EP0803012B1 - Procede de fabrication de papier mousseline au moyen d'un agent de traitement - Google Patents

Procede de fabrication de papier mousseline au moyen d'un agent de traitement Download PDF

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Publication number
EP0803012B1
EP0803012B1 EP95932724A EP95932724A EP0803012B1 EP 0803012 B1 EP0803012 B1 EP 0803012B1 EP 95932724 A EP95932724 A EP 95932724A EP 95932724 A EP95932724 A EP 95932724A EP 0803012 B1 EP0803012 B1 EP 0803012B1
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EP
European Patent Office
Prior art keywords
weight
parts
polysiloxane
treatment medium
process according
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EP95932724A
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German (de)
English (en)
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EP0803012A1 (fr
Inventor
Harald Elstner
Peter Von Paleske
Walter Hill
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Essity Germany GmbH
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SCA Hygiene Products GmbH
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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22Addition to the formed paper
    • D21H23/24Addition to the formed paper during paper manufacture
    • D21H23/26Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
    • D21H23/28Addition before the dryer section, e.g. at the wet end or press section
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22Agents rendering paper porous, absorbent or bulky

Definitions

  • the present invention relates to a method for Manufacture of tissue paper and products made from it using a treatment agent as well as use a treatment agent.
  • Softness is an important characteristic of tissue products such as Handkerchiefs, facial tissues, toilet paper, napkins and also hand or kitchen towels and describes the feeling which the tissue paper produces when it touches the skin.
  • Softness can be characterized by its main characteristics: Surface softness and softness, break down:
  • Under softness is meant the sensory impression, a tissue squeezed by hand during the Squeeze process created.
  • tissue papers require different properties. So are kitchen towels and to an even greater extent with towels strength, in particular Strength when wet and high suction power required to meet the needs of the consumer.
  • towels strength in particular Strength when wet and high suction power required to meet the needs of the consumer.
  • handkerchiefs or facial tissues are softness of the surface and very smooth outstanding properties that in addition to strength Determine the utility value of these products.
  • toilet paper determines a combination of dry strength in addition to good Softness and good thickness appearance, suitability for use and Consumer acceptance.
  • the tissue making process includes regardless of its different variants the following procedural Steps:
  • the processing process for example, to folding products such as Handkerchiefs or facial tissues are made in downstream, separate operations in special, for the task constructed processing machines, the processes like smoothing the tissue again, edge embossing, partially combined with flat and / or selective gluing to create layer adhesion of the composite individual layers (raw tissue) as well as longitudinal section, folding, Cross-section, storage and merging of several individual tissues and their packaging in so-called cloth bags or special jewelry boxes and their merging contain larger packaging or containers.
  • Edge generation can also be achieved by layer adhesion Knurling are generated, as z. B. in cosmetic wipes is common.
  • Tissue manufacturing processes are particularly common in the United States, today increasingly also in Europe, modified Process technologies in use, where a special Type of drying inside the tissue machine Improvement of specific volume and in this way a Improvement of the softness of the tissue produced in this way is achieved.
  • TAD Through Air Drying
  • Throughflow drying Its characteristic is that the "primary" nonwoven leaving the sheet formation before final contact drying on the Yankee cylinder a dry content of about 80% is pre-dried by Hot air is blown through the nonwoven.
  • the nonwoven is supported by an air-permeable sieve or belt and led over the surface of one during its transport air-permeable, rotating cylinder drum.
  • the support sieve or belt can be structured any pattern of compressed and by deformation in the damp state are generated on loosened zones that too increased, medium, specific volume and related thus lead to an increase in softness without the Strength of the nonwoven below that for use necessary measure drops.
  • Another possibility to influence the Raw tissue production for softness and firmness consists in the Applying a stratification in which the primary to be formed Nonwoven fabric through a specially designed headbox in Form of different material layers is fed to the sheet formation together as a material jet become.
  • nonwovens include consisting of two, three or more layers to the state of the Technology, for example DE-C 43 47 499.
  • the use of chemicals is in the form of a Lotion order on the raw tissue during the raw tissue production process, the duplication or the subsequent one Processing known to improve softness.
  • the term "Lotion” encompasses in general cosmetic usage Understanding aqueous or aqueous-alcoholic preparations emulsifying agents.
  • EP-A-0 347 154 relates to tissue paper with a basis weight of 10 to 65 g / m 2 and a density of not more than 0.6 g / ml, this paper containing cellulosic fibers and a polysiloxane material, the amount at least 0.004% polysiloxane, based on the dry (fiber) weight of this nonwoven.
  • US Patent 50 59 282 which results from this is correspondingly restricted a tissue paper with a basis weight of 10 to 65 g / m 2 and a density of not more than 0.6 g / ml, this paper being cellulose fibers and an effective content of a polysiloxane material contains, said polysiloxane being applied uniformly to the outward-facing surfaces of the tissue paper, this effective content of the polysiloxane being 0.004% to 2% of polysiloxane, based on the dry (fiber) weight of the tissue paper, which polysiloxane has a viscosity of 25 centistokes and has more and has a wetting time of not more than 2 minutes after an aging time of two weeks after its production.
  • a manufacturing process for such a paper is the subject of EP-A-347 153 or the corresponding US patent 52 15 626.
  • WO93 / 02252 relates to a production process for soft tissue paper with the step sequence of forming a sheet from aqueous suspension (wet laying) of cellulose fibers with formation of a nonwoven fabric (nonwoven fabric), drying the nonwoven fabric while increasing the temperature of the nonwoven fabric to at least 43 ° C., and creping the nonwoven fabric a temperature of at least 43 ° C, treating the nonwoven fabric at a temperature of at least 43 ° C with a sufficient amount of a polysiloxane so that 0.004% to 0.75% of this polysiloxane based on the dry (fiber) weight of this tissue paper in this nonwoven fabric remain, this tissue paper has a basis weight of 10 to 65 g / m 2 and a density of less than 0.6 g / m 3 .
  • a water-soluble surfactant can be added at the same time as the polysiloxane. This subject is also described in US-A-50 59 282.
  • WO94 / 05857 relates to a method for applying a chemical papermaking additive to a dry Tissue paper fleece (tissue paper fleece, raw tissue), whereby this method is characterized in that it follows Steps includes:
  • plasticizers and their Mixtures preferably plasticizers, selected are made of lubricants, plasticizers and their Mixtures, these lubricants being polysiloxanes.
  • a chemical softener which is primarily used as Plasticizer should serve, is desired, it can be made selected from a group of chemicals, for which purpose other polyethylene glycol, for example polyethylene glycol a molecular weight of 400 counts. From this U.S. Patent No. 5,246,545 has been filed.
  • DE-A-28 00 132 relates to a soft, pliable Skin cleaning article with a fleece with a wiping surface and a low density wiping zone, the wiping surface represents a boundary of the low density wiping zone that Wipe zone low density is permeable to dirt and a Plenty of cavities in and under the surface and wherein the low density wiping zone is about 10 up to 150% lipophilic cleaning enamel, based on the Weight of the fleece, is treated.
  • Lipophilic cleaning moles also fall, among other things Silicone oils and non-ionic surfactants.
  • DE-C 34 20 940 relates to an agent for cleaning and Wiping the circuminal area comprising at least one Oil selected from the group of vegetable oils, animal oils and synthetic oils, characterized in that it is considered another Component comprises a silicone oil.
  • EP-A-0 459 501 relates to a method for reducing the static charge and destruction during a Wet printing process, which is characterized in that on the paper is a silicone polymer emulsion, which is a Has particle size of less than 200 nm, a cationic Surfactant and a nonionic surfactant is applied.
  • patents are known that use a Mixture of polyethylene glycol with quaternary amines Describe (cationic surfactants) as a treatment agent for example, US-A-5312522.
  • So DE-C-34 47 499 relates to a non-drying Cleaning cloth, which is characterized in that an emulsion is applied to a carrier material at least from a moisture regulator, preferably Polyethylene glycol and at least one other liquid substance consists.
  • a moisture regulator preferably Polyethylene glycol and at least one other liquid substance consists.
  • EP-A-03 47 177 relates to a process for the production of Soft tissue paper, which has the following steps:
  • Sheet formation from an aqueous suspension (wet laying) of cellulose fibers to form a fleece application of a sufficient amount of a water-soluble non-cationic surfactant in such a way that 0.01 to 2% of this non-cationic surfactant, based on the dry (fiber) weight of this tissue paper through the fleece are withheld, this application being carried out with a fiber consistency of 10 to 80% and drying and creping of the fleece, this tissue paper having a basis weight of 10 to 65 g / m 2 and a density of less than 0.6 g / m 3 .
  • EP-A-0607796 relates to an organosilicon compound containing nonwovens, the improvement being that the organosilicon compound contains 45 to 98 wt .-% of a water soluble or water dispersible Polyether polysiloxane, the polyether groups being 30 to 100 mol% of oxyethylene units and oxypropylene units as the rest exist and the polysiloxane block 10 to 100 siloxane units comprises 1 to 20% by weight of a water-soluble or water-dispersible organopolysiloxane with at least one Ammonium group attached to the carbon atom and 1 to 20% by weight of water or a water-soluble alkylene glycol.
  • the pre-filed post-published EP-A-0688901 relates a tissue paper containing 3 to 30% by weight of an aqueous softness mediating composition have been added, wherein said softening composition 20 to 98 wt .-% glycerol and 0.2 to 5% by weight of at least one quaternary Contains ammonium compound, which is, among others a special one containing a quaternary ammonium compound Polysiloxane compound of the general formula (6), such as defined below, can act.
  • glycerol instead of glycerol in amounts of 0.5 to 50 % By weight either 0.5 to 50% by weight, based on the Main component, propylene glycol and / or polyethylene glycol to use.
  • the present invention is based on the object Process for the production of tissue paper products under Use of a polysiloxane-containing treatment agent Provide improvement in softness, being it it is irrelevant which of the prescribed raw tissue production and processing methods the tissue product produces has been.
  • a treatment agent is obtained from a mixture of special amounts of at least one polyhydroxy compound, except natural or chemically modified natural polymers especially one at room temperature, i.e. at 20 ° C, liquid polyethylene glycol and / or glycerin as further component, a portion of a polysiloxane and optionally up to 25 weight percent water.
  • the Application of such a mixture surprisingly leads to a significantly improved softness of tissue products compared to a pure polysiloxane application as well as a pure polyethylene glycol or glycerin application (Synergy effect).
  • the present invention thus relates to a process for the production of tissue paper products, characterized in that a treatment agent containing polysiloxane, which comprises 25 to 95 parts by weight, preferably 30 to 90 parts by weight of at least one polyhydroxy compound, in particular at least one polyethylene glycol and / or glycerol which is liquid at room temperature , 5 to 75 parts by weight, preferably 10 to 70 parts by weight of polysiloxane and, based on 100 parts by weight of this mixture, 0 to 35 parts by weight, preferably 1 to 30 parts by weight of water, with the exception of a treatment agent containing 5% by weight of a quaternary ammonium group-containing polysiloxane general formula in which and R 19 is a long-chain C 12 - C 18 alkyl group, onto the nonwoven or the "tissue web" within the wire / press section and / or dryer section, that is to say with a fiber density of 20 to 97%, based on the dry fiber weight of the web, in one Applied amount of
  • polyhydroxy compound in the sense of Method used according to the invention is understood to be a low and macromolecular organic compound, the two or contain more hydroxy groups in the molecule.
  • polyols called polyols belong by definition, especially polyhydric alcohols such as for example glycerol, polyethylene glycols, pentaerythritol, Sugar alcohols, such as B.
  • tetrides pentites, hexites etc., especially threit, erythritol, adonite, arabitol, xylitol, dulcitol, Mannitol and sorbitol, carbohydrates for example D (+) - glucose, D (+) - fructose, D (+) - galactose, D (+) - mannose, L-gulose, Sucrose, galactose or maltose and synthetic polymers such as polyvinyl alcohol.
  • any water-soluble component can be used as the polysiloxane component and / or water-dispersible compound which at Room temperature (20 ° C) liquid, pasty or waxy is present.
  • This polysiloxane component includes polymers, oligomers, copolymers and others polymonomeric siloxanes. In the following one should under the Term polysiloxane any polymeric, oligomeric or understand other multi-monomeric siloxane material. Farther can the polysiloxane material both a linear structure, a have a branched structure or a cyclic structure.
  • the polysiloxane component has monomeric siloxane units of the following structure: where R 1 and R 2 are the same or different for each monomeric siloxane unit and each is an alkyl, aryl, alkenyl, alkylaryl, arylalkyl, cycloalkyl, halogenated hydrocarbon or other group. Each of these groups can be substituted or unsubstituted. R 1 and R 2 groups of each particular monomeric unit may differ from the corresponding functional groups of the next attached monomeric unit. Furthermore, these groups can be both straight-chain and branched or have a cyclic structure.
  • the groups R 1 and R 2 can furthermore and independently of one another be other silicone groups, but are not limited to siloxanes, polysiloxanes and polysilanes.
  • the groups R 1 and R 2 can furthermore contain a large number of organic functional groups, for example alcohol, carboxylic acid and amino-functional groups.
  • the degree of substitution and the type of substitution effect that relative degree of softness, silky feel and Hydrophilicity imparted to the tissue paper structure in the generally the degree of softness and silky increases Griffs, which is caused, among other things, by the polysiloxane, provided the hydrophilicity of the substituted Polysiloxane component decreases.
  • Amino functional polysiloxanes and Polyetherpolysiloxane are as polysiloxane component in Treatment agent particularly preferred.
  • Preferred polysiloxanes include linear organopolysiloxane compounds of the following general formula, where in each case the R 1 to R 9 groups are, independently of one another, C 1 to C 10 unsubstituted alkyl or aryl groups and R 10 is any substituted C 1 to C 10 alkyl or aryl radical.
  • R 1 to R 9 group is independently a C 1 to C 10 unsubstituted alkyl group. It is known to those skilled in the art that it makes little difference whether, for example, R 9 or R 10 is the substituted group.
  • the molar ratio of b to (a + b) is preferably between 0 and 20%, preferably between 0 and 10% and in particular between 1 and 5%.
  • R 1 to R 9 are methyl groups and R 10 is a substituted or unsubstituted alkyl, aryl or alkenyl group.
  • Such materials are generally referred to here as polydimethylsiloxanes, which have a special functionality as used in the present case.
  • polydimethylsiloxanes can be: polydimethylsiloxanes such as Dow Corning® 200 Fluid, polydimethylcyclosiloxanes such as Dow Corning® 344 and 345, polydimethylsiloxane with an R 10 alkyl hydrocarbon group and a polydimethylsiloxane with one or more amino, carboxyl, hydroxyl Polyether, aldehyde, ketone, amide, ester, thiol and / or other R 10 functional groups, including alkyl and alkenyl analogs of such functional groups.
  • an amino functional alkyl group such as R 10 can be an amino functional or an amino alkyl functional polydimethylsiloxane.
  • the exemplary list of these polydimethylsiloxanes does not mean that others, not specifically mentioned here, are excluded from this.
  • the viscosity of the polysiloxanes used as a component in the process according to the invention can vary over a wide range, as long as the polysiloxane remains fluid and can be liquefied for use in the treatment agent according to the invention for application to the tissue paper. This includes, for example, viscosities from 25 x 10 -6 m 2 / s to 20,000,000 x 10 -6 m 2 / s or even higher. Viscosities of 15,000 x 10 -6 m 2 / s to 3,400,000 x 10 -6 m 2 / s are preferred here.
  • Highly viscous polysiloxanes that are not themselves flowable can be applied as an ingredient of the treatment agent to tissue paper in an effective manner, for example by emulsifying the polysiloxane component according to the invention in PEG or glycerol or water or in a mixture thereof together with a surfactant or the polysiloxane, if it is not soluble in PEG or glycerol or water, by means of a solvent such as hexane. Special methods for applying the polysiloxane component to tissue paper are discussed below.
  • polysiloxane components are, for example, in US-A-2826551, US-A-3964550, US-A-4364837, US-A-4395454, US-A-4950545, US-A-4921895 and British Patent 849433 described.
  • the monograph "Silicon Compounds" pages 181 - 217, edited by Petrarch Systems, 1984, a detailed listing and description such polysiloxanes.
  • polyethersiloxanes of the general average formula can be used as polysiloxane component in the treatment agents, in which R 12 in the molecule are the same or different and are an alkyl group having 1 to 12 carbon atoms or a polyether group - (C n H 2n O) x R 13 , where R 13 is hydrogen, hydroxyl, alkyl or an acyl group and n is a numerical value from 2 to 2.7 and x has a numerical value from 2 to 200, with the proviso that at least one of the R 12 groups in the average molecule is a polyether group; a has a numerical value from 0 to 98, b has a numerical value from 0 to 98 and a + b is 8 to 98.
  • R 12 can be an alkyl group having 1 to 12 carbon atoms or a polyether group. However, the condition must be met that at least one R 12 in the average molecule is a polyether group. Preferably 2 to 5 of the R 12 groups are polyether groups and the remaining R 12 groups then have the meaning of an alkyl group, the methyl group being particularly preferred.
  • the alkyl group can also have up to 12 carbon atoms. In this way it is possible to vary the properties of the treatment agent and in this way to improve the handling on tissue paper products.
  • the polyether groups correspond to the formula (C n H 2n O) x R 13 .
  • the index n has a numerical value from 2 to 2.7.
  • the index x means the number of oxyalkylene units. This value is an average numerical value since a mixture of products of different chain lengths is usually obtained in the synthesis of polyethers.
  • the index x has a numerical value of 2 to 200 and is preferably 10 to 50. Polyether groups with an average molecular weight of 600 to 4,000 are preferred.
  • the index a means the number of methylsiloxane units carried by the R 12 group.
  • the siloxanes with positive values for a are modified by the R 12 side chains. Siloxanes in which the R 12 groups are arranged in the side chain are preferred.
  • the R 13 group can be hydrogen, hydroxyl, alkyl or also acyl. R 13 is preferably a hydrogen atom. If R 13 is an alkyl group, lower alkyl groups with 1 to 4 carbon atoms are preferred. The acetyl group is the preferred acyl group.
  • the polysiloxane component has the following formula: where R 14 is a group of the formula and in which R 15 is a divalent hydrocarbon group whose carbon chain is interrupted by an oxygen atom, R 16 , R 17 , R 18 are the same or different and represent alkyl groups with 1 to 18 carbon atoms, one of the groups R 16 , R 17 , R 18 is a - (CH 2 ) 3 NHCOR 19 group, in which R 19 has an alkyl group with 7 to 17 carbon atoms and X- is a monovalent anion and c has a numerical value of 5 to 100.
  • R 15 is a divalent hydrocarbon group, for example the group of the formula -CH 2 -C (OH) H-CH 2 -O- (CH 2 ) 3 -.
  • the R 16 , R 17 , R 18 groups can be the same or different and are alkyl groups with 1 to 18 carbon atoms. However, one of the aforementioned groups R 16 , R 17 , R 18 can also have the meaning of a (CH 2 ) 3 NHCOR 19 group.
  • R 16 , R 17 , R 18 groups are alkyl groups, these have 1 to 18 carbon atoms.
  • R 14 groups are particularly preferred in which two of the aforementioned R 16 , R 17 and R 18 groups have 1 to 4 carbon atoms and the third group has up to 18 carbon atoms.
  • one of the R 16 , R 17 and R 18 groups is a (CH 2 ) 3 NHCOR 19 group, the R 19 group is an alkyl group with 7 to 17 carbon atoms.
  • X - is a monovalent anion, generally an acetate group. However, X can also be an inorganic group such as Cl - .
  • the index "c” indicates the number of dimethylsiloxy units in the linear siloxane and has a numerical value from 5 to 100 and preferably 10 to 80.
  • Particularly preferred of the aforementioned siloxanes are such polydimethylsiloxanes as well for example polyether, alkyl, and with quaternary or betainic groups, especially nitrogen groups modified polydimethylsiloxanes.
  • Particularly preferred polysiloxanes are those under Designation Tegopren® distributed by Th. Goldschmidt AG organo-modified siloxanes with pronounced surface and Interface activity in aqueous and organic systems.
  • polyether siloxanes as described in the company publication "Tegopren® Informative", undated, from Th. Goldschmidt AG at the trade name Tegopren® 3012, Tegopren® 3020, Tegopren® 3021, Tegopren® 3022, Tegopren® 3070, Tegopren® 5830, Tegopren® 5840, Tegopren® 5842, Tegopren® 5843, Tegopren® 5847, Tegopren® 5851, Tegopren® 5852, Tegopren® 5863, Tegopren® 5873, Tegopren® 5878, Tegopren® 5884 and Tegopren® 7006 are sold and Usually mean cloud points in the range below 25 ° C to 71 ° C and modified siloxanes in the form of Teopren silicone quats and betaines, such as those among the Designations Tegopren® 6920, Tegopren® 6922 and Tegopren
  • tissue paper or tissue for short in the sense of the present invention is understood to mean all types of creped papers produced from aqueous dispersion with a basis weight range between 10 and 65 g / m 2 .
  • tissue paper covers both the entire area of creped base papers, also called raw tissue, in particular the area of dry creped base tissue papers, regardless of whether single-layer or multilayer, as well as all end products made from these creped base papers, such as handkerchiefs , Facial and facial tissues, toilet paper, kitchen towels, hand towels and serviettes.
  • tissue paper is still to be seen regardless of the fiber raw material to be used, in particular regardless of whether the fiber raw material is produced exclusively or predominantly from native pulps by the sulfate or sulfite process, or is used in a mixture with chemo-thermomechanical wood pulps (CTMP), or whether the fiber raw material used originates from a secondary fiber preparation process and accordingly the fiber raw material required for tissue production consists entirely or partially of "recycled fibers".
  • CTMP chemo-thermomechanical wood pulps
  • nonwovens nonwovens
  • vegetable pulp fibers is characteristic for tissue paper production, a proportionate use by refinement of modified pulp fibers in a range of 10 to 50% or even one Use of plastic fibers suitable for papermaking in a proportion of 10 to 30% falls under the aforementioned definition of tissue.
  • An application of the treatment agent is possible beyond the area of tissue production to corresponding areas of the non-woven area and the textile area in analog transmission.
  • the binary, polysiloxane-containing treatment agent from 5 to 75 parts by weight (or% by weight) of at least one aforementioned polysiloxane and 25 to 95 parts by weight (or % By weight) of the aforementioned polyethylene glycol.
  • 10 to 70 is preferred in this treatment agent Parts by weight of polysiloxane, in particular 40 to 60 parts by weight Polysiloxane and as a further component 30 to 90 parts by weight, but in particular 40 to 60 parts by weight of the aforementioned use liquid polyethylene glycol.
  • the present invention is what is used in the method Treatment agent from 5 to 75 parts by weight (or% by weight) at least one polysiloxane and 25 to 95 parts by weight (or% by weight) glycerin.
  • Treatment agent with 10 to 70 parts by weight, preferably 40 up to 60 parts by weight of at least one polysiloxane and 30 to 90 parts by weight, in particular 40 to 60 parts by weight Glycerin.
  • Polyethylene glycol and glycerin can be used in the treatment agent can be exchanged in any quantity. But also mixtures of polyethylene glycol and glycerin can in particular under Economic aspects are used, whereby preferably the mixing ratios 20 to 80% by weight or Parts by weight, preferably 30 to 70% by weight or parts by weight of the aforementioned polyethylene glycol and 20 to 80% by weight or Parts by weight, preferably 30 to 70 wt .-% glycerol turn off.
  • the treatment agent 30 to 90 parts by weight at least one polyhydroxy compound, i.e. at 20 ° C, in particular at least one liquid at room temperature Polyethylene glycol and / or glycerin, 10 to 70 parts by weight Polysiloxane and, based on 100 parts by weight of this Mixture, 1 to 30 parts by weight of water.
  • such a ternary Treatment mixture 20 to 70 parts by weight of at least one Polyhydroxy compound, in particular at least one Polyethylene glycol and / or glycerin liquid at room temperature, 30 to 70 parts by weight of polysiloxane and, based on 100 Parts by weight of this mixture, 5 to 25 parts by weight of water contains.
  • the treatment agents then consist of 5 to 75 parts by weight at least one polysiloxane, 25 to 95 parts by weight at least one polyhydroxy compound, especially the aforementioned polyethylene glycol and, based on 100 1 to 30 parts by weight of the above mixture Parts by weight of water.
  • Treatment agent as a further agent with cosmetic agents special properties as well as other usual auxiliary substances contain.
  • skin active ingredients are to be mentioned here based on vitamins or plant extracts, such as for example extracts of horse chestnut seeds, birch, arnica, Chamomile or bisabolol itself, St. John's wort, cucumber, aloe vera or witch hazel, which is partly due to their astringent and healing effects are known.
  • Other active ingredients here are skin care products, for example sorbitan fatty acid esters and oxyethylated, homologous compounds of glycerin, esters of oxethylated Fatty alcohols, fatty alcohol alkanolamides, oxetylated Fatty alcohols, ethoxylated wool fatty alcohols, Glycerol monostearate, stearic acid, cetylstearyl alcohol, To name Vaseline and Lanolin.
  • lanolin itself lanolin derivatives are also used, for example Lanolin alcohols or wool wax alcohols, which under the Designation Amerchol® from Union Carbide Inc. in conjunction are sold with mineral oils.
  • lanolin derivatives are the acetylated lanolins, and hydrophilic lanolin derivatives, for example lanolin-polyoxyethylene compounds.
  • treatment agents can also be used as other additives hydrotropic solubilizers for fatty substances, such as Polyalcohol ethers and ethoxylated fatty alcohols are used become.
  • Another group that is used as an additional component in the treatment agents according to the invention can be used are quaternary ammonium compounds, but especially quaternary ammonium salts, as described, for example, in the US patents 5312522, 5397435, 5405501, 5427696 and the international patent applications WO 95/11344, WO95 / 11343, WO 95/01478, WO 95/01479, WO94 / 29521, WO94 / 29520, WO94 / 16143 and WO94 / 19381 are described.
  • fragrances of the usual type can also be added that are selected from natural, nature-identical or artificial fragrances, the corresponding Fragrances are preferred.
  • Agricultural oils such as lemon oil, bergamot oil, orange oil, Petitgrain oil, softwood oils, foin-coupe fragrance compositions or flower oils such as B. Rose, Jasmine, lilac, lavender, as well as synthetic fragrances based on menthol etc.
  • An overview is provided by Ullmanns Encyclopedia of Technical Chemistry, 4th ed. 1981, volume 20, p. 199-285.
  • inorganic pigment or organic dyes can be added, as is usually the case with Tissue paper production can be used.
  • physiologically safe and non-irritating dyes, especially the corresponding natural dyes preferred. All of the aforementioned additives and auxiliaries in Treatment agents used method according to the invention can be contained individually or as a combination.
  • the treatment agent for Tissue paper products come in an order quantity in the range of 0.01 to 15 percent by weight, preferably 0.5 to 10 Percent by weight, most preferably 2 to 6 percent by weight, based on the dry weight of the fibers.
  • a single or multi-layer, preferably at least two-layer and particularly preferably three or four-layer unembossed or embossed tissue paper is preferably used as the carrier material to which the treatment agent is to be applied.
  • the individual paper webs can be mechanically connected to one another by edge embossing or knurling, glued flat or punctually or else connected to one another in some other way.
  • the Carrier material can also be solidified wet, the usual safe wet strength agents, such as Epichlorohydrin resins, urea-formaldehyde resins, melamine-formaldehyde resins as well as cross-linked cationic polyalkylene amines be used.
  • the usual safe wet strength agents such as Epichlorohydrin resins, urea-formaldehyde resins, melamine-formaldehyde resins as well as cross-linked cationic polyalkylene amines be used.
  • the treatment agent which in a preferred Embodiment is in the form of an emulsion, can be used with any any roller and spray application process or in one Impregnation process can be applied to the carrier material. It is always important to ensure that it does not become a Segregation of the emulsion can occur, d. that is, during the Applying the components of the treatment agent well must be mixed to prevent segregation. This happens, for example, by high shear forces for example due to high-speed stirrers, frequent pumping or by ultrasonic mixing.
  • the treatment agent which to a noticeably improved Softness of tissue products can be used in can be used in a wide variety of product areas. As Its use, for example, has proven to be particularly advantageous on napkins, toilet paper and hand and kitchen towels, Handkerchiefs, facial tissues and facial tissues.
  • composition of the treatment solution is sized so that it can be used during the period at the consumer at the usually annual average prevailing air humidity due to the water content Long-term use does not cause skin irritation (drying out due to the hygroscopic properties of polyethylene glycol or Glycerin) can come. Also a water vapor proof, reclosable packaging is no longer necessary.
  • the treatment solution can both in the wet part Tissue paper machine (cotton machine), at the end of the wire section, in front of or within the press section (mechanical Drainage), d. H. with solids contents between 20 and 50% just as in the one arranged after the press section Dryer section with solids contents from 40 to 97% Dry fiber weight can be added.
  • State of the art Dispatch locations on the transfer screen / belt, e.g. B. before Fleece transfer with a TAD arrangement and the feed on the moist nonwoven fabric after its transfer to the transport (Dry) felt in a conventional one- or two-felt tissue production machine.
  • Treatment chemicals are sprayed onto the Yankee cylinder.
  • An addition of the treatment agent is preferred in the Tissue production machine by spraying on the Pope-Roller producing a treatment agent film and its then transfer to the tissue web during the Roll-up process - usually the already creped one "Tissue web" as a result of the previous drying process a residual temperature between 20 ° C on the Yankee cylinder and about 70 ° C, which for the distribution of Treatment agent and its penetration into the raw tissue is favorable - on the contact surface of the single-layer Tissue web with the surface of the drum of the Pope-Roller.
  • the Use of centrifugal rotors or brushing plants as well as the indirect transmission of a treatment agent film via Roller applicators come into question.
  • the job can also directly on the tissue paper web.
  • Particularly preferred is an addition of the treatment agent within the Duplicating machine or within the processing machine the outer layers of the multilayered web before or during calibration / smoothing. The order is most preferred of the treatment agent within the processing machine the single or multi-layer web.
  • the Get tissue paper products in such a way that one polysiloxane-containing treatment agent of the above type the tissue web or the nonwoven fabric after the dryer section in the tissue paper machine and particularly preferably within the Doubling machine or within the processing machine in an amount of 0.01 to 15% applied to the web and that Subsequent smoothing of fiber fleece after application.
  • one polysiloxane-containing treatment agent of the above type the tissue web or the nonwoven fabric after the dryer section in the tissue paper machine and particularly preferably within the Doubling machine or within the processing machine in an amount of 0.01 to 15% applied to the web and that Subsequent smoothing of fiber fleece after application.
  • polysiloxane-containing treatment agents at one Fiber density from 35 to 97%, based on the Dry fiber weight of the single-ply web, in an amount of 0.5 up to 10% applied to the single-layer web.
  • a multi-layer web as a tissue web and that Treatment agent with a fiber density of more than 90%, based on the dry fiber weight, on at least one of the The outer layers of the multilayered web amount to 1 to 7% apply. It is very particularly preferred that Treatments on the multi-layer tissue web on both Apply outer layers in an amount of 3 to 6%.
  • the Smoothing through at least one pass of the tissue web through a nip of a pair of rollers in which one Roll with a steel surface of a counter roll with a Steel, plastic, paper or rubber surface, preferably but is assigned to a plastic surface.
  • the smoothing of the tissue web after application of the treatment agent is therefore usually carried out in the manner that the tissue webs sprayed on both sides by a smoothing unit be performed.
  • This calender generally consists of two smooth rollers with steel surfaces (steel rollers) whose Surfaces are usually hard chrome-plated. These reels will be hydraulically or pneumatically compressed or for Calibration run on gap. That is, one of the two Rolling is firmly positioned. The second or counter roll will pressed against a stop, so that the two Can not touch steel rollers, but in a certain, measurable and reproducible distance from each other.
  • the tissue webs guided through this gap are opened Gap width compressed and smoothed.
  • the Structural structure of the surface unified, d. H. a uniform thickness.
  • the result is smoothing by leveling the surface in connection with a Uniformity of the thickness profile under the premise of a as little volume loss as possible.
  • a calender can also be used, whereby together with a steel roller or steel counter roller a roller or counter roll is used, which is a rubber or Has paper surface.
  • German patent DE-A-1804418 the German DE-A-2455895, the German patent specification DE-A-2528803, EP-A-0033559, US patent US-A-2179057, US patent US-A-3337388, British patent GB-A-827735, and the German Patents DE-C-822228 and DE-B-1045783.
  • the present invention relates to the use of the aforementioned polysiloxane-containing treatment agent for Softening tissue paper products, in particular Handkerchiefs, facial tissues, facial tissues, napkins, Toilet paper, hand and kitchen towels.
  • the application was carried out symmetrically on the outer surfaces of this fabric.
  • the product thus obtained was referred to as A.
  • Example 2 The application procedure according to Example 1 was repeated, however, instead of a ternary mix, it became a binary one Mixture of 50 percent by weight polyethylene glycol, Molecular weight 200 and 50 percent by weight of the polysiloxane used according to Example 1. The sample thus obtained was called B designated.
  • Example 1 The procedure of Example 1 was repeated, however was instead of the ternary mixture according to the invention pure polysiloxane according to Example 1 in an amount of 6% applied and designated the product obtained with C.
  • Example 1 The procedure of Example 1 was repeated, however instead of the ternary mixture according to the invention, a pure one Polyethylene glycol with a molecular weight of 200 in one amount applied by 6%. The product obtained in this way was treated with D designated. All wipes of Examples 1 and 2 and the Comparative tests 1 and 2 were carried out in a 2-roll (steel / plastic) smoothing unit under identical conditions (Speed, temperature, contact pressure) reproducible smoothed.
  • the haptic properties of the products A and B were compared with the corresponding haptic results of the Comparative products C (pure polysiloxane) and D (pure Polyethylene glycol) (PEG) compared and these products in As part of a so-called panel test (based on "Manual on Sensory Testing Methods, ASTM, Special Technical Publication 434, p. 22; Test form D-Ranking Methods-Rank Order, Elevents Printings February 1993) was evaluated.
  • panel test based on "Manual on Sensory Testing Methods, ASTM, Special Technical Publication 434, p. 22; Test form D-Ranking Methods-Rank Order, Elevents Printings February 1993.
  • the increasing softness defined here as the sum of Surface softness and softness of one Group of 9 people according to the following procedure rated:
  • the paper tissues to be checked were two halves folded so that the sample identifier is not for the test subject is recognizable and in any case the same outside of the Evaluation is presented.
  • the cloths folded in this way were given to the test subjects with the instruction that folded towels between thumb, ball of thumb and finger rubbing and crumpling with regard to their softness and Check the surface softness and then the cloths to put increasing, subjective feeling of quality in line.
  • the patterns were ranked 1, i.e. H. best to 4, d. H. worst rated.
  • the test showed that products A and B according to the invention out of 7 of the 9 test subjects as very good in softness referred to and in relation to the comparative products C and D as were clearly labeled softer. In contrast felt only one of the 9 test subjects compared the product D as softer the product A according to the invention, and one of 9 test subjects the comparative product C softer than that of the invention Products A and B.
  • the panel test also shows that the Products A and B according to the invention are significantly better in relation on crumple softness and surface softness are than that Comparative products C and D.
  • Example 1 In addition to this first in-house panel test, it continued conducted a studio consumer test with 160 people. Here were samples with a lotion composition Polyethylene glycol / polysiloxane / water in a ratio of 72/10/18 with a 3% order quantity as significantly softer judged as a corresponding comparison pattern with pure Siloxane.
  • polysiloxane used in Example 1 described polysiloxane and as polyethylene glycol in Example 1 described polyethylene glycol with a Molecular weight of 200 used.

Claims (22)

  1. Procédé de fabrication de produits en papier mousseline, caractérisé en ce qu'on applique sur le non-tissé ou sur la « bande de tissu ouaté », à l'intérieur de la table de fabrication/section de presses et/ou du train de séchage, donc avec une densité de matière fibreuse, rapportée au poids des fibres sèches du non-Lissé, de 20 à 97%, en quantité de 0,01 à 15%, un agent de traitement contenant un polysiloxane qui contient de 25 à 95 parties en poids, de préférence de 30 à 90 parties en poids, d'un composé polyhydroxy, en particulier au moins un polyéthylèneglycol et/ou une glycérine fluides à température ambiante, de 5 à 75 parties en poids, de préférence 10 à 70 parties en poids de polysiloxane ainsi que, rapportée aux 100 parties en poids de ce mélange, de 0 à 35 parties en poids, de préférence de 1 à 30 parties en poids d'eau, à l'exception d'un agent de traitement, contenant 5% en poids d'un polysiloxane contenant des groupes ammonium quaternaire de formule générale
    Figure 00420001
    dans laquelle
    Figure 00420002
    et R19 est un groupe alkyle à chaíne longue en C12-C18, et on soumet le non-tissé, après l'application, à un post-lissage.
  2. Procédé de fabrication de produits en papier mousseline, caractérisé en ce qu'on applique sur le non-tissé ou la bande de tissu, après le train de séchage dans la machine à papier mousseline, de manière particulièrement préférée à l'intérieur de la bobineuse ou respectivement à l'intérieur de la machine de confectionnement, en quantité de 0,01 à 15%, un agent de traitement contenant un polysiloxarie qui contient de 25 à 95 parties en poids, de préférence de 30 à 90 parties en poids, d'un composé polyhydroxy, en particulier au moins un polyéthylèneglycol et/ou une glycérine fluides à température ambiante, de 5 à 75 parties en poids, de préférence 10 à 70 parties en poids de polysiloxane ainsi que, rapportée aux 100 parties en poids de ce mélange, de 0 à 35 parties en poids, de préférence de 1 à 30 parties en poids d'eau, à l'exception d'un agent de traitement, contenant 5% en poids d'un polysiloxane contenant des groupes ammonium quaternaire de formule générale
    Figure 00430001
    dans laquelle
    Figure 00430002
    et R19 est un groupe alkyle à chaíne longue en C12-C18, et on soumet le non-tissé, après l'application, à un post-lissage.
  3. Procédé selon la revendication 2,
    caractérisé en ce qu'on applique l'agent de traitement contenant un polysiloxane avec une densité de fibres de 35 à 97%, rapportée au poids de fibres sèches de la bande monocouche, en quantité de 0,5 à 10%.
  4. Procédé selon les revendications 1 à 3,
    caractérisé en ce que la bande de tissu est une bande à plusieurs couches et que l'agent de traitement, pour une densité de fibres de plus de 90%, rapportée au poids de fibres sèches, est appliqué en quantité de 1 à 7% sur au moins une des couches extérieures de la bande à plusieurs couches.
  5. Procédé selon la revendication 4,
    caractérisé en ce que l'agent de traitement est appliqué sur la bande de tissu à plusieurs couches, en quantité de 3 à 6%, sur les deux couches extérieures.
  6. Procédé selon la revendication 1 ou 2,
    caractérisé en ce que l'application de l'agent de traitement dans la machine de fabrication de tissu ouaté est effectué par application par pulvérisation sur l'enrouleuse en générant un film d'agent de traitement et son transfert suivant sur la bande de tissu ouaté pendant le processus de bobinage.
  7. Procédé selon les revendications 1 et 2,
    caractérisé en ce que le post-lissage est réalisé par au moins un passage de la bande de tissu ouaté à travers une fente d'une paire de cylindres dans laquelle un contre-cylindre à surface en acier, en matière synthétique ou en caoutchouc, de préférence une surface en matière synthétique, est adjoint à un cylindre à surface en acier.
  8. Procédé selon les revendications 1 et 2,
    caractérisé en ce que le post-lissage est réalisé par un double passage de la bande de tissu ouaté à travers une fente d'une paire de cylindres dans laquelle un contre-cylindre à surface en matière synthétique est d'abord adjoint à un cylindre à surface en acier et ensuite, de manière reflétée dans un miroir, un contre-cylindre à surface en acier est adjoint à un cylindre à surface en matière synthétique.
  9. Procédé selon les revendications 1 à 8,
    caractérisé en ce que l'application de l'agent de traitement sur le non-tissé est réalisée dans le cadre d'un processus conventionnel de fabrication de tissu ouaté.
  10. Procédé selon les revendications 1 à 8,
    caractérisé en ce que l'application de l'agent de traitement sur le non-tissé est réalisée dans le cadre d'un séchage circulaire à bobine ou respectivement un processus TAD.
  11. Procédé selon les revendications 1 à 5,
    caractérisé en ce qu'on utilise un agent de traitement qui contient de 30 à 70 parties en poids d'au moins un composé polyhydroxy, en particulier au moins un polyéthylèneglycol et/ou une glycérine fluides à température ambiante, de 30 à 70 parties en parties en poids d'un polysiloxane et rapportées à 100 parties en poids de ce mélange, de 5 à 25 parties en poids d'eau.
  12. Procédé selon les revendications 1 à 5,
    caractérisé en ce qu'il contient de 5 à 75 parties en poids d'au moins un polysiloxane et de 25 à 95 parties en poids d'un polyéthylèneglycol fluide à température ambiante.
  13. Procédé selon la revendication 12,
    caractérisé en ce qu'on utilise un agent de traitement qui contient de 10 à 70 parties en poids, en particulier de 40 à 60 parties en poids d'au moins un polysiloxane, ainsi que de 30 à 90 parties en poids, en particulier de 40 à 60 parties en poids, du polyéthylèneglycol.
  14. Procédé selon les revendications 1 à 5,
    caractérisé en ce qu'on utilise un agent de traitement contenant 5 à 75 parties en poids d'au moins un polysiloxane et de 25 à 95 parties en poids de glycérine.
  15. Procédé selon la revendication 14,
    caractérisé en ce qu'on utilise un agent de traitement qui contient de 10 à 70 parties en poids, de préférence de 40 à 60 parties en poids, d'au moins un polysiloxane et de 30 à 90 parties en poids, en particulier de 40 à 60 parties en poids, de glycérine.
  16. Procédé selon les revendications 1 à 3,
    caractérisé en ce qu'on utilise un agent de traitement dans lequel le composé polyhydroxy contient de 20 à 80, de préférence de 30 à 70 parties en poids du polyéthylèneglycol précité et de 20 à 80 parties en poids, de préférence de 30 à 70 parties en poids de la glycérine précitée.
  17. Procédé selon les revendications 1 à 5 ou 13 à 16,
    caractérisé en ce qu'on utilise un agent de traitement qui présente le polysiloxane ayant une viscosité de 25 x 10-6 m2/s à 20.000.000 x 10-6 m2/s.
  18. Procédé selon la revendication 17,
    caractérisé en ce qu'on utilise un agent de traitement, dans lequel le polysiloxane est un polydiméthylsiloxane qui présente le cas échéant dans sa chaíne latérale un groupe bétaïne, en particulier un groupe tétraalkylammonium.
  19. Procédé selon les revendications 17 ou 18,
    caractérisé en ce qu'on utilise un agent de traitement dans lequel le polysiloxane est un polyéthersiloxane, en particulier avec une température de trouble dans la plage d'en-dessous de 25°C à 71°C.
  20. Procédé selon les revendications 11 à 19,
    caractérisé en ce qu'on utilise un agent de traitement qui contient en outre un agent cosmétique à propriétés spéciales, par exemple des agents de soins de la peau et/ou des agents actifs sur la peau à base d'extraits de plantes et/ou des parfums.
  21. Procédé selon les revendications 11 à 20,
    caractérisé en ce qu'on utilise un agent de traitement qui contient en outre des produits auxiliaires tels que par exemples, des composés ammonium quaternaire et/ou des solubilisateurs et/ou des agents de résistance à l'humidité.
  22. Utilisation d'un agent de traitement qui contient de 25 à 95 parties en poids, de préférence de 30 à 90 parties en poids, d'au moins un composé polyhydroxy, en particulier au moins un polyéthylèneglycol et/ou une glycérine fluides à température ambiante, de 5 à 75 parties en poids, de préférence 10 à 70 parties en poids de polysiloxane ainsi que, rapportée aux 100 parties en poids de ce mélange, de 0 à 35 parties en poids, de préférence de 1 à 30 parties en poids d'eau, à l'exception d'un agent de traitement, contenant 5% en poids d'un polysiloxane contenant des groupes ammonium quaternaire de formule générale
    Figure 00470001
    dans laquelle
    Figure 00470002
    et R19 est un groupe alkyle à chaíne longue en C12-C18, pour le traitement de produits en papier mousseline en particulier de mouchoirs, de serviettes cosmétiques, de serviettes de démaquillage, de papier hygiéniques ou de serviettes de table.
EP95932724A 1994-09-16 1995-09-12 Procede de fabrication de papier mousseline au moyen d'un agent de traitement Expired - Lifetime EP0803012B1 (fr)

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PCT/EP1995/003588 WO1996008601A1 (fr) 1994-09-16 1995-09-12 Agent de traitement de papier mousseline, procede de fabrication de papier mousseline au moyen de cet agent de traitement et son utilisation

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US6860967B2 (en) 2001-01-19 2005-03-01 Sca Hygiene Products Gmbh Tissue paper penetrated with softening lotion
US6905697B2 (en) 2001-01-19 2005-06-14 Sca Hygiene Products Gmbh Lotioned fibrous web having a short water absorption time
US8545861B2 (en) 2001-01-19 2013-10-01 Sca Hygiene Products Gmbh Lotioned fibrous web having a short water absorption time
US7867361B2 (en) 2008-01-28 2011-01-11 The Procter & Gamble Company Soft tissue paper having a polyhydroxy compound applied onto a surface thereof
US7972475B2 (en) 2008-01-28 2011-07-05 The Procter & Gamble Company Soft tissue paper having a polyhydroxy compound and lotion applied onto a surface thereof
US8070913B2 (en) 2008-01-28 2011-12-06 The Procter & Gamble Company Soft tissue paper having a polyhydroxy compound applied onto a surface thereof
US8187419B2 (en) 2008-01-28 2012-05-29 The Procter & Gamble Company Soft tissue paper having a polyhydroxy compound and lotion applied onto a surface thereof
US10794007B2 (en) 2016-03-24 2020-10-06 Kimberly-Clark Worldwide, Inc. Lotion treated through-air dried tissue

Also Published As

Publication number Publication date
AU3566295A (en) 1996-03-29
EP0803012A1 (fr) 1997-10-29
HUT77476A (hu) 1998-05-28
ATE181754T1 (de) 1999-07-15
NO971198L (no) 1997-05-07
PL319139A1 (en) 1997-07-21
CZ77897A3 (en) 1997-07-16
FI971103A0 (fi) 1997-03-14
FI971103A (fi) 1997-03-14
ES2136307T3 (es) 1999-11-16
GR3031031T3 (en) 1999-12-31
DE59506319D1 (de) 1999-08-05
CA2200049A1 (fr) 1996-03-21
NO971198D0 (no) 1997-03-14
HU220737B1 (hu) 2002-05-28
PL183481B1 (pl) 2002-06-28
WO1996008601A1 (fr) 1996-03-21
SK32497A3 (en) 1997-10-08

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