual on Sensory Testing Methods, ASTM, Spexial Technical Publication 434, page 22, Testform D-Ranking Methods-Rank Order, Elevants Printings February 1993). The increasing softness was defined here as the sum

-34from the pleasant feel of the surface and the softness of the flickering detected by a group of 9 persons according to the following method:

The paper tissues tested were folded two times in half, so that the specimens could not be identified by the test persons and in all cases the same outer side was offered for evaluation. The folded handkerchiefs were sold to test subjects, instructed to test the folded handkerchiefs by rubbing and snapping between the thumb, thumb, and fingers, and then placing the handkerchiefs in line with an increasing, subjective sense of quality.

The samples were ranked from 1, i.e. best, to 4, i.e. worst, evaluated.

The test showed that products A and B were marked as very good in terms of softness in terms of softness and in comparison with products C and D as clearly softer. In contrast, only a third of the test subjects felt product D as softer than product A according to the invention, and one person in 9 test subjects considered comparative product C as softer than products A and B according to the invention. The panel test further shows that the products A and B according to the invention are significantly better in terms of cracking softness and surface softness than the compared products C and D.

The results of this panel test are reproduced in the following table.

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-36In addition to this first operational internal panel test, a consumer test was also conducted in a study of 160 persons. Samples with a polyethylene glycol / polysiloxane / water wash composition of 72/10/18 at 3% loading were considered to be considerably softer than the corresponding comparative samples with pure siloxane. Here, the polysiloxane described in Example 1 and the polyethylene glycol described in Example 1 with a molecular weight of 200 were used again as the polysiloxane described in Example 1.

Claims (22)

Composition comprising polysiloxane for processing tissue paper products, in particular in the form of a lotion, characterized in that it contains 25 to 95 parts by weight of at least one polyhydroxy compound selected from the group of natural or chemically modified natural polymers, in particular at least one liquid polyethylene glycol at room temperature. and / or glycerin, 5 to 75 parts by weight of polysiloxane, as well as 0 to 35 parts by weight of water, based on 100 parts by weight of the mixture. Composition according to claim 1, characterized in that it contains 30 to 90 parts by weight of at least one polyhydroxy compound, in particular one at room temperature of liquid polyethylene glycol and / or glycerin, 10 to 70 parts by weight of polysiloxane and 1 to 30 parts by weight of water, based on 100 parts by weight of the composition. 3. Device. according to characterized by parts by weight of at least at least one for polyethylene glycol and / or claim 1 or 2, comprising 30 to 70 parts of one polyhydroxy compound, liquid temperature of 30 to 70 parts by weight of room glycerin, polysiloxane by weight, and 5 to 25 water, based per 100 parts by weight of the composition. -384. Composition according to the preceding claims, characterized in that it contains 5 to 75 parts by weight of at least one polysiloxane and 25 to 95 parts by weight of polyethylene glycol liquid at room temperature. Composition according to claim 4, characterized in that it contains 10 to 75 parts by weight, in particular 40 to 60 parts by weight, in particular 40 to 60 parts by weight of polyethylene glycol. Composition according to claims 1 to 3, characterized in that it contains 5 to 75 parts by weight of at least one polysiloxane and 25 to 95 parts by weight of glycerin. Composition according to claim 6, characterized in that it contains 10 to 70 parts by weight, preferably 40 to 60 parts by weight of at least one polysiloxane and 30 to 90 parts by weight, in particular 40 to 60 parts by weight of glycerin. Composition according to the preceding claims 1 to 7, characterized in that it comprises a first component of 20 to 80, preferably 30 to 70 parts by weight of the aforementioned polyethylene glycol and 20 to 80 parts by weight, preferably 30 to 70 parts by weight of the aforementioned glycerin. . Composition according to the preceding claims 1 to 8, characterized in that the polysiloxane has a viscosity of 25 x 10 ⁶ m ² / sec to 20,000,000 x 10 ⁶ m ² / sec. -3910. The composition of the preceding claims 9, characterized in that the polysiloxane is a polydimethylsiloxane which optionally has in its side chain at least one betaine group, in particular a tetraalkylammonium group. Composition according to the preceding claims 1 to 11 10, characterized in that the polysiloxane is a polyether siloxane, in particular with a mean cloud point in the range of less than 25 ° C to 71 ° C. Composition according to the preceding claims 1 to 12 11, characterized in that it further comprises cosmetic compositions having special properties, for example skin care compositions and / or skin-extracting agents based on plant extracts and / or fragrances. Composition according to the preceding claims 1 to 12 12, characterized in that it further comprises auxiliaries such as quaternary ammonium compounds and / or dissolution aids and / or wet solids. Method for producing tissue paper products, characterized in that the processing composition according to claims 1 to 13, comprising polysiloxane, is applied to the fibrous web or web within the sieve / press section and / or the dry section, i.e. at the fiber density. 20 to 97%, based on the dry weight of the fibers, in an amount of 0.01 to 20% 15%, and the fibrous web is subjected to additional screening after application. -4015. Method for producing tissue paper products, characterized in that the processing composition according to claims 1 to 13, comprising polysiloxane, is applied to the fibrous web or web of fabric after the dry part in a tissue paper machine and particularly preferably inside a double-action tissue paper machine. inside the machine for processing in an amount of 0.01 to 15% per belt and the belt is subjected to an additional polishing after application. 16. The method according to claim 15, wherein the composition is applied to the polysiloxane at a density based on dry weight in an amount of 0.5 to 10%. characterized by processing, comprising a fiber content of 35 to 97%, of a monolayer web, The method according to claims 14 to 16, characterized in that the fabric web is a single-layer web and the treatment agent is applied at a fiber density of greater than 90%, based on the dry weight of the fibers, to at least one outer layer of the multi-layer web. up to 7%. The method of claim 17, wherein the processing means is applied to the multi-layer web of fabric on both outer layers in an amount of 3 to 6%. Method according to claim 15 or 16, characterized in that the deposition of the processing agent is carried out in a tissue paper machine by spraying on a pop-up machine in the production of the film of the agent and subsequently transferring it to the web of fabric during the winding process. -41 Method according to claims 14 and 15, characterized in that the additional screening is carried out by means of at least one pass of the web of fabric through a slot of a pair of rollers in which one steel surface roll is assigned a counterpart to the steel, plastic, paper or rubber surface. preferably with a plastic surface. Method according to claims 14 and 15, characterized in that the additional polishing is carried out by passing the fabric strip twice through the slot of a pair of rollers, in which the steel surface roll is first assigned to the plastic surface and then the mirror surface is plastic assigned to the opponent with a steel surface. Method according to claims 14 to 21, characterized in that the deposition of the processing agent on the fibrous web is carried out in a conventional tissue paper production process. Method according to claim 14, characterized by. in that up to 21, the deposition of the processing agent on the fibrous web is carried out in a flow-drying or TAD process. Use of a processing agent according to claims 1 to 13 for processing tissue paper products, in particular handkerchiefs, cosmetic handkerchiefs, facial tissues, toilet tissues, paper and towels.