EP0742858B1 - Method for manufacturing paper or a non-woven web in a foam medium using a non-ionic surfactant - Google Patents

Method for manufacturing paper or a non-woven web in a foam medium using a non-ionic surfactant Download PDF

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Publication number
EP0742858B1
EP0742858B1 EP95908293A EP95908293A EP0742858B1 EP 0742858 B1 EP0742858 B1 EP 0742858B1 EP 95908293 A EP95908293 A EP 95908293A EP 95908293 A EP95908293 A EP 95908293A EP 0742858 B1 EP0742858 B1 EP 0742858B1
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EP
European Patent Office
Prior art keywords
surfactant
paper
foam
witconol
mixture
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EP95908293A
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German (de)
French (fr)
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EP0742858A1 (en
Inventor
Corinne Munerelle
Frank D. Harper
Gary L. Schroeder
Antony D. Awofeso
Henry S. Ostrowski
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Essity Operations France SAS
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Fort James France
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/002—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines by using a foamed suspension
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H21/00—Non-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
    • D21H21/14—Non-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
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants

Definitions

  • the subject of the invention is a method of manufacturing a sheet of paper or of nonwoven in foam medium.
  • the invention finds application in the paper industry for the manufacture of paper or nonwoven, for household, household or sanitary use.
  • desired properties of the sheet of paper or nonwoven are the softness, the wet or dry resistance, bulk, absorbency, etc. A balance between these different properties is sought.
  • foam-based process here means a process for manufacturing wet paper or nonwoven where water is replaced by an aqueous solution comprising a surfactant forming a foam.
  • a process for manufacturing paper in a foam medium is described in EP-A-0 481 746 on behalf of JAMES RIVER CORPORATION OF VIRGINIA.
  • This process consists in preparing a composition of manufacturing in the form of a foaming dispersion of fibers by mixing a suspension of fibers in water with a foaming liquid comprising an agent surfactant, form a fibrous web on a paper machine, recover liquid foaming, recycle part of the foaming liquid to prepare the manufacturing composition and treating another part of the foaming liquid recovered in separating the surfactant from the liquid.
  • surfactants anionic, cationic and non-ionic suitable for the formation of a web fibrous and certain amphoteric surfactants.
  • EP-A-0 481 746 refers to American patents US-A-4,056,456, US-A-3,716,449 and US-A-3,871,952, which describe anionic surfactants, cationic and non-ionic.
  • Cationic type surfactants such as lauramine oxide have no not retained because they were adsorbed on the anionic sites present in the dough paper used for the manufacture of paper for household use.
  • anionic surfactants one has been selected and selected, presenting the best industrial performances, i.e. having a good foam generating power, a good gas (air) content: approximately 60% by volume for the foam formed from this agent, and a good rate of recovery of the surfactant in the foam, while being a compound not showing no toxicity. It is a compound of the ⁇ -olefin-sulfonate or AOS type.
  • the other known nonionic agents did not provide as good process results of the anionic agent mentioned above (rate of recovery, enrichment in surfactant, ).
  • anionic ⁇ -olefin sulfonate compounds in the processes of the prior art however has major drawbacks when the incorporation cationic additives is necessary to improve certain properties of paper such as as softness, tensile strength in the wet or dry state.
  • a cationic agent is added during a process foam medium using an anionic surfactant, in this case OSA, anionic compound and cationic compound chemically react with each other and thus lose their effectiveness.
  • This translates for the added cationic agent, by a loss of its effectiveness, and for the surfactant, by a reduction in the content gas formed foam, which leads to the addition of additional quantities significant amounts of AOS in the foaming liquid.
  • the present invention aims to overcome all of the drawbacks mentioned above when using as surfactant, OSA, while keeping the advantageous performances of this same agent both in terms of implementation advantageous mechanical and other properties observed on the product from this process.
  • Another object of the present invention is to be able to use additives cationic without chemical incompatibility with the surfactant, i.e. does not not reacting with the latter.
  • the object of the present invention is to provide a process which offers better results with regard to the consumption of surfactant and with relates to the recovery of the surfactant during recycling, compared to prior art foam processes.
  • the present invention preferably aims to provide a process which, in the presence cationic additives, improves the smoothness and other properties of the paper sheet obtained by this process, in particular the tensile strength at break in the state dry or wet and the rate of water absorption.
  • the subject of the invention is a process for manufacturing a sheet of paper or nonwoven in a foam medium, the essential characteristic of which is to use, as surfactant for forming the foam, a mixture of ethoxylated alcohols, of formula general (I): R- (OCH 2 CH 2 ) n -OH in which n is an integer ranging from 4 to 20, and R is a linear alkyl group having 8 to 16 carbon atoms, the ethoxylated alcohols having a linear alkyl group of 10, 12 and 14 carbon atoms being present in the mixed.
  • a mixture of ethoxylated alcohols of formula general (I): R- (OCH 2 CH 2 ) n -OH in which n is an integer ranging from 4 to 20, and R is a linear alkyl group having 8 to 16 carbon atoms, the ethoxylated alcohols having a linear alkyl group of 10, 12 and 14 carbon atoms being present in the mixed.
  • the process includes the incorporation of cationic additives for papermaking such as softeners, agents improving tensile strength at break in the dry state, agents improving the tensile strength in the wet state, and / or breaking agents.
  • cationic additives for papermaking such as softeners, agents improving tensile strength at break in the dry state, agents improving the tensile strength in the wet state, and / or breaking agents.
  • dry resistance will be used and "wet strength” respectively for the tensile strength at break dry and wet.
  • the nonionic surfactant used in the invention is a mixture of ethoxylated alcohols corresponding to the general formula (I) below: R- (OCH 2 CH 2 ) n -OH as previously described.
  • One of the preferred agents is the product sold under the brand WITCONOL® SN-120, by WITCO CORPORATION, Houston, Texas, USA.
  • This agent has the formula (I) in which n varies in the range from 4 to 20 and R is a linear alkyl group of 8 to 16 carbon atoms.
  • the identification of the ethoxylated group of this compound has been established by FAB type mass spectrometry.
  • the spectrum obtained clearly shows that the ethoxylation interval varies from 4 to 20 ethoxy groups with a peak around from 8 to 9 groups.
  • the distribution of the alkyl chains of this compound is measured by liquid chromatography. This distribution is not Gaussian.
  • This technique shows that the WITCONOL® SN-120 compound has the particularity of not not present C6 and C8 alkyl chains which are more irritating. Indeed, the compounds comprising these C6 and C8 alkyl chains have been shown to be irritating during rabbit eye test.
  • the WITCONOL® SN-120 also has the advantageous characteristic of have even lower toxicity than the ⁇ -olefin sulfonate (AOS) agents.
  • AOS ⁇ -olefin sulfonate
  • LC50 lethal dose to kill tested aquatic species
  • this agent has received US and European authorization to be used in the manufacture of paper intended for food contact such as paper towels.
  • WITCONOL® SN-120 is preferably used in the form of a mixture 20% water and 80% of the compound in pure form, to be liquid at temperature ambient. This mixture is marketed under the brand WITCONOL® SN-120D.
  • Another nonionic surfactant which can be used in the present invention is the product sold under the brand DESOMC® 12-8.
  • This compound marketed by WITCO CORPORATION is also a mixture of ethoxylated alcohols. It differs from WITCONOL® SN-120 only by the distribution of carbon chains according to their length. Indeed, for this compound, the most important proportion is the C 12 chain: approximately 90% whereas for WITCONOL® SN-120, the most important proportion is the C 10 chain.
  • the cationic additives used in the present invention are softening agents, agents improving wet or dry resistance, or agents improving mechanical properties.
  • Softening agents used are illustrated in the following description by quaternary amines, for example of formula (III): in which R and R 'are alkyl groups of 10 to 14 carbon atoms. This additive is sold under the brand BEROCELL® 595 and is used as a softening agent in the manufacture of paper.
  • BEROCELL® 595 This additive is sold under the brand BEROCELL® 595 and is used as a softening agent in the manufacture of paper.
  • the term “BEROL” will be used in the following text for "BEROCELL®”.
  • additives cationic and more specifically polycationic additives.
  • KYMENE® 557 H is commonly used in the papermaking as an agent increasing the wet strength properties of the piece of paper.
  • a cationic agent improving the dry resistance is illustrated in the text which followed by a quaternary cationic starch ether sold under the brand SOLVITOSE® N.
  • agent mixtures surfactants described previously had at least as good foaming properties as the surfactant ⁇ -olefin sulfonate (AOS) and used to make paper sheets with mechanical properties at least as good as those made with AOS.
  • AOS ⁇ -olefin sulfonate
  • WITCONOL® SN-120 is used, as a surfactant for carrying out the process according to the invention, and the formettes obtained by this process with control formets obtained by a foam-based process using AOS and other control forms obtained by a conventional process in water.
  • BEROL a surfactant for carrying out the process according to the invention
  • SOLVITOSE® N another equally cationic agent
  • a paper composition consisting of a 50/50 mixture of a pulp disintegrated eucalyptus and refined softwood pulp in a Valley pile during 30 minutes.
  • the latter component is added in a proportion of 2 kg / ton of dry paste. After a contact time of approximately 15 minutes of this component with the paper mixture, the whole is diluted in order to reach a concentration of the order of 5 g / l.
  • SOLVITOSE® N SOLVITOSE, in the table below
  • it is added in an amount of 7 kg / ton of dough.
  • the WITCONOL® SN-120 (SN-120 in the table below) has a concentration of 200 ppm (the component is 100% active) and in the control process, OSA at a concentration of 200 ppm (the AOS component being only active at 40%).
  • the foam is formed using an ERNST type continuous foamer. BENZ. A mixture of water and surfactant at a concentration of 200 mg / l is introduced into the device. The foam obtained has an air content of 60% by volume.
  • the paste is mixed at a concentration of 5 g / l for a short time: 1 to 2 seconds with two liters of foam, in a blender. Then the paper mixture comprising the foam is used to make the form according to standard NF Q50-002 on a former of the FRANK type.
  • the measurements are carried out on the formulas after a period of conditioning for at least 48 hours at 23 ° C and an ambient humidity of 50%.
  • the effect of the softening or debinding additive: BEROL is evidence with the surfactant WITCONOL® SN-120.
  • the softening character of BEROL induces a deliant effect which leads to a decrease in interactions between fibers resulting in a reduction of the breaking length of 25% in the case present.
  • the sheet of paper obtained by this process has in particular a another interesting property: softness.
  • This embodiment of the invention is not limiting and any other implementation work of a paper manufacturing process in foam medium, can be considered.
  • the paper machine 10 corresponds to a machine of the “crescent former” type described in American patent US Pat. No. 3,326,745.
  • the part wet forming the sheet comprises a felt 11 permeable to liquid and a fabric 12, of the type used in the manufacture of nonwoven.
  • the canvas 12 is supported by rollers 18 and 19 which are positioned with the head roller 15 so as to make converge the canvas 12 on the felt 11 at the head roller at an angle precise with respect to the felt 11.
  • the felt 11 and the fabric 12 move in the same direction, at the same speed and in the direction of rotation of the head roller 15.
  • the fabric 12 and the felt 11 converge on the surface top of the head roller 15 to form a gap inside which projects a jet of foaming dispersion of fibers from the headbox 20.
  • a multijet system (bi- or trijet) can also be provided for the manufacture of a laminate product.
  • the fabric 12 is stretched so as to pass over the felt 11 on the surface of the head roller 15, the foaming dispersion of fibers is pressed between the fabric 12 and the felt 11 forcing the liquid to pass through the fabric 12 in the Bacholle 22 where the foaming liquid is recovered.
  • the sheet formed in the process is transported by the felt 11 to a suction press 16 where it is transferred to the cylinder 26 of a drying cylinder.
  • the tablecloth forming the paper is dried, then creped by the doctor blade 27.
  • the paper is collected on the take-up roller 28.
  • the surfactant used to prepare the foaming liquid remains in the paper made.
  • the foaming liquid, aqueous solution comprising the surfactant is prepared and stored in silo 30.
  • the silo 30 in water via line 31.
  • the concentration of surfactant in the liquid foaming at the headbox is preferably in the range of about 100 at about 350 parts per million by weight.
  • a gas content, here in air of about 55 to 75% by volume for the foam formed from the nonionic surfactant of formula (I), is recommended for the whole process and in particular at the headbox.
  • the paper pulp from tank 36 is fed through line 33 with the foaming liquid in the headbox 20 by means of a displacement pump positive 32.
  • the formation of the foam takes place at the time of the projection of the composition from the headbox between the fabric 12 and the felt 11 on the face head roller 15.
  • the pressure of the fabric 12 on the felt 11 and the force of the sprayed liquid cause the flow of foaming liquid through the fabric 12 in the Bacholle 22.
  • the foaming liquid recovered in the Bacholle 22 is reintroduced by the line 28 in the silo 30 containing the foaming liquid. And the excess liquid foam recovered in the Bacholle 22, is brought to a separation unit liquid 45 via line 42. Decantation carried out in the separation unit 45 leads to the recovery of a foam phase enriched in surfactant which is separated and recovered by line 47, from the foaming liquid introduced into the liquid separation unit 45. A liquid phase depleted in surfactant is then separated from the foam phase enriched in surfactant and is recovered by driving 56.
  • the foam phase enriched in agent surfactant, broken in the unit 48 is then recycled in the silo 30 for the preparation of the manufacturing composition.
  • the liquid phase depleted in surfactant at the outlet of the separation of the liquid 45 is brought via line 56 to a recovery unit for the surfactant.
  • Foaming liquid is also recovered during the draining which takes place at during the manufacture of the fibrous web, at the suction press 16 or again from the suction box 84, by means of a collector 82. This foaming liquid is then fed into the surfactant recovery unit 55 by means of the line 86 which joins line 56 for supplying foaming liquid already depleted in surfactant, from the liquid separation unit 45.
  • the unit 55 includes specific means 60 for introducing gas or air to generate foam from the foaming liquid introduced into this unit separation 55.
  • the foam formed is recovered by line 64 and is broken in unit 65, then the surfactant is recycled into the silo 30 via line 51.
  • the resulting liquid, even more depleted of surfactant, is recovered in line 68 and can be treated again by another recovery unit 69 of the surfactant, mounted in series with the first unit. Two to six units of recovery can be mounted in series.
  • the machine has a "crescent former" configuration.
  • a surfactant recovery unit has been used.
  • the foaming liquid recovered when the felt is drained is sent to the recovery of the surfactant.
  • WITCONOL® SN-120 is used for these tests as surfactant non-ionic for the process according to the invention, and for comparison, the process water medium, and the foam medium process using AOS.
  • Different refining rates and different concentrations of KYMENE® 557 H, have been tested in the processes in foam medium using WITCONOL® SN-120 and AOS.
  • the concentration in WITCONOL® SN-120 in the headbox is around 225 ppm.
  • the foam obtained from WITCONOL® SN-120 has an identical appearance to that obtained from the AOS, from a visual examination of the size of the bubbles.
  • the initial water absorption rate was also compared, in the presence 6 kg of KYMENE® 557 H per tonne of dough.
  • the initial speed water absorption is 25% higher for the sheet prepared from WITCONOL® SN-120 only for the sheet prepared according to the process in water medium.
  • the method according to the invention can be implemented according to another mode of embodiment which is a variant of that applied to the pilot apparatus, which has been described previously.
  • This second embodiment is illustrated by the diagram shown in Figure 6 and is described in detail in US Patent US-A-5,200,035. It differs from the first embodiment by the stages of preparation of the composition of manufacturing introduced into the headbox.
  • the paper pulp from the pulp castle 100 diluted in a solution aqueous is introduced into a press 101.
  • the latter concentrates the mixture stationer by removing water.
  • the concentrated mixture then passes into a needle shredder 102.
  • the foaming liquid from silo 103 is also fed into the shredder 102.
  • a foaming dispersion of fibers is thus formed and conducted in a positive displacement pump 104, then in the headbox 105.
  • This process eliminates the step of processing the excess liquid recovered in the Bacholle, and therefore allows the separation unit to be eliminated.
  • Another consequence of this device for carrying out the process in a foam medium is the reduction in the recovery unit size. Indeed, in the first embodiment described previously, generally six recovery units are connected in series. Gold, according to this second embodiment, three foam recovery units are sufficient.
  • WITCONOL® as surfactant SN-120, more specifically a solution of WITCONOL® SN-120 active at 80% (i.e. the mixture sold under the brand WITCONOL® SN-120D), for the method according to the invention, and the AOS, more specifically an active AOS solution to 40%, for the control process.
  • WITCONOL® SN-120D surfactant recovery was measured that we compared to that of AOS.
  • the water recovered at the outlet of the recovery units has a concentration of nonionic surfactant of formula (I) such as WITCONOL® SN-120D, plus low, at most equal to about 3 ppm and can then be rejected or reused, having no more foaming character. This characteristic is important with regard to the environmental legislation.
  • the concentration of residual surfactant in the sheet of paper for the WITCONOL® SN-120D decreases by 65% compared to that of products made from OSA.
  • the fixed amount of this component in the sheet in the case of the process in foam medium according to the invention is completely identical to that fixed in a sheet obtained according to the process in water medium.
  • the softness property is assessed by a physical measurement test and in parallel by a panel.
  • the sheet obtained by the process has an even higher softness which can exceed 100 for mother reels and the processed product.

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Description

L'invention a pour objet un procédé de fabrication d'une feuille de papier ou de nontissé en milieu mousse.The subject of the invention is a method of manufacturing a sheet of paper or of nonwoven in foam medium.

L'invention trouve application dans l'industrie papetière pour la fabrication de papier ou nontissé, à usage domestique, ménager ou sanitaire. Selon les utilisations, les propriétés recherchées de la feuille de papier ou de nontissé sont la douceur, la résistance humide ou sèche, le bouffant, le pouvoir absorbant etc... Un équilibre entre ces différentes propriétés est recherché.The invention finds application in the paper industry for the manufacture of paper or nonwoven, for household, household or sanitary use. Depending on the uses, desired properties of the sheet of paper or nonwoven are the softness, the wet or dry resistance, bulk, absorbency, etc. A balance between these different properties is sought.

Or, les produits finis obtenus par les procédés connus de fabrication de papier, en milieu mousse, ne permettent pas d'optimiser toutes les propriétés recherchées.Now, the finished products obtained by known processes for manufacturing paper, in a foam medium, do not allow all the desired properties to be optimized.

Le terme procédé "en milieu mousse" signifie ici un procédé de fabrication de papier ou de nontissé par voie humide où l'eau est substituée par une solution aqueuse comprenant un agent tensio-actif formant une mousse.The term "foam-based" process here means a process for manufacturing wet paper or nonwoven where water is replaced by an aqueous solution comprising a surfactant forming a foam.

Un procédé de fabrication de papier en milieu mousse est décrit dans EP-A-0 481 746 au nom de JAMES RIVER CORPORATION OF VIRGINIA. Ce procédé consiste à préparer une composition de fabrication sous la forme d'une dispersion moussante de fibres en mélangeant une suspension de fibres dans l'eau avec un liquide moussant comprenant un agent tensio-actif, former une nappe fibreuse sur une machine à papier, récupérer du liquide moussant, recycler une partie du liquide moussant pour la préparation de la composition de fabrication et traiter une autre partie du liquide moussant récupéré en séparant l'agent tensio-actif du liquide.A process for manufacturing paper in a foam medium is described in EP-A-0 481 746 on behalf of JAMES RIVER CORPORATION OF VIRGINIA. This process consists in preparing a composition of manufacturing in the form of a foaming dispersion of fibers by mixing a suspension of fibers in water with a foaming liquid comprising an agent surfactant, form a fibrous web on a paper machine, recover liquid foaming, recycle part of the foaming liquid to prepare the manufacturing composition and treating another part of the foaming liquid recovered in separating the surfactant from the liquid.

De nombreux agents tensio-actifs peuvent être utilisés : des agents tensio-actifs anioniques, cationiques et non-ioniques appropriés pour la formation d'une nappe fibreuse et certains agents tensio-actifs amphotères. En ce qui concerne les agents tensio-actifs utilisables, EP-A-0 481 746 fait référence aux brevets américains US-A-4 056 456, US-A-3 716 449 et US-A-3 871 952, qui décrivent des agents tensio-actifs anioniques, cationiques et non-ioniques.Many surfactants can be used: surfactants anionic, cationic and non-ionic suitable for the formation of a web fibrous and certain amphoteric surfactants. With regard to the surfactants which can be used, EP-A-0 481 746 refers to American patents US-A-4,056,456, US-A-3,716,449 and US-A-3,871,952, which describe anionic surfactants, cationic and non-ionic.

Les agents tensio-actifs du type cationique tels que l'oxyde de lauramine n'ont pas été retenus car ils étaient adsorbés sur les sites anioniques présents dans la pâte à papier utilisée pour la fabrication du papier à usage ménager.Cationic type surfactants such as lauramine oxide have no not retained because they were adsorbed on the anionic sites present in the dough paper used for the manufacture of paper for household use.

Par ailleurs, parmi les différents agents tensio-actifs anioniques, un agent a été retenu et sélectionné, présentant les meilleures performances industrielles, c'est-à-dire ayant un bon pouvoir générateur de mousse, une bonne teneur en gaz (en air) : environ 60 % en volume pour la mousse formée à partir de cet agent, et un bon taux de récupération de l'agent tensio-actif dans la mousse, tout en étant un composé ne présentant aucune toxicité. Il s'agit d'un composé du type α-oléfine-sulfonate ou AOS. Furthermore, among the various anionic surfactants, one has been selected and selected, presenting the best industrial performances, i.e. having a good foam generating power, a good gas (air) content: approximately 60% by volume for the foam formed from this agent, and a good rate of recovery of the surfactant in the foam, while being a compound not showing no toxicity. It is a compound of the α-olefin-sulfonate or AOS type.

Les autres agents connus de type non-ioniques ne procuraient pas d'aussi bons résultats que l'agent anionique mentionné ci-dessus sur le plan du procédé (taux de récupération, enrichissement en agent tensio-actif, ...).The other known nonionic agents did not provide as good process results of the anionic agent mentioned above (rate of recovery, enrichment in surfactant, ...).

L'utilisation des composés α-oléfine-sulfonates anioniques dans les procédés de l'art antérieur présente cependant des inconvénients majeurs lorsque l'incorporation d'additifs cationiques est nécessaire pour améliorer certaines propriétés du papier telles que la douceur, la résistance à la rupture par traction à l'état humide ou sec. En effet, le problème qui se pose lorsqu'un agent cationique est ajouté au cours d'un procédé en milieu mousse utilisant un agent tensio-actif anionique, en l'occurrence l'AOS, le composé anionique et le composé cationique réagissent chimiquement l'un avec l'autre et perdent ainsi de leur efficacité. Ceci se traduit pour l'agent cationique ajouté, par une perte de son efficacité, et pour l'agent tensio-actif, par une diminution de la teneur en gaz de la mousse formée, ce qui entraíne l'addition de quantités supplémentaires importantes d'AOS dans le liquide moussant. Or, de par ses propriétés déliantes, l'incorporation excessive d'AOS conduit à un produit qui n'est plus suffisamment résistant à l'état sec. De ce fait, un raffinage plus important de la pâte ou l'incorporation d'autres additifs tels qu'un amidon modifié, pour remédier à la perte de résistance, est nécessaire.The use of anionic α-olefin sulfonate compounds in the processes of the prior art however has major drawbacks when the incorporation cationic additives is necessary to improve certain properties of paper such as as softness, tensile strength in the wet or dry state. Indeed, the problem that arises when a cationic agent is added during a process foam medium using an anionic surfactant, in this case OSA, anionic compound and cationic compound chemically react with each other and thus lose their effectiveness. This translates for the added cationic agent, by a loss of its effectiveness, and for the surfactant, by a reduction in the content gas formed foam, which leads to the addition of additional quantities significant amounts of AOS in the foaming liquid. However, by its deliant properties, excessive incorporation of OSA leads to a product that is no longer sufficient resistant to dryness. Therefore, a more refined refining of the dough or the incorporation of other additives such as a modified starch, to remedy the loss of resistance, is necessary.

La présente invention a pour but de pallier l'ensemble des inconvénients précités rencontrés lorsqu'on utilise comme agent tensio-actif, l'AOS, tout en gardant les performances avantageuses de ce même agent tant au niveau de la mise en oeuvre du procédé que des propriétés avantageuses, mécaniques et autres, observées sur le produit issu de ce procédé.The present invention aims to overcome all of the drawbacks mentioned above when using as surfactant, OSA, while keeping the advantageous performances of this same agent both in terms of implementation advantageous mechanical and other properties observed on the product from this process.

La présente invention a encore pour but de pouvoir utiliser des additifs cationiques sans incompatibilité chimique avec l'agent tensio-actif, c'est-à-dire ne réagissant pas avec ce dernier.Another object of the present invention is to be able to use additives cationic without chemical incompatibility with the surfactant, i.e. does not not reacting with the latter.

La présente invention a pour but de fournir un procédé qui offre de meilleurs résultats en ce qui concerne la consommation en agent tensio-actif et en ce qui concerne la récupération de l'agent tensio-actif au cours du recyclage, par rapport aux procédés en milieu mousse de l'art antérieur.The object of the present invention is to provide a process which offers better results with regard to the consumption of surfactant and with relates to the recovery of the surfactant during recycling, compared to prior art foam processes.

La présente invention a de préférence pour but de fournir un procédé qui, en présence d'additifs cationiques, améliore la douceur et d'autres propriétés de la feuille de papier obtenue par ce procédé, dont notamment la résistance à la rupture par traction à l'état sec ou humide et la vitesse d'absorption en eau.The present invention preferably aims to provide a process which, in the presence cationic additives, improves the smoothness and other properties of the paper sheet obtained by this process, in particular the tensile strength at break in the state dry or wet and the rate of water absorption.

L'invention a pour objet un procédé de fabrication d'une feuille de papier ou de nontissé en milieu mousse, dont la caractéristique essentielle est d'utiliser comme agent tensio-actif pour former la mousse, un mélange d'alcools éthoxylés, de formule générale (I) : R-(OCH2CH2)n-OH dans laquelle n est un nombre entier allant de 4 à 20, et R est un groupement alkyle linéaire ayant de 8 à 16 atomes de carbone, les alcools éthoxylés ayant un groupement alkyle linéaire de 10, 12 et 14 atomes de carbone étant présents dans le mélange.The subject of the invention is a process for manufacturing a sheet of paper or nonwoven in a foam medium, the essential characteristic of which is to use, as surfactant for forming the foam, a mixture of ethoxylated alcohols, of formula general (I): R- (OCH 2 CH 2 ) n -OH in which n is an integer ranging from 4 to 20, and R is a linear alkyl group having 8 to 16 carbon atoms, the ethoxylated alcohols having a linear alkyl group of 10, 12 and 14 carbon atoms being present in the mixed.

De préférence, le procédé comprend l'incorporation d'additifs cationiques pour la fabrication du papier tels que des agents adoucissants, des agents améliorant la résistance à la rupture par traction à l'état sec, des agents améliorant la résistance à la rupture par traction à l'état humide, et/ou des agents déliants.Preferably, the process includes the incorporation of cationic additives for papermaking such as softeners, agents improving tensile strength at break in the dry state, agents improving the tensile strength in the wet state, and / or breaking agents.

D'autres caractéristiques et avantages de l'invention apparaítront à la lecture détaillée de l'invention qui suit, en référence aux dessins annexés dans lesquels :

  • la figure 1 représente schématiquement un dispositif pour la mise en oeuvre du procédé selon l'invention suivant un mode de réalisation, reprenant la figure 1 simplifiée de la demande de brevet européen EP-A-0,481,746 ;
  • la figure 2 représente des courbes illustrant la consommation d'agent tensio-actif nécessaire pour maintenir constante la teneur en air en fonction de la quantité d'additif cationique ajoutée ;
  • la figure 3 représente des courbes où la force de résistance à la rupture par traction de la feuille à l'état sec est fonction de la quantité d'additif cationique ajoutée pour différents agents tensio-actifs;
  • la figure 4 représente des courbes de la force de résistance à la rupture par traction à l'état humide en fonction de la quantité d'additif cationique ajoutée pour différents agents tensio-actifs ;
  • la figure 5 illustre la vitesse d'absorption en eau par la feuille pour différents agents tensio-actifs ; et
  • la figure 6 est un diagramme schématique illustrant une variante du procédé de fabrication de papier, décrite dans le brevet américain N° 5 200 035.
Other characteristics and advantages of the invention will appear on detailed reading of the invention which follows, with reference to the appended drawings in which:
  • FIG. 1 schematically represents a device for implementing the method according to the invention according to an embodiment, using FIG. 1 simplified from European patent application EP-A-0,481,746;
  • FIG. 2 represents curves illustrating the consumption of surfactant necessary to keep the air content constant as a function of the amount of cationic additive added;
  • FIG. 3 represents curves in which the strength of tensile strength of the sheet in the dry state is a function of the amount of cationic additive added for different surfactants;
  • FIG. 4 represents curves of the tensile strength strength in the wet state as a function of the amount of cationic additive added for different surfactants;
  • FIG. 5 illustrates the speed of absorption of water by the sheet for various surfactants; and
  • Figure 6 is a schematic diagram illustrating a variant of the paper manufacturing process, described in US Patent No. 5,200,035.

Dans la description qui suit, on utilisera les termes "résistance sèche" et "résistance humide" respectivement pour la résistance à la rupture par traction à l'état sec et à l'état humide.In the following description, the terms "dry resistance" will be used and "wet strength" respectively for the tensile strength at break dry and wet.

L'agent tensio-actif non-ionique utilisé dans l'invention, est un mélange d'alcools éthoxylés répondant à la formule générale (I) ci-dessous : R-(OCH2CH2)n-OH tel que décrit précédemment.The nonionic surfactant used in the invention is a mixture of ethoxylated alcohols corresponding to the general formula (I) below: R- (OCH 2 CH 2 ) n -OH as previously described.

Ces composés résultent de la condensation de l'oxyde d'éthylène et d'alcools. Ces composés sont encore dénommés "éthers de polyéthylène-glycols". These compounds result from the condensation of ethylene oxide and alcohols. These compounds are still called "polyethylene glycol ethers".

De tels agents tensio-actifs ont été testés et décrits pour illustrer l'invention.Such surfactants have been tested and described to illustrate the invention.

Un des agents préférés est le produit commercialisé sous la marque WITCONOL® SN-120, par WITCO CORPORATION, Houston, Texas, Etats-Unis.One of the preferred agents is the product sold under the brand WITCONOL® SN-120, by WITCO CORPORATION, Houston, Texas, USA.

Cet agent a pour formule (I) dans laquelle n varie dans l'intervalle de 4 à 20 et R est groupement alkyle linéaire de 8 à 16 atomes de carbone.This agent has the formula (I) in which n varies in the range from 4 to 20 and R is a linear alkyl group of 8 to 16 carbon atoms.

L'identification du groupement éthoxylé de ce composé a été établie par spectrométrie de masse de type FAB. Le spectre obtenu montre avec évidence que l'intervalle d'éthoxylation varie de 4 à 20 groupements éthoxy avec un pic aux environs de 8 à 9 groupements. La répartition des chaínes alkyles de ce composé est mesurée par chromatographie liquide. Cette répartition n'est pas gaussienne. Cette technique permet de montrer que le composé WITCONOL® SN-120 a pour particularité de ne pas présenter de chaíne alkyle en C6 et C8 qui sont plus irritantes. En effet, les composés comportant ces chaínes alkyles en C6 et C8 se sont révélés irritants lors de test sur les yeux de lapin.The identification of the ethoxylated group of this compound has been established by FAB type mass spectrometry. The spectrum obtained clearly shows that the ethoxylation interval varies from 4 to 20 ethoxy groups with a peak around from 8 to 9 groups. The distribution of the alkyl chains of this compound is measured by liquid chromatography. This distribution is not Gaussian. This technique shows that the WITCONOL® SN-120 compound has the particularity of not not present C6 and C8 alkyl chains which are more irritating. Indeed, the compounds comprising these C6 and C8 alkyl chains have been shown to be irritating during rabbit eye test.

La répartition des chaínes alkyles est la suivante :

  • chaíne carbonée en C8 : 2,0 % maximum
  • chaíne carbonée en C10 : 83-89 %
  • chaíne carbonée en C12 : 5-9 %
  • chaíne carbonée en C14 : 3-7 %
  • chaíne carbonée en C16 : 0,5 % maximum
The distribution of the alkyl chains is as follows:
  • C8 carbon chain: 2.0% maximum
  • carbon chain in C10: 83-89%
  • carbon chain in C12: 5-9%
  • carbon chain in C14: 3-7%
  • carbon chain in C16: 0.5% maximum

Le WITCONOL® SN-120 a également pour caractéristique avantageuse de présenter une encore plus faible toxicité que les agents α-oléfine-sulfonates (AOS). En effet, le LC50 (dose léthale pour tuer des espèces aquatiques testées) pour le WITCONOL® SN-120 est au moins deux fois plus élevé que pour l'AOS. De plus, cet agent a reçu l'autorisation américaine et européenne pour être utilisé dans la fabrication de papier destiné au contact alimentaire tel que l'essuie-tout.The WITCONOL® SN-120 also has the advantageous characteristic of have even lower toxicity than the α-olefin sulfonate (AOS) agents. In indeed, LC50 (lethal dose to kill tested aquatic species) for the WITCONOL® SN-120 is at least twice as high as for AOS. In addition, this agent has received US and European authorization to be used in the manufacture of paper intended for food contact such as paper towels.

Le WITCONOL® SN-120 est utilisé de préférence sous la forme d'un mélange de 20 % d'eau et 80 % du composé sous forme pure, pour être liquide à température ambiante. Ce mélange est commercialisé sous la marque WITCONOL® SN-120D. WITCONOL® SN-120 is preferably used in the form of a mixture 20% water and 80% of the compound in pure form, to be liquid at temperature ambient. This mixture is marketed under the brand WITCONOL® SN-120D.

Un autre agent tensio-actif non-ionique pouvant être utilisé dans la présente invention est le produit commercialisé sous la marque DESOMC® 12-8.Another nonionic surfactant which can be used in the present invention is the product sold under the brand DESOMC® 12-8.

Ce composé commercialisé par WITCO CORPORATION est également un mélange d'alcools éthoxylés. Il diffère du WITCONOL® SN-120 uniquement par la répartition des chaínes carbonées suivant leur longueur. En effet, pour ce composé, la proportion la plus importante est la chaíne en C12 : environ 90 % alors que pour le WITCONOL® SN-120, la proportion la plus importante est la chaíne en C10.This compound marketed by WITCO CORPORATION is also a mixture of ethoxylated alcohols. It differs from WITCONOL® SN-120 only by the distribution of carbon chains according to their length. Indeed, for this compound, the most important proportion is the C 12 chain: approximately 90% whereas for WITCONOL® SN-120, the most important proportion is the C 10 chain.

Par ailleurs, les additifs cationiques utilisés dans la présente invention sont des agents adoucissants, des agents améliorant la résistance humide ou sèche, ou encore des agents améliorant les propriétés mécaniques.Furthermore, the cationic additives used in the present invention are softening agents, agents improving wet or dry resistance, or agents improving mechanical properties.

Des agents adoucissants utilisés sont illustrés dans la description qui suit par des amines quaternaires, par exemple de formule (III) :

Figure 00050001
dans laquelle R et R' sont des groupements alkyles de 10 à 14 atomes de carbone. Cet additif est commercialisé sous la marque BEROCELL® 595 et est utilisé comme agent adoucissant dans la fabrication du papier. On utilisera le terme "BEROL" dans le texte qui suit pour "BEROCELL®".Softening agents used are illustrated in the following description by quaternary amines, for example of formula (III):
Figure 00050001
in which R and R 'are alkyl groups of 10 to 14 carbon atoms. This additive is sold under the brand BEROCELL® 595 and is used as a softening agent in the manufacture of paper. The term "BEROL" will be used in the following text for "BEROCELL®".

Les agents améliorant la résistance humide ou sèche sont des additifs cationiques, et plus précisément des additifs polycationiques. L'un d'entre eux, commercialisé sous la marque KYMENE® 557 H, est couramment utilisé dans la fabrication du papier comme agent augmentant les propriétés de résistance humide de la feuille de papier.Agents improving wet or dry resistance are additives cationic, and more specifically polycationic additives. One of them, marketed under the brand name KYMENE® 557 H, is commonly used in the papermaking as an agent increasing the wet strength properties of the piece of paper.

C'est un produit de réaction de l'épichlorhydrine avec un poly(aminoamide) de condensation obtenue à partir de l'acide adipique et de la diéthylène triamine. Les sites cationiques sont probablement formés par conversion d'une fonction amine primaire fixée sur la chaíne de poly(aminoamide) et issue de la réaction de la diéthylène triamine, qui réagit avec l'épichlorhydrine, selon la publication "The Structure of Kymene, Matiur Rahman, Teepak, Inc., 1991 Nonwoven Conference, 299-303".It is a reaction product of epichlorohydrin with a poly (aminoamide) of condensation obtained from adipic acid and diethylene triamine. The sites cationic are probably formed by conversion of a primary amine function attached to the poly (aminoamide) chain and resulting from the reaction of diethylene triamine, which reacts with epichlorohydrin, according to the publication "The Structure of Kymene, Matiur Rahman, Teepak, Inc., 1991 Nonwoven Conference, 299-303 ".

Un agent cationique améliorant la résistance sèche est illustré dans le texte qui suit par un éther d'amidon cationique quaternaire commercialisé sous la marque SOLVITOSE® N.A cationic agent improving the dry resistance is illustrated in the text which followed by a quaternary cationic starch ether sold under the brand SOLVITOSE® N.

Dans un premier temps, on a vérifié à l'échelle expérimentale que les mélanges agents tensio-actifs décrits précédemment présentaient au moins d'aussi bonnes propriétés moussantes que l'agent tensio-actif α-oléfine sulfonate (AOS) et permettaient de réaliser des formettes de papier présentant des propriétés mécaniques au moins aussi bonnes que celles fabriquées avec l'AOS.First, it was verified on an experimental scale that the agent mixtures surfactants described previously had at least as good foaming properties as the surfactant α-olefin sulfonate (AOS) and used to make paper sheets with mechanical properties at least as good as those made with AOS.

Dans l'essai réalisé et décrit ci-après, on utilise le WITCONOL® SN-120, comme agent tensio-actif pour réaliser le procédé selon l'invention, et l'on compare les formettes obtenues par ce procédé avec des formettes témoins obtenues par un procédé en milieu mousse utilisant l'AOS et avec d'autres formettes témoins obtenues par un procédé classique en milieu eau. On vérifie par ailleurs l'incorporation possible d'additifs cationiques tels que le BEROL, et d'un autre agent également cationique, la SOLVITOSE® N, qui est ajouté pour compenser la baisse de résistance à la rupture entraínée par l'addition du BEROL, agent adoucissant et déliant.In the test carried out and described below, WITCONOL® SN-120 is used, as a surfactant for carrying out the process according to the invention, and the formettes obtained by this process with control formets obtained by a foam-based process using AOS and other control forms obtained by a conventional process in water. We also check the possible incorporation cationic additives such as BEROL, and another equally cationic agent, SOLVITOSE® N, which is added to compensate for the drop in breaking strength driven by the addition of BEROL, softening and loosening agent.

On utilise une composition papetière constituée d'un mélange 50/50 d'une pâte d'eucalyptus désintégrée et d'une pâte de résineux raffinée dans une pile Valley pendant 30 minutes.A paper composition is used consisting of a 50/50 mixture of a pulp disintegrated eucalyptus and refined softwood pulp in a Valley pile during 30 minutes.

Pour les essais comportant l'incorporation de BEROL, agent déliant, ce dernier composant est ajouté dans une proportion de 2 kg/tonne de pâte sèche. Après un temps de contact d'environ 15 minutes de ce composant avec le mélange papetier, l'ensemble est dilué afin d'atteindre une concentration de l'ordre de 5 g/l. Lorsque la SOLVITOSE® N (SOLVITOSE, dans le tableau qui suit) est présente, elle est ajoutée dans une quantité de 7 kg/tonne de pâte.For tests involving the incorporation of BEROL, a debonding agent, the latter component is added in a proportion of 2 kg / ton of dry paste. After a contact time of approximately 15 minutes of this component with the paper mixture, the whole is diluted in order to reach a concentration of the order of 5 g / l. When the SOLVITOSE® N (SOLVITOSE, in the table below) is present, it is added in an amount of 7 kg / ton of dough.

Par ailleurs, on prépare une mousse en utilisant dans le procédé selon l'invention, le WITCONOL® SN-120 (SN-120 dans le tableau qui suit) à une concentration de 200 ppm (le composant est 100 % actif) et dans le procédé témoin, l'AOS à une concentration de 200 ppm (le composant AOS n'étant actif qu'à 40 %).Furthermore, a foam is prepared using in the process according to the invention, the WITCONOL® SN-120 (SN-120 in the table below) has a concentration of 200 ppm (the component is 100% active) and in the control process, OSA at a concentration of 200 ppm (the AOS component being only active at 40%).

La mousse est formée à l'aide d'un mousseur en continu de type ERNST BENZ. Un mélange d'eau et d'agent tensio-actif à une concentration de 200 mg/l est introduit dans l'appareil. La mousse obtenue a une teneur en air de 60 % en volume.The foam is formed using an ERNST type continuous foamer. BENZ. A mixture of water and surfactant at a concentration of 200 mg / l is introduced into the device. The foam obtained has an air content of 60% by volume.

Pour réaliser une formette de papier d'un grammage de 25 g/m2, on mélange la pâte à une concentration de 5 g/l pendant un temps court : 1 à 2 secondes avec deux litres de mousse, dans un mixeur. Puis on utilise le mélange papetier comportant la mousse pour réaliser la formette selon la norme NF Q50-002 sur un formeur de type FRANK.To make a paper form with a grammage of 25 g / m 2 , the paste is mixed at a concentration of 5 g / l for a short time: 1 to 2 seconds with two liters of foam, in a blender. Then the paper mixture comprising the foam is used to make the form according to standard NF Q50-002 on a former of the FRANK type.

Les mesures sont effectuées sur les formettes après une période de conditionnement d'au moins 48 heures à 23°C et à une humidité ambiante de 50 %. On mesure le grammage, l'épaisseur, le bouffant de chaque formette ainsi que la résitance à la rupture par traction à l'état sec, ce qui permet de déterminer la force de rupture, l'allongement et la longueur de rupture.The measurements are carried out on the formulas after a period of conditioning for at least 48 hours at 23 ° C and an ambient humidity of 50%. We measures the grammage, the thickness, the bulk of each form and the resistance at rupture by tensile strength in the dry state, which makes it possible to determine the breaking force, elongation and break length.

Les mesures des différents paramètres (épaisseur, bouffant, rupture) sont rapportés dans le tableau I ci-après.

Figure 00070001
The measurements of the various parameters (thickness, bulk, rupture) are reported in Table I below.
Figure 00070001

Il ressort du Tableau I qui précède que le WITCONOL® SN-120 peut tout à fait être substitué à l'AOS sans modification des caractéristiques mécaniques des formettes. En effet, les propriétés des formettes obtenues à partir de l'agent tensio-actif WITCONOL® SN-120 sont au moins aussi bonnes que celles des formettes obtenues en utilisant l'AOS.It appears from Table I above that the WITCONOL® SN-120 can is substituted for the AOS without modifying the mechanical characteristics of the formettes. Indeed, the properties of the formulas obtained from the surfactant WITCONOL® SN-120 are at least as good as those of the formulas obtained using the AOS.

De plus, l'effet de l'additif adoucissant ou déliant : le BEROL, est mis en évidence avec l'agent tensio-actif WITCONOL® SN-120. Le caractère adoucissant du BEROL induit un effet déliant qui entraíne une diminution des interactions entre fibres ayant pour conséquence une diminution de la longueur de rupture de 25 % dans le cas présent.In addition, the effect of the softening or debinding additive: BEROL, is evidence with the surfactant WITCONOL® SN-120. The softening character of BEROL induces a deliant effect which leads to a decrease in interactions between fibers resulting in a reduction of the breaking length of 25% in the case present.

Aucun résultat n'est rapporté quant à l'utilisation du BEROL avec l'AOS. L'agent tensio-actif anionique réagissant avec l'additif cationique, ce procédé n'est pas réalisable industriellement.No results are reported on the use of BEROL with OSA. Since the anionic surfactant reacts with the cationic additive, this process is not industrially feasible.

Par ailleurs, l'incorporation de SOLVITOSE® N, additif cationique, avec l'agent tensio-actif non-ionique est tout à fait compatible et le résultat escompté, augmentation de la résistance, est obtenu.In addition, the incorporation of SOLVITOSE® N, cationic additive, with the nonionic surfactant is entirely compatible and the expected result, increased resistance, is obtained.

Enfin, la combinaison WITCONOL® SN-120, BEROL et SOLVITOSE® N a été testée. Les résultats prouvent que la SOLVITOSE® N corrige facilement la perte de résistance sèche et peut ainsi être ajouté le cas échéant dans la pratique industrielle pour compenser cette perte, afin d'obtenir un bon compromis entre les propriétés de douceur et de résistance à la rupture de la feuille de papier.Finally, the combination WITCONOL® SN-120, BEROL and SOLVITOSE® N a been tested. Results show that SOLVITOSE® N easily corrects loss of dry resistance and can thus be added if necessary in industrial practice to compensate for this loss, in order to obtain a good compromise between the properties of softness and breaking strength of the sheet of paper.

D'autres caractéristiques avantageuses du procédé selon l'invention apparaissent à l'échelle industrielle au cours de la mise en oeuvre du procédé. La consommation en agent tensio-actif, le recyclage du liquide moussant, la récupération de l'agent tensio-actif rendent ce procédé très intéressant d'un point de vue économique.Other advantageous characteristics of the process according to the invention appear on an industrial scale during the implementation of the process. The consumption of surfactant, recycling of foaming liquid, recovery of surfactant make this process very interesting from a point of view economic.

De plus, la feuille de papier obtenue par ce procédé présente notamment une autre propriété intéressante : la douceur.In addition, the sheet of paper obtained by this process has in particular a another interesting property: softness.

Un des procédés mousse qui peut être utilisé dans la présente invention est décrit dans EP-A-0 481 746, et est résumé ci-dessous, en référence à la figure 1.One of the foam processes which can be used in the present invention is described in EP-A-0 481 746, and is summarized below, with reference to Figure 1.

Ce mode de réalisation de l'invention n'est pas limitatif et toute autre mise en oeuvre d'un procédé de fabrication du papier en milieu mousse, peut être envisagée.This embodiment of the invention is not limiting and any other implementation work of a paper manufacturing process in foam medium, can be considered.

Dans le procédé illustré ici, la machine à papier 10 correspond à une machine du type "crescent former" décrite dans le brevet américain US-A-3 326 745. La partie humide formant la nappe comprend un feutre 11 perméable au liquide et une toile 12, du type utilisés dans la fabrication du nontissé. La toile 12 est supportée par des rouleaux 18 et 19 qui sont positionnés avec le rouleau de tête 15 de manière à faire converger la toile 12 sur le feutre 11 au niveau du rouleau de tête suivant un angle précis par rapport au feutre 11. Le feutre 11 et la toile 12 se déplacent dans la même direction, à la même vitesse et dans la direction de rotation du rouleau de tête 15.In the process illustrated here, the paper machine 10 corresponds to a machine of the “crescent former” type described in American patent US Pat. No. 3,326,745. The part wet forming the sheet comprises a felt 11 permeable to liquid and a fabric 12, of the type used in the manufacture of nonwoven. The canvas 12 is supported by rollers 18 and 19 which are positioned with the head roller 15 so as to make converge the canvas 12 on the felt 11 at the head roller at an angle precise with respect to the felt 11. The felt 11 and the fabric 12 move in the same direction, at the same speed and in the direction of rotation of the head roller 15.

Dans cette machine, la toile 12 et le feutre 11 convergent à la surface supérieure du rouleau de tête 15 pour former un écartement à l'intérieur duquel on projette un jet d'une dispersion moussante de fibres provenant de la caisse de tête 20. Un système multijets (bi- ou trijets) peut également être prévu pour la fabrication d'un produit stratifié.In this machine, the fabric 12 and the felt 11 converge on the surface top of the head roller 15 to form a gap inside which projects a jet of foaming dispersion of fibers from the headbox 20. A multijet system (bi- or trijet) can also be provided for the manufacture of a laminate product.

La toile 12 est tendue de manière à passer au-dessus du feutre 11 sur la surface du rouleau de tête 15, la dispersion moussante de fibres est pressée entre la toile 12 et le feutre 11 forçant le liquide à passer à travers la toile 12 dans le Bacholle 22 où le liquide moussant est récupéré. La nappe formée dans le procédé est transportée par le feutre 11 vers une presse aspirante 16 où elle est transférée vers le cylindre 26 d'un cylindre sécheur.The fabric 12 is stretched so as to pass over the felt 11 on the surface of the head roller 15, the foaming dispersion of fibers is pressed between the fabric 12 and the felt 11 forcing the liquid to pass through the fabric 12 in the Bacholle 22 where the foaming liquid is recovered. The sheet formed in the process is transported by the felt 11 to a suction press 16 where it is transferred to the cylinder 26 of a drying cylinder.

La nappe formant le papier est séchée, puis crêpée par le râcle 27.The tablecloth forming the paper is dried, then creped by the doctor blade 27.

Le papier est récupéré sur le rouleau cylindre récepteur 28. Une partie de l'agent tensio-actif utilisé pour préparer le liquide moussant, reste dans le papier fabriqué.The paper is collected on the take-up roller 28. the surfactant used to prepare the foaming liquid, remains in the paper made.

Le liquide moussant, solution aqueuse comprenant l'agent tensio-actif est préparé et stocké dans le silo 30. Pour initier la formation de la mousse, on alimente le silo 30 en eau par la conduite 31. La concentration en agent tensio-actif dans le liquide moussant au niveau de la caisse de tête est de préférence dans l'intervalle d'environ 100 à environ 350 parties par million en poids.The foaming liquid, aqueous solution comprising the surfactant is prepared and stored in silo 30. To initiate the formation of foam, the silo 30 in water via line 31. The concentration of surfactant in the liquid foaming at the headbox is preferably in the range of about 100 at about 350 parts per million by weight.

Une teneur en gaz, ici en air d'environ 55 à 75 % en volume pour la mousse formée à partir de l'agent tensio-actif non-ionique de formule (I), est préconisée pour l'ensemble du procédé et en particulier au niveau de la caisse de tête.A gas content, here in air of about 55 to 75% by volume for the foam formed from the nonionic surfactant of formula (I), is recommended for the whole process and in particular at the headbox.

La pâte à papier provenant de la cuve 36 est alimentée par la conduite 33 avec le liquide moussant dans la caisse de tête 20 au moyen d'une pompe à déplacement positif 32.The paper pulp from tank 36 is fed through line 33 with the foaming liquid in the headbox 20 by means of a displacement pump positive 32.

La formation de la mousse a lieu au moment de la projection de la composition de fabrication provenant de la caisse de tête entre la toile 12 et le feutre 11 sur la face supérieure du rouleau de tête 15.The formation of the foam takes place at the time of the projection of the composition from the headbox between the fabric 12 and the felt 11 on the face head roller 15.

La pression de la toile 12 sur le feutre 11 et la force du liquide projeté entraínent l'écoulement du liquide moussant à travers la toile 12 dans le Bacholle 22.The pressure of the fabric 12 on the felt 11 and the force of the sprayed liquid cause the flow of foaming liquid through the fabric 12 in the Bacholle 22.

Les forces produites par le rapprochement de la toile 12 sur le feutre 11, la vitesse linéaire et la force du jet sur la toile 12 produisent des forces de compression et de cisaillement sur le liquide suffisantes pour entraíner le transport de l'air dans la toile et ses interstices générant ainsi la mousse contenant de 55 à 75 % en volume d'air.The forces produced by the bringing together of the fabric 12 on the felt 11, the linear velocity and the force of the jet on the fabric 12 produce compressive forces and sufficient shear on the liquid to cause the transport of air in the fabric and its interstices thus generating the foam containing 55 to 75% by volume of air.

Le liquide moussant récupéré dans le Bacholle 22, est ré-introduit par la conduite 28 dans le silo 30 contenant le liquide moussant. Et l'excès de liquide moussant récupéré dans le Bacholle 22, est amené dans une unité de séparation du liquide 45 par la conduite 42. La décantation réalisée dans l'unité de séparation 45 conduit à la récupération d'une phase mousse enrichie en agent tensio-actif qui est séparée et récupérée par la conduite 47, à partir du liquide moussant introduit dans l'unité de séparation du liquide 45. Une phase liquide appauvrie en agent tensio-actif est alors séparée de la phase mousse enrichie en agent tensio-actif et est récupérée par la conduite 56.The foaming liquid recovered in the Bacholle 22 is reintroduced by the line 28 in the silo 30 containing the foaming liquid. And the excess liquid foam recovered in the Bacholle 22, is brought to a separation unit liquid 45 via line 42. Decantation carried out in the separation unit 45 leads to the recovery of a foam phase enriched in surfactant which is separated and recovered by line 47, from the foaming liquid introduced into the liquid separation unit 45. A liquid phase depleted in surfactant is then separated from the foam phase enriched in surfactant and is recovered by driving 56.

A la sortie de l'unité de séparation 45, la phase mousse enrichie en agent tensio-actif, brisée dans l'unité 48 est ensuite recyclée dans le silo 30 pour la préparation de la composition de fabrication.At the outlet of the separation unit 45, the foam phase enriched in agent surfactant, broken in the unit 48 is then recycled in the silo 30 for the preparation of the manufacturing composition.

La phase liquide appauvrie en agent tensio-actif à la sortie de l'unité de séparation du liquide 45 est amenée par la conduite 56 à une unité de récupération de l'agent tensio-actif.The liquid phase depleted in surfactant at the outlet of the separation of the liquid 45 is brought via line 56 to a recovery unit for the surfactant.

On récupère également du liquide moussant lors de l'égouttage qui a lieu au cours de la fabrication de la nappe fibreuse, au niveau de la presse aspirante 16 ou encore de la caisse aspirante 84, au moyen d'un collecteur 82. Ce liquide moussant est ensuite alimenté dans l'unité de récupération du tensio-actif 55 au moyen de la conduite 86 qui rejoint la conduite 56 d'amenée de liquide moussant déjà appauvri en tensio-actif, provenant de l'unité de séparation du liquide 45.Foaming liquid is also recovered during the draining which takes place at during the manufacture of the fibrous web, at the suction press 16 or again from the suction box 84, by means of a collector 82. This foaming liquid is then fed into the surfactant recovery unit 55 by means of the line 86 which joins line 56 for supplying foaming liquid already depleted in surfactant, from the liquid separation unit 45.

L'unité 55 comprend des moyens spécifiques 60 pour introduire du gaz ou de l'air afin de générer de la mousse à partir du liquide moussant introduit dans cette unité de séparation 55.The unit 55 includes specific means 60 for introducing gas or air to generate foam from the foaming liquid introduced into this unit separation 55.

Ces moyens ou aérateurs 60 sont du type de ceux décrits dans la demande de brevet européen EP-A-0,481,746 au nom de JAMES RIVER CORPORATION OF VIRGINIA.These means or aerators 60 are of the type described in the request for European patent EP-A-0,481,746 in the name of JAMES RIVER CORPORATION OF VIRGINIA.

La mousse formée est récupérée par la conduite 64 et est brisée dans l'unité 65, puis l'agent tensio-actif est recyclé dans le silo 30 par la conduite 51.The foam formed is recovered by line 64 and is broken in unit 65, then the surfactant is recycled into the silo 30 via line 51.

Le liquide résultant encore plus appauvri en agent tensio-actif est récupéré dans la conduite 68 et peut être à nouveau traité par une autre unité de récupération 69 de l'agent tensio-actif, montée en série avec la première unité. Deux à six unités de récupération peuvent être montées en série.The resulting liquid, even more depleted of surfactant, is recovered in line 68 and can be treated again by another recovery unit 69 of the surfactant, mounted in series with the first unit. Two to six units of recovery can be mounted in series.

Le procédé selon l'invention suivant le mode de réalisation décrit ci-dessus, a été testé sur un appareil pilote à vitesse élevée.The method according to the invention according to the embodiment described above, has been tested on a high speed pilot device.

La machine a une configuration "crescent former".The machine has a "crescent former" configuration.

Une unité de récupération de l'agent tensio-actif a été mise en utilisation. Le liquide moussant récupéré lors de l'égouttage du feutre est envoyé dans l'unité de récupération de l'agent tensio-actif.A surfactant recovery unit has been used. The foaming liquid recovered when the felt is drained is sent to the recovery of the surfactant.

Dans un premier temps, on a vérifié que les agents tensio-actifs non-ioniques utilisés selon l'invention présentaient de bonnes performances dans le procédé en milieu mousse. First, it was verified that the nonionic surfactants used according to the invention exhibited good performance in the foam medium process.

On utilise pour ces essais, le WITCONOL® SN-120 comme agent tensio-actif non-ionique pour le procédé selon l'invention, et pour comparaison, le procédé en milieu eau, et le procédé en milieu mousse utilisant l'AOS. Différents taux de raffinage et différentes concentrations en KYMENE® 557 H, ont été testés dans les procédés en milieu mousse utilisant le WITCONOL® SN-120 et l'AOS. La concentration en WITCONOL® SN-120 dans la caisse de tête est d'environ 225 ppm.WITCONOL® SN-120 is used for these tests as surfactant non-ionic for the process according to the invention, and for comparison, the process water medium, and the foam medium process using AOS. Different refining rates and different concentrations of KYMENE® 557 H, have been tested in the processes in foam medium using WITCONOL® SN-120 and AOS. The concentration in WITCONOL® SN-120 in the headbox is around 225 ppm.

La mousse obtenue à partir du WITCONOL® SN-120 a un aspect identique à celle obtenue à partir de l'AOS, à partir d'un examen visuel de la taille des bulles.The foam obtained from WITCONOL® SN-120 has an identical appearance to that obtained from the AOS, from a visual examination of the size of the bubbles.

La formation de la feuille de papier dans le cas du procédé avec WITCONOL® SN-120 est similaire à celle de la feuille issue du procédé utilisant l'AOS.The formation of the sheet of paper in the case of the process with WITCONOL® SN-120 is similar to that of the sheet resulting from the process using the AOS.

Comme l'illustre la courbe de la figure 2 représentant la concentration en agent tensio-actif en fonction de la quantité de KYMENE® 557 H ajoutée par tonne de pâte pour la fabrication d'essuie-tout, on a pu vérifier qu'aucune interaction entre le WITCONOL® SN-120 et le KYMENE n'intervenait.As illustrated by the curve in Figure 2 representing the concentration of agent surfactant depending on the amount of KYMENE® 557 H added per ton of paste for the production of paper towels, we could verify that no interaction between the WITCONOL® SN-120 and KYMENE did not intervene.

En outre, des résistances sèches plus élevées ont été atteintes en utilisant le WITCONOL® SN-120 dans le procédé selon l'invention par rapport à l'AOS. Ceci est illustré par la courbe représentée en figure 3 où la force de résistance à la rupture de la feuille à l'état sec est fonction de la quantité de KYMENE® 557 H ajoutée par tonne de pâte.In addition, higher dry resistances were achieved using the WITCONOL® SN-120 in the process according to the invention compared to AOS. this is illustrated by the curve shown in Figure 3 where the tensile strength of the sheet in the dry state is a function of the amount of KYMENE® 557 H added per ton paste.

Les courbes de la figure 4 représentent la force de résistance humide en fonction de la quantité de KYMENE® 557 H ajoutée par tonne de pâte, pour différents agents tensio-actifs.The curves in Figure 4 represent the wet resistance force in depending on the amount of KYMENE® 557 H added per tonne of dough, for different surfactants.

On peut observer que la courbe de résistance humide en fonction de la quantité de KYMENE® 557 H ajoutée dans le procédé selon l'invention utilisant le WITCONOL® SN-120, est parallèle à la courbe de résistance humide dans le procédé en milieu eau. L'évolution de l'augmentation de résistance humide pour le procédé utilisant le WITCONOL® SN-120 est donc similaire à celle du procédé en milieu eau. Par contre, l'addition de KYMENE® 557 H ne procure bien sûr aucun gain en résistance humide dans le procédé utilisant l'AOS.We can observe that the wet resistance curve as a function of the quantity of KYMENE® 557 H added in the process according to the invention using the WITCONOL® SN-120, is parallel to the wet resistance curve in the process in water. The evolution of the increase in wet resistance for the process using WITCONOL® SN-120 is therefore similar to that of the process in water. On the other hand, the addition of KYMENE® 557 H obviously does not provide any gain in wet resistance in the process using AOS.

La vitesse d'absorption initiale en eau a été également comparée, en présence de 6 kg de KYMENE® 557 H par tonne de pâte. Comme le montrent les courbes de la figure 5 qui représentent la vitesse d'absorption initiale en eau en fonction d'une force de traction moyenne pour une feuille formée de 2 plis, la vitesse initiale d'absorption en eau est 25 % plus élevée pour la feuille préparée à partir du WITCONOL® SN-120 que pour la feuille préparée suivant le procédé en milieu eau.The initial water absorption rate was also compared, in the presence 6 kg of KYMENE® 557 H per tonne of dough. As the curves of FIG. 5 which represent the initial rate of absorption of water as a function of a average tensile force for a sheet formed by 2 plies, the initial speed water absorption is 25% higher for the sheet prepared from WITCONOL® SN-120 only for the sheet prepared according to the process in water medium.

Les essais réalisés sur l'appareil pilote ont donc montré que le procédé en milieu mousse suivant l'invention, utilisant le WITCONOL® SN-120, est non seulement aussi performant que le procédé utilisant l'AOS, mais procure des avantages supplémentaires et inattendus.The tests carried out on the pilot apparatus have therefore shown that the process foam medium according to the invention, using WITCONOL® SN-120, is not only as efficient as the OSA process, but provides benefits additional and unexpected.

Le procédé selon l'invention peut être mis en oeuvre suivant un autre mode de réalisation qui est une variante de celui appliqué sur l'appareil pilote, qui a été décrit précédemment.The method according to the invention can be implemented according to another mode of embodiment which is a variant of that applied to the pilot apparatus, which has been described previously.

Ce second mode de réalisation est illustré par le diagramme représenté en figure 6 et est décrit de manière détaillée dans le brevet américain US-A-5 200 035. Il diffère du premier mode de réalisation par les étapes de préparation de la composition de fabrication introduite dans la caisse de tête.This second embodiment is illustrated by the diagram shown in Figure 6 and is described in detail in US Patent US-A-5,200,035. It differs from the first embodiment by the stages of preparation of the composition of manufacturing introduced into the headbox.

En effet, la pâte à papier issue du château de pâte 100 diluée dans une solution aqueuse, est introduite dans une presse 101. Cette dernière concentre le mélange papetier en éliminant de l'eau. Le mélange concentré passe ensuite dans un déchiqueteur à aiguilles 102. Le liquide moussant provenant du silo 103 est également alimenté dans le déchiqueteur 102. Une dispersion moussante de fibres est ainsi formée et conduite dans une pompe à déplacement positif 104, puis dans la caisse de tête 105. Ce procédé élimine l'étape de traitement de l'excès de liquide récupéré dans le Bacholle, et permet donc de supprimer l'unité de séparation. Une autre conséquence de ce dispositif pour la réalisation du procédé en milieu mousse est la diminution de la taille de l'unité de récupération. En effet, dans le premier mode de réalisation décrit précédemment, généralement six unités de récupération sont montées en série. Or, suivant ce second mode de réalisation, trois unités de récupération de la mousse sont suffisantes.Indeed, the paper pulp from the pulp castle 100 diluted in a solution aqueous, is introduced into a press 101. The latter concentrates the mixture stationer by removing water. The concentrated mixture then passes into a needle shredder 102. The foaming liquid from silo 103 is also fed into the shredder 102. A foaming dispersion of fibers is thus formed and conducted in a positive displacement pump 104, then in the headbox 105. This process eliminates the step of processing the excess liquid recovered in the Bacholle, and therefore allows the separation unit to be eliminated. Another consequence of this device for carrying out the process in a foam medium is the reduction in the recovery unit size. Indeed, in the first embodiment described previously, generally six recovery units are connected in series. Gold, according to this second embodiment, three foam recovery units are sufficient.

On a mis en oeuvre à l'échelle industrielle le procédé selon l'invention suivant ce second mode de réalisation. On a mesuré certains paramètres de fabrication : consommation en agent tensio-actif, récupération de cet agent, etc... et on a pu observer des résultats avantageux.The process according to the invention has been implemented on an industrial scale this second embodiment. We measured certain manufacturing parameters: consumption of surfactant, recovery of this agent, etc ... and we were able to observe beneficial results.

On a réalisé des essais en utilisant comme agent tensio-actif le WITCONOL® SN-120, plus précisément une solution de WITCONOL® SN-120 active à 80 % (c'est-à-dire le mélange commercialisé sous la marque WITCONOL® SN-120D), pour le procédé selon l'invention, et l'AOS, plus précisément une solution d'AOS active à 40 %, pour le procédé témoin.Tests have been carried out using WITCONOL® as surfactant SN-120, more specifically a solution of WITCONOL® SN-120 active at 80% (i.e. the mixture sold under the brand WITCONOL® SN-120D), for the method according to the invention, and the AOS, more specifically an active AOS solution to 40%, for the control process.

On a comparé les consommations en agent tensio-actif pour le WITCONOL® SN-120D et l'AOS. Les résultats sont rapportés dans le tableau II ci-dessous.

Figure 00130001
We compared the surfactant consumption for WITCONOL® SN-120D and AOS. The results are reported in Table II below.
Figure 00130001

Une caractéristique avantageuse de l'invention apparaít à la lecture de ce tableau. La consommation en agent tensio-actif, ici de WITCONOL® SN-120D, pour maintenir la teneur en air dans l'intervalle souhaité, est plus faible que la consommation en AOS.An advantageous characteristic of the invention appears on reading this board. The consumption of surfactant, here from WITCONOL® SN-120D, to keep the air content in the desired range, is lower than consumption in OSA.

Du fait de la plus faible consommation en agent tensio-actif, dans le cas du WITCONOL® SN-120D, la charge à l'entrée de l'unité de récupération est nettement plus faible.Due to the lower consumption of surfactant, in the case of WITCONOL® SN-120D, the load at the inlet of the recovery unit is clearly weaker.

On a mesuré la récupération de l'agent tensio-actif WITCONOL® SN-120D que l'on a comparée à celle de l'AOS.WITCONOL® SN-120D surfactant recovery was measured that we compared to that of AOS.

Les résultats sont résumés dans le tableau III ci-dessous pour une teneur en air similaire.

Figure 00140001
The results are summarized in Table III below for a similar air content.
Figure 00140001

Il découle du tableau III qu'à consommation égale en agent tensio-actif, la récupération en WITCONOL® SN-120D est largement supérieure à celle de l'AOS dans les mêmes conditions.It follows from Table III that with equal consumption of surfactant, the recovery in WITCONOL® SN-120D is much higher than that of OSA under the same conditions.

Compte-tenu de cette bonne récupération en agent tensio-actif, il serait possible de supprimer avantageusement l'une des trois unités de récupération.Given this good recovery of surfactant, it would be it is possible to advantageously remove one of the three recovery units.

L'eau récupérée à la sortie des unités de récupération a une concentration en agent tensio-actif non-ionique de formule (I) tel que le WITCONOL® SN-120D, plus faible, au plus égale à environ 3 ppm et peut être alors rejetée ou réutilisée, n'ayant plus aucun caractère moussant. Cette caractéristique est importante au regard de la législation sur l'environnement.The water recovered at the outlet of the recovery units has a concentration of nonionic surfactant of formula (I) such as WITCONOL® SN-120D, plus low, at most equal to about 3 ppm and can then be rejected or reused, having no more foaming character. This characteristic is important with regard to the environmental legislation.

Par ailleurs, la concentration en agent tensio-actif résiduelle dans la feuille de papier pour le WITCONOL® SN-120D diminue de 65 % par rapport à celle des produits fabriqués à partir de l'AOS. Et lorsque du BEROL est incorporé dans la pâte au cours de la fabrication, la quantité fixée de ce composant dans la feuille dans le cas du procédé en milieu mousse selon l'invention, est tout à fait identique à celle fixée dans une feuille obtenue suivant le procédé en milieu eau.Furthermore, the concentration of residual surfactant in the sheet of paper for the WITCONOL® SN-120D decreases by 65% compared to that of products made from OSA. And when BEROL is incorporated into the dough during manufacture, the fixed amount of this component in the sheet in the case of the process in foam medium according to the invention, is completely identical to that fixed in a sheet obtained according to the process in water medium.

On a également remarqué que la substitution de l'AOS par le WITCONOL® SN-120D et vice-versa dans le procédé de fabrication, ne rencontraient pas de problèmes techniques. We also noticed that the substitution of AOS by WITCONOL® SN-120D and vice versa in the manufacturing process, did not meet any technical problems.

Enfin, les propriétés de la feuille de papier ont été mesurées sur des feuilles de papier toilette obtenues par le procédé selon l'invention utilisant du WITCONOL® SN-120D et le cas échéant, l'agent adoucissant BEROL. Ces feuilles de papier sont fabriquées industriellement, toujours suivant le second mode de réalisation décrit précédemment.Finally, the properties of the sheet of paper were measured on sheets of toilet paper obtained by the process according to the invention using WITCONOL® SN-120D and, if necessary, the softening agent BEROL. These sheets of paper are industrially manufactured, always according to the second embodiment described previously.

La propriété de douceur est appréciée par un test de mesure physique et parallèlement par un panel.The softness property is assessed by a physical measurement test and in parallel by a panel.

Une feuille de papier, produit fini, c'est-à-dire transformée, présentant une bonne douceur suivant ce test, obtient une notation qui doit se situer dans l'intervalle de 90 à 95. Or, les feuilles des bobines-mères avant transformation, obtenues suivant le procédé selon l'invention utilisant le WITCONOL® SN-120D, présentent une valeur de douceur élevée dans l'intervalle de 92 à 96. Les feuilles une fois transformées, présentent des valeurs améliorées de douceur entre 96 et 100.A sheet of paper, finished product, that is to say processed, having a good sweetness following this test, obtains a notation which must be in the interval from 90 to 95. However, the sheets of the mother reels before transformation, obtained according to process according to the invention using WITCONOL® SN-120D, have a value high sweetness in the range of 92 to 96. The leaves once transformed, have improved softness values between 96 and 100.

Lorsque l'on incorpore du BEROL dans la pâte, la feuille obtenue par le procédé présente une douceur encore plus élevée qui peut dépasser 100 pour les bobines-mères et le produit transformé.When incorporating BEROL into the dough, the sheet obtained by the process has an even higher softness which can exceed 100 for mother reels and the processed product.

Claims (6)

  1. Process for manufacturing a sheet of paper or of a non-woven in a foam medium, characterized in that the surface active agent for forming the foam is a mixture of ethoxylated alcohols having the general formula (I) R-(OCH2CH2)n-OH in which n is a whole number from 4 to 20, R is a linear alkyl group having 8 to 16 carbon atoms, ethoxylated alcohols having a linear alkyl group with 10, 12 and 14 carbon atoms being present in the mixture.
  2. Process according to claim 1, characterized in that the said ethoxylated alcohol mixture having a linear alkyl group with 10 carbon atoms is in the greater proportion.
  3. Process according to claim 1 or 2, characterized in that the distribution of ethoxylated alcohols as a function of the linear alkyl group is as follows:
    alkyl with C8 : 2.0 % maximum
    alkyl with C10 : 83-89 %
    alkyl with C12 : 5-9 %
    alkyl with C14 : 3-7 %
    alkyl with C16 : 0.5 % maximum.
  4. Process according to claim 1, characterized in that in the said mixture, the ethoxylated alcohol mixture having a linear alkyl group with 12 carbon atoms is in the greater proportion.
  5. Process according to one of the preceding claims, characterized in that it comprises the incorporation of cationic additives for the manufacture of paper such as softening agents, agents for improving wet strength, agents for improving dry strength and/or dispersing agents.
  6. Process according to claim 5, characterized in that the said cationic additive is a quaternary polyamine.
EP95908293A 1994-02-01 1995-02-01 Method for manufacturing paper or a non-woven web in a foam medium using a non-ionic surfactant Expired - Lifetime EP0742858B1 (en)

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FR9401085A FR2715671B1 (en) 1994-02-01 1994-02-01 Method of manufacturing a sheet of paper or nonwoven in a foam medium, using a nonionic surfactant.
FR9401085 1994-02-01
PCT/FR1995/000118 WO1995021299A1 (en) 1994-02-01 1995-02-01 Method for manufacturing paper in a foam medium using a non-ionic surfactant

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US11255051B2 (en) 2017-11-29 2022-02-22 Kimberly-Clark Worldwide, Inc. Fibrous sheet with improved properties
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ES2133733T3 (en) 1999-09-16
EP0742858A1 (en) 1996-11-20
FR2715671B1 (en) 1996-03-15
FR2715671A1 (en) 1995-08-04
US6103060A (en) 2000-08-15

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