EP1433898A1 - Feste und weiche Tissue- oder Vliesstoff- Bahnen aus hochgemahlenen zellulosischen Fasern - Google Patents

Feste und weiche Tissue- oder Vliesstoff- Bahnen aus hochgemahlenen zellulosischen Fasern Download PDF

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Publication number
EP1433898A1
EP1433898A1 EP02028783A EP02028783A EP1433898A1 EP 1433898 A1 EP1433898 A1 EP 1433898A1 EP 02028783 A EP02028783 A EP 02028783A EP 02028783 A EP02028783 A EP 02028783A EP 1433898 A1 EP1433898 A1 EP 1433898A1
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EP
European Patent Office
Prior art keywords
cellulose
fibres
polymer
water
fibrous web
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EP02028783A
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English (en)
French (fr)
Inventor
Dirk Mauler
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Essity Germany GmbH
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SCA Hygiene Products GmbH
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Publication date
Application filed by SCA Hygiene Products GmbH filed Critical SCA Hygiene Products GmbH
Priority to EP02028783A priority Critical patent/EP1433898A1/de
Priority to ES03813562T priority patent/ES2300661T3/es
Priority to EP03813562A priority patent/EP1583869B1/de
Priority to AU2003296627A priority patent/AU2003296627A1/en
Priority to AT03813562T priority patent/ATE387541T1/de
Priority to DE60319434T priority patent/DE60319434T2/de
Priority to PL03376004A priority patent/PL376004A1/xx
Priority to PCT/EP2003/013904 priority patent/WO2004057109A1/en
Publication of EP1433898A1 publication Critical patent/EP1433898A1/de
Withdrawn legal-status Critical Current

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    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • 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
    • D21H17/20—Macromolecular organic compounds
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • 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
    • D21H21/18—Reinforcing agents
    • D21H21/20—Wet strength agents
    • 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
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply

Definitions

  • the present invention relates to a soft and strong web, in particular tissue paper, which is prepared from highly refined cellulosic fibres to which specific chemical additives are given.
  • the present invention also pertains to a process for the manufacture of such web.
  • Cellulosic webs such as non-woven or paper tissue webs, find extensive use in modern society. Facial tissues, toilet tissues, kitchen paper or tissue handkerchiefs are staple items of commerce.
  • Tissue paper products are often exposed to extremely varied strength requirements in the wet and dry states. For instance, it must be ensured, in the case of household paper (kitchen towels) that they retain their strength at least for a specific period of time when exposed to aqueous liquids or moisture-containing food.
  • toilet paper should dissolve in water, some time after use, in order to prevent the sewage systems from clogging up. At the same time, toilet paper must not immediately use its strength properties during use for apparent reasons.
  • dry strength and wet strength properties the latter being divided in further categories such as initial wet strength, temporary wet strength and permanent wet strength depending on the point of time of measuring the wet strength after re-wetting a dry tissue paper.
  • a paper of an untreated cellulose-containing fibrous material usually looses 95% to 97% of its dry strength when saturated with water so that it normally cannot be used in the moistened or wet state. This is due to the fact that the paper develops dry strength as a result of inter-fibre hydrogen bonds which are broken up by water.
  • wet strength resins such as polyamidoamine-epichlorohydrine resin
  • polyamidoamine-epichlorohydrine resin is a widely known counter measure.
  • these resins are used alone, they typically lead to tissue paper which is fairly stiff and has almost the haptic properties of normal paper.
  • softeners such as the typically employed quaternary ammonium compounds, on the other hand, reduces the strength since softeners also interact with inter-fibre hydrogen bonds. Further, they can decrease the absorbency due to hydrophobic effects.
  • WO 00/39398 relates to chemically modified cellulosic materials that can have improved properties such as wet strength, softness or absorbency. This document discloses a process comprising:
  • the cationic additive is selected from the group consisting of a wet strength resin, a debonder, a softening agent, a dewatering aid and a sizing agent.
  • US 3,755,220 discloses soft cellulosic sheet materials having an improved ratio of wet tensile strength to dry tensile strength. This is achieved by including in the papermaking furnish at least one water-soluble, thermosetting cationic resin, such as polyamide-epichlorohydrin resin and at least one debonder including anionic and cationic surface active agents, in particular cationic, quaternary ammonium compounds.
  • at least one water-soluble, thermosetting cationic resin such as polyamide-epichlorohydrin resin
  • at least one debonder including anionic and cationic surface active agents, in particular cationic, quaternary ammonium compounds.
  • EP 0 672 787 A2 discloses pre-wettable high softness paper having temporary wet strength. According to the teaching of this document, temporary wet strength agents and cationic nitrogenous softeners are preferably combined.
  • US 5,573,637 discloses a multi-layered tissue paper product comprising a softener composition (quaternary ammonium compound and polysiloxane) and binders materials, either wet strength binders, such as polyamido-epichlorohydrine resins and/or dry strength binders such as carboxymethyl cellulose (CMC) where the majority of the softener composition is contained in the outer layers.
  • a softener composition quaternary ammonium compound and polysiloxane
  • binders materials either wet strength binders, such as polyamido-epichlorohydrine resins and/or dry strength binders such as carboxymethyl cellulose (CMC) where the majority of the softener composition is contained in the outer layers.
  • US 3,998,690 relates to a process for the preparation of fibrous assemblies such as paper having advantageous properties such as wet strength, absorbency, softness, good drape and enhanced bulk which exhibit compaction resistance.
  • the process for the preparation of these fibrous assemblies comprises the steps of
  • the cationic materials for the practice of this invention include quaternary ammonium compounds and common wet strength additives, such as aminopolyamide reaction products with epichlorohydrine.
  • Carboxymethyl cellulose is mentioned as one among many additives for anionically charging the fibres.
  • US 5,437,766 aims at providing soft, absorbent, lint resistant multiply-tissue paper products. For this purpose
  • the majority of the softener composition (biodegradable quaternary ammonium compound and polyhydroxy compound) is contained in the outer layers of the plies.
  • the inner layer is prepared from a gently refined NSK (northern softwood Kraft) fibre slurry to which 2% Kymene wet strength resin and 1% CMC were given.
  • NSK non softwood Kraft
  • the second slurry being intended for the outer layer is prepared from eucalyptus fibres which were treated with Kymene, CMC and a 1% solution of the above-explained chemical softener mixture.
  • the present invention relates to soft and strong cellulose-based fibrous web, in particular tissue paper, comprising
  • the webs obtained are distinguished by a high wet-strength and a suitable balance of other properties such as softness, dry strength, bulk and absorbency.
  • Figure 1 is a schematic drawing showing the creping process on a Yankee cylinder (9) with a creping blade.
  • Figure 1 gives a survey on the terminology used for the various angles influencing the creping process.
  • Figure 1 represents
  • cellulose-based fibrous web is used for planar assemblies comprising cellulosic fibres as disclosed below as major component, preferably in an amount of at least 70 weight%, based on the total fibre mixture. Contents of at least 80, or at least 90 weight % are even more preferred.
  • This cellulose-based fibrous web can, for instance, be a non-woven or a paper, for instance writing paper, packaging paper, filter paper or, in particular, a tissue paper.
  • the web may be one-ply or multiple-ply. Each ply may have more than one, typically two or three layers. If the web contains more than one ply, it is preferred that the highly refined fibres (a), the cationic polymer (b), the anionic polymer (c) and the softener (d) are combined in one ply. Where one ply contains more than one layer, it is preferred that highly refined fibres (a), the cationic polymer (b), the anionic polymer (c) and the softener (d) are combined in one layer. This does not exclude that one or more of chemicals (b), (c ) or (d) are also present in other plies or layers.
  • the invention in that ply or those plies which are primarily responsible for the overall strength of the multi-ply assembly while using for that outer ply or outer plies which come in contact with the skin of the user a ply distinguished by an even greater softness.
  • nonwoven As to the term “nonwoven” (German terms “Vlies” and “Vliesstoffe”), this is applied to a wide range of products which in terms of their properties are located between the groups of paper, paperboard, and cardboard on the one hand and the textile products on the other (see ISO 9092 - EN 29092).
  • the invention allows the application of known processes using aqueous slurries of cellulosic materials for producing nonwovens for instance by so-called “hydroentanglement”.
  • Nonwovens may also be called textile-like composite materials, which represent flexible porous fabrics that are not produced by the classic methods of weaving warp and weft or by looping, but by intertwining and/or by cohesive and/or adhesive bonding of fibres which may, for example, be present in the form of endless fibres or prefabricated fibres of a finite length, as synthetic fibres produced in situ or in the form of staple fibres.
  • the nonwovens according to the invention may thus consist of mixtures of synthetic fibres in the form of staple fibres (e.g. up to 30 % by weight based on the total fibre mixture) and cellulosic fibres treated according to the invention.
  • tissue production is counted among the paper making techniques.
  • the production of tissue is distinguished from paper production by its extremely low basis weight and its much higher tensile energy absorption index.
  • the total basis weight of multiple-ply tissue products preferably does not exceed 75 g/m 2 and more preferably is equal to a maximum of 45 g/m 2 .
  • the tensile energy absorption index is arrived at from the tensile energy absorption in which the tensile energy absorption is related to the test sample volume before inspection (length, width, thickness of sample between the clamps before tensile load). Paper and tissue paper also differ in general with regard to the modulus of elasticity that characterizes the stress-strain properties of these planar products as a material parameter.
  • a tissue's high tensile energy absorption index results from the outer or inner creping.
  • the former is produced by compression of the paper web adhering to a dry cylinder as a result of the action of a crepe doctor or in the latter instance as a result of a difference in speed between two wires ("fabrics"). This causes the still moist, plastically deformable paper web to be internally broken up by compression and shearing, thereby rendering it more stretchable under load than an uncreped paper.
  • a high tensile energy absorption index can also be achieved by imparting the tissue a 3D structure through the wires themselves. Most of the functional properties typical of tissue and tissue products result from the high tensile energy absorption index (see DIN EN 12625-4 and DIN EN 12625-5).
  • tissue paper as used herein covers the "raw tissue paper” as obtained from the tissue paper machine as well as one-ply or multi-ply final products (“tissue paper products”) made of raw tissue and tailored to the end user's needs by further converting steps.
  • tissue paper Typical properties include the ready ability to absorb tensile stress energy, their drapability, good textile-like flexibility, properties which are frequently referred to as bulk softness, a high surface softness, a high specific volume with a perceptible thickness, as high a liquid absorbency as possible and, depending on the application, a suitable wet and dry strength as well as an interesting visual appearance of the outer product surface.
  • tissue paper to be used, for example, as cleaning cloths, sanitary products (e.g. toilet paper), paper handkerchiefs, cosmetic wipes (facials) or as serviettes/napkins.
  • the cellulosic fibres to be used in the invention typically contain as main structure-building component the long chain fibrous cellulose portion which is present in naturally occurring cellulose-containing cells, in particular those of lignified plants.
  • the fibres are isolated from lignified plants by digestion steps removing or reducing the content of lignin and other extractables and optional bleaching steps.
  • the cellulosic fibres to be used may be of regenerated type (e.g. Lyocell), although the use of other types of pulps is preferred.
  • the pulps employed can be a primary fibrous material or a secondary fibrous material (recycled pulps).
  • the pulp can stem from lignin-free or low lignin sources, such as cotton linters, esparto (alfa) grass, bagasse (e.g. cereal straw, rice straw, bamboo, or hemp), kemp fibres or flax.
  • ligno-cellulosic material such as softwood (which typically originates from conifers) or hardwood (typically from deciduous trees).
  • “Chemical pulps” are, according to DIN 6730, fibrous materials obtained from plant raw materials of which most non-cellulosic components have been removed by chemical pulping without substantial mechanical post treatment.
  • “Mechanical pulp” is the general term for fibrous material made of wood entirely or almost entirely by mechanical means, optionally at increased temperatures. Mechanical pulp can be sub-divided into the purely mechanical pulps (groundwood pulp and refined mechanical pulp) as well as mechanical pulps subjected to chemical pre-treatment, such as chemo-mechanical pulp (CMP), or chemo-thermo mechanical pulp (CTMP).
  • CMP chemo-mechanical pulp
  • CTMP chemo-thermo mechanical pulp
  • the present inventors have found that the gentle refining (beating) of cellulosic fibrous materials to a freeness value of about 18-25°SR (all °SR freeness values mentioned herein are measured according to DIN-ISO 5267/1, March 1999) does not lead to sufficient wet strength, if further the typically used cationic wet strength resins, such as polyamidoamine-epichlorohydrine resins, are added to the fibrous materials. Without being bound to theory, it is believed that this may be due to the insufficient retention of the wet strength resin on the fibre surface.
  • the inventors have found that further increasing the degree of refinement and treating the resultant fibres with a suitable combination of additives as explained below increases the wet strength of the fibrous web, in particular tissue paper obtained, but simultaneously maintains a suitable balance of other properties.
  • the cellulosic fibres are refined to a freeness value of at least 27, more preferably at least 28, in particular at least 29°SR. Ranges of from 30 to 40, in particular 32 to 38°SR are even more preferred.
  • the cellulosic fibres to be used can represent a mixture of unrefined or gently refined fibres (about more than 15 to 26 °SR) and refined fibres (more than 26°SR) in accordance with the invention.
  • the present invention in the formation of multi-layered tissue paper by leading at least two different pulp streams, i.e. at least one of highly refined fibres treated according to the invention and at least one different pulp stream, to a multi-layered headbox.
  • the softer type of fibres for instance unrefined or gently refined hardwood fibres or unrefined or gently refined softwood fibres.
  • Unrefined fibres is used for fibres as naturally occurring or being obtained by their respective preparation process (chemical or mechanical pulping, recycling etc.). Unrefined fibres, typically have a freeness value of about 12 to 15°SR.
  • long fibres to be used are refined.
  • Long fibres typically stem from softwood (Gymnosperms) and have a fibre length in the range from 3.5 to 5.0 mm. They are normally pulped by Kraft processes. Preferred sources for the refined fibres are thus pine, spruce and Douglas fir.
  • the unrefined or gently refined fibres can be short fibres which generally stem from hardwood (Angiosperms) and have a size in the order from 1.0 to 2.0 mm. Hardwood is preferably pulped by sulfite processes. Preferred sources for the unrefined short fibres are eucalyptus, aspen or birch.
  • the unrefined or gently refined fibres can also stem from softwood, e.g. softwood like spruce digested by sulfite processes.
  • long refined fibres and gently refined or unrefined fibres are to be combined, be it in a single-layered ply as a true mixture or in multi-layered plies based on separate pulp streams, they are preferably used in a ratio of from 90/10 to 10/90, more preferably 80/20 to 20/80, most preferably from 75/25 to 40/60.
  • the water-soluble cationic polymer is preferably added to the cellulosic fibres in such an amount that 0.01 to 5 weight % , more preferably 0.01 to 3 weight %, in particular 0.5 to 2 weight % (e.g. 0.5 to 1.5 weight %), based on the total amount of untreated cellulosic fibres (dry weight, EN 20638:1993) is retained.
  • the cationic polymer to be used contains cationic groups, such as positively charged quaternary nitrogen atoms in sufficient amounts to impart the molecule water solubility.
  • water-soluble means solubility in water (at 20°C) of at least 1g/l, preferably at least 10g/l, in particular at least 20g/l.
  • the cationic water-soluble polymer is a wet strength agent. It can be selected from, but is not limited to urea-formaldehyde resins, melamine-formaldehyde resins, polyvinylamine, polyureide-formaldehyde resins, glyoxal-acrylamide resins and cationic materials obtained by the reaction of polyalkylene polyamines with polysaccharides such as starch and various natural gums, as well as 3-hydroxyazetidinium ion-containing resins, which are obtained by reacting nitrogen-containing polymers with epichlorohydrine.
  • urea-formaldehyde resins melamine-formaldehyde resins
  • polyvinylamine polyureide-formaldehyde resins
  • glyoxal-acrylamide resins glyoxal-acrylamide resins
  • cationic materials obtained by the reaction of polyalkylene polyamines with polysaccharides such as starch and various
  • the most preferred type of cationic polymer are 3-hydroxy azetidinium ion-containing resins. They include, but are not limited to, neutral or alkaline-curing thermosetting wet strength resins which can be selected from polyaminoamide-epichlorohydrine resins, polyamine-epichlorohydrine resins and aminopolymer-epichlorohydrine resins. In this context, explicit reference is made to a more detailed description of these wet strength agents in the section from column 2, line 43 to column 3, line 23 of US 5,316,623. Examples of these are the well known Kymene ® resins available from Hercules Inc. or EKA XP 4016 available from Eka Chemicals.
  • the water soluble anionic polymer is preferably added to the cellulosic fibres in such an amount that 0.01 to 3 weight %, more preferably 0.1 to 2 weight %, in particular 0.2 to 1 weight %, based on the total amount of untreated cellulosic fibres (dry weight according to DIN EN 20638) is retained by the fibres.
  • water-soluble anionic polymers we understand those polymers having a sufficient amount of anionic groups, preferably carboxy groups to be water soluble.
  • water-soluble means solubility in water (at 20°C) of at least 1g/l, preferably at least 10g/l in particular at least 20g/l.
  • the anionic polymer can be selected among known anionic dry strength agents.
  • the water soluble anionic polymer is preferably selected from polycarboxylic acids and anhydrides such as starch-based polymers, (meth)acrylic acid-derived polymers and copolymers, maleic-anhydride-derived copolymers, vinyl copolymers of carboxylic acids and cellulose-based polymers.
  • polyacrylates polymethacrylates, maleic anhydride-vinyl acetate polymers, polyvinylmethylether-maleic anhydride copolymers, methacrylic acid-acryl amide copolymers, isopropenyl acetate-maleic anhydride copolymers, itaconic acid-vinylacetate colpoymers, alpha-methyl styrene-maleic anhydride copolymers, styrene-maleic anhydride copolymers, methyl methacrylate-maleic anhydride copolymers, acrylic acid-styrene copolymers, carboxymethyl cellulose, succinic half esters of cellulose, graft polymerised polyacrylate-polyssacharide copolymers, succinic half esters of starch and oxidation products of the above-listed polyssacharides.
  • starch-based polymers vinyl copolymers of carboxylic acids and cellulose-based polymers are used.
  • carboxyalkylated polysaccharides in particular carboxyalkylated cellulose, is most preferred.
  • the water-soluble carboxyalkylated polysaccharides include carboxymethyl cellulose (CMC), carboxymethyl hydroxycellulose (CMHEC), carboxymethyl hydroxypropylcellulose (CMHPC), carboxymethylguar (CMG), carboxymethylated locust bean gum, carboxymethyl starch and the like, and their alkali metal salts or ammonium salts.
  • Carboxymethylated polyssacharides are available with various degrees of substitution (D.S.), defined as the average number of (carboxymethyl) substituents per anhydroglucose unit in the polyssacharide.
  • Carboxymethyl cellulose (CMC) is operable for use in the invention between D.S. about 0.4 (below which it is insoluble) to about 3.
  • the range D.S. about 0.6 to about 1.5 is preferred; that of about 0.7 to about 1.2 is more preferred.
  • Carboxymethylguar (CMG) between D.S. about 0.05 and about 2.0 is operable; preferred is the range about 0.1 to about 1.0, and more preferred is the range about 0.2 to about 0.5.
  • anionic polymers also include anionic polymers of acrylamide. These can be made by hydrolysis of an acrylamide polymer or copolymer by means known to the art, or by colpolymerising acrylamide with acrylic acid or sodium acrylate and optionally another monomer under radical initiation, again by means known to the art. Also operable are poly(acrylic acid) or its salts such as sodium polyacrylate or ammonium poylacrylate. Other operable polymers in this group are poly(acrylic acid) and its salts, and poly(sodium acrylate).
  • Anionic polyacrylamides are available in various molecular weight ranges, and with mole fractions of acrylic acid or acrylate salt per units between about 5 and about 70 mole percent. For convenience, those with weight-average molecular weights (Mw) below about 1 million are preferred.
  • Mw weight-average molecular weights
  • One suitable example is a polymer named Accostrength ® 86, produced by the American Cyanamid Company.
  • Preferred anionic polymers are those available commercially, having carboxyl (or carboxylate salt) contents of about 0.5 to about 14 millequivalents per gram. CMC is most preferred of all the polymers.
  • the above-explained water soluble cationic polymer is used in higher amounts than the water soluble anionic polymer.
  • the weight ratio cationic polymer/anionic polymer is from 1/1 to 10/1, more preferably 2/1 to 7/1, most preferably 3/1 to 5/1.
  • This type of softener (in the prior art sometimes referred to as debonder) is preferably added to the cellulosic fibres in such an amount that 0.005 to 3 weight %, more preferably 0.01 to 2.5 weight %, in particular 0.5 to 2 weight %, based on the total amount of untreated cellulosic fibres (dry weight according DIN EN 20638) are retained by the fibres.
  • the softener to be used has a smaller molecular weight than the above-explained anionic and cationic polymers. Whereas the latter preferably has molecular weights of at least 5000, in particular at least 10,000, preferred upper molecular weights for the softener are maximally 2,000, in particular maximally 1,000 (weight average molecular weight in each case).
  • the softener may be selected from quaternary ammonium compounds (e.g. quaternized protein compounds, silicone quaternaries or quaternized protein compounds) or cationic phopholipids of the type as described in WO 97/04171. All suitable surfactant-based softeners have the presence of a cationic unit (preferably quaternary ammonium unit) and a long chain aliphatic group having preferably 8 to 24, more preferably 14 to 22 carbon atoms in common. The long chain aliphatic group is preferably directly linked to the cationic group.
  • quaternary ammonium compounds e.g. quaternized protein compounds, silicone quaternaries or quaternized protein compounds
  • cationic phopholipids of the type as described in WO 97/04171. All suitable surfactant-based softeners have the presence of a cationic unit (preferably quaternary ammonium unit) and a long chain aliphatic group having preferably 8 to 24, more preferably 14 to 22 carbon
  • water-soluble or at least emulsifiable molecules it is preferred to use water-soluble or at least emulsifiable molecules.
  • the softener shows a solubility/emulsifiability in water (at 20°C) of at least 1g/l, preferably at least 10g/l in particular at least 20g/l.
  • the quaternary ammonium compounds include, but are not limited to, compounds of the following formula (I), (II), (III) or (IV):
  • R 1 , R 2 and X - have the following meanings:
  • X- is a compatible anion, such as halide (e.g. chloride or bromide) or methyl sulfate.
  • R 1 may also represent a mixture of alkyl groups derived from natural sources, such as "tallow”.
  • tallow is a naturally occurring material having a variable composition.
  • Table 6.13 in the above-identified reference edited by Swern indicates that typically 78% or more of the fatty acids of tallow contain 16 or 18 carbon atoms. Typically, half of the fatty acids present in tallow are unsaturated, primarily in the form of oleic acid. Synthetic as well as natural "tallows" fall within the scope of the present invention.
  • each R 1 is C16-C18 alkyl, most preferably each R 1 is straight-chain C18 alkyl.
  • Biodegradable mono and di-ester variations of the quaternary ammonium compound can also be used, and are meant to fall within the scope of the present invention.
  • These compounds preferably have the formulae (II), (III) or (IV) as follows: wherein each R 2 substituent is a C1-C6 alkyl or-hydroxyalkyl group, benzyl group or mixtures thereof; each R 1 substituent is a C12-C22 hydrocarbyl group, or substituted hydrocarbyl group or mixtures thereof, such as alkyl; each R 3 substituent is a C11-C21 hydrocarbyl group, or substituted hydrocarbyl, or substituted hydrocarbyl mixtures thereof, such as alkyl; Y is -O-C(O)-, -C(O)-O-, -NH-C(O)- or -C(O)-NH- or mixtures thereof, n is 1 to 4 and X- is suitable anion, for example, chloride, bromide,
  • substituents R 1 , R 2 and R 3 may optionally be substituted with various groups such as alkoxyl, hydroxyl, or can be branched.
  • each R 1 is C12-C18 alkyl and/or alkenyl, most preferably each R 1 is straight-chain C16-C18 alkyl and/or alkenyl.
  • each R 2 is methyl or hydroxylethyl.
  • each R 3 is C13-C17 alkyl and/or alkenyl, most preferably R 3 is straight-chain C15-C17 alkyl and/or alkenyl, and X - is chloride or methyl sulphate.
  • ester functional quaternary ammonium compounds can optionally contain up to about 10% of the mono(long chain alkyl) derivatives, e.g. (R 2 ) 2 -N + -((CH 2 ) 2 OH) ((CH 2 ) 2 OC(O)R 3 )X - as minor ingredients. These minor ingredients can act as emulsifiers and are useful in the present invention.
  • each R 2 is a C1-C6 alkyl or hydroxyalkyl group
  • R 3 is C11-C21 hydrocarbyl group
  • n is 2 to 4
  • X- is a suitable anion, such as an halide (e.g. chloride or bromide) or methyl sulphate.
  • each R 3 is C13-C17 alkyl and/or alkenyl, most preferably each R3 is straight-chain C15-C17 alkyl and/or alkenyl, and R 2 is a methyl.
  • Analysis of treatment chemicals herein retained on tissue paper webs can be performed by any method accepted in the applicable art.
  • the level of quaternary ammonium compound retained on the tissue paper can be determined by solvent extraction by an organic solvent followed by an anionic/cationic titration using Dimidium Bromide as indicator;
  • the level of wet strength resin, such as polyamido epichlorohydrin resin can be determined by subtraction from the total nitrogen level, as obtained via a nitrogen analyser, the amount of quaternary ammonium compound level, determined by the above titration method.
  • an indirect determination of the amount of wet strength resin retained by the tissue paper web can be performed by measuring adipic acid levels.
  • tissue paper web it is possible to determine the amount of treatment chemicals retained by the tissue paper web indirectly by measuring the amount remaining in the treatment solution after treatment and subtracting the same from the total amount used.
  • These methods are exemplary and are not meant to exclude other methods, which may be useful for determining levels of particular compounds retained by the tissue paper. Further, the applicable methods are to be determined according to the general knowledge of a skilled person for the individual system to be measured.
  • the present process for the preparation of a cellulose based fibrous web comprises the steps of:
  • the cellulosic fibrous material, the additives and their properties are preferably as described before.
  • the manufacture process comprises preferably the following steps:
  • the cellulosic material is transported to a refiner unit. Fibrillation of the fibres during refinement (beating) occurs either by the fibres themselves or by the refiner knives. During refinement, the fibres are subjected to a variety of physical loads. Axial and tangential shearing and compressive forces acting upon the fibre play a particular role as regards fibre refining.
  • the associate change in fibre morphology involves but is not limited to tearing open and removing the fibrous materials outer wall layer (primary wall) and/or exposing the fibres and fibrillation out of the wall layers and/or partially shorting the total fibre unit and/or shearing off fibrils.
  • fibres are shortened (cut) or fibrillated as stated above.
  • an operating mode leading to fibrillated fibres is preferred since it is believed to substantially increase the surface accessibility and the binding capacity of the fibres.
  • an aqueous slurry is produced therefrom.
  • the slurry preferably contains the cellulosic fibres in an amount of from 3 to 4 weight %, based on the water content.
  • this slurry is treated with the anionic and cationic water soluble polymer.
  • aqueous solutions are used for adding these chemicals but it is also possible to add them in substance.
  • the anionic polymer first (prior to the cationic polymer) in order to ensure an optimal interaction with the cellulosic fibres.
  • the cationic polymer is also given to the aqueous slurry. Again it is preferred to let a certain period of time pass (preferably from 1 to 30 min) before the aqueous slurry is conducted to the headbox and dewatered.
  • the third chemical, the cationic surfactant-based softener is preferably added (as solution or in substance) to the aqueous slurry.
  • all three chemicals are preferably added in an order and amounts ensuring a streaming current potential of white-water of the paper machine which ranges from -50 to -30 ⁇ eq/g.
  • TAD machines can for instance be run with a positive streaming current potential of white-water, e.g. +5 to + 20 ⁇ eq/g.
  • the streaming current potential is measured in a teflon-coated device equipped with an oscillating piston which shears off charges from the fiber surfaces being present in the white-water.
  • Such devices e.g. streaming current detector PCD 03 pH, available from Mütek Analytic GmbH, Germany
  • the procedure and requirements given by Mütek Analytic GmbH for detector PCD 03 pH are preferably to be followed.
  • aqueous slurries having pH-values in the order of 6,5 to 8, more preferably >7 to 7,5 to ensure an optimal interaction with the fibre surface.
  • the wet laying step and the further production steps are performed in line with methods known in the art.
  • tissue paper is to be made from the pulp according to the invention, the process essentially comprises:
  • Paper can be formed by placing the fibres, in an oriented or random manner, on one or between two continuously revolving wires of a paper making machine while simultaneously removing the main quantity of water of dilution until dry-solids contents of usually between 8 and 35 % are obtained.
  • the forming wire is often referred to in the art as a Fourdrinier wire.
  • a web Once the furnish is deposited on the forming wire, it is referred to as a web.
  • the web is dewatered by transferring to a dewatering felt, pressing the web and drying at elevated temperature.
  • the particular techniques and typical equipment for making webs according to the process just described are well known to those skilled in the art.
  • a low consistency pulp furnish is provided in a pressurized headbox.
  • the headbox has an opening for delivering a thin deposit of pulp furnish onto the Fourdrinier wire to form a wet web.
  • the web is then typically dewatered to a fibre consistency of between about 8% and about 35% (total web weight basis) by vacuum dewatering and further dewatered by pressing operations wherein the web is subjected to pressure developed by opposing mechanical members, for example, cylindrical rolls.
  • Drying the formed primary fibrous web occurs in one or more steps by mechanical and thermal means until a final dry-solids content of usually about 93 to 97 %.
  • this stage is followed by the crepe process which crucially influences the properties of the finished tissue product in conventional processes.
  • the conventional dry crepe process involves creping on a usually 4.5 to 6 m diameter drying cylinder, the so-called Yankee cylinder, by means of a crepe doctor with the aforementioned final dry-solids content of the raw tissue paper (wet creping can be used if lower demands are made of the tissue quality).
  • the creped, finally dry raw tissue paper (raw tissue) is then available for further processing into the tissue paper product according to the invention.
  • the set up angle (reference number (2) in Figure 1) is preferably determined to be from 10 to 35 °. For non-TAD processes values of 11 to 13° are typically employed. If TAD technology as explained below is used, the set up angle preferably ranges from 20 to 35°, in particular 22 to 30°.
  • the geometry of the doctor blade relative to the tissue surface may also have an impact of the properties of the product obtained.
  • thickness and relative wet strength may increase, when the grind angle is increased from 20° over 25° to 30°. This applies in particular to TAD processes as follows. As "grind angle” we understand the angle (1) given in Figure 1.
  • the invention gives preference to the use of a modified technique in which an improvement in specific volume is achieved by a special kind of drying within process section (c) and in this way an improvement in the bulk softness of the thus made tissue paper is achieved.
  • This process which exists in a variety of subtypes, is termed the TAD (through air drying) technique. It is characterized by the fact that the "primary" fibrous web that leaves the sheet making stage is pre-dried to a dry-solids content of e.g. about 80% before final contact drying on the yankee cylinder by blowing hot air through the fibrous web.
  • the fibrous web is supported by an air-permeable wire or belt and during its transport is guided over the surface of an air-permeable rotating cylinder drum. Structuring the supporting wire or belt makes it possible to produce any pattern of compressed zones broken up by deformation in the moist state, resulting in increased mean specific volumes and consequently leading to an increase in bulk softness without decisively decreasing the strength of the fibrous web.
  • Such a pattern is fixed in the area of the TAD-cylinder. Thereafter the pattern is further imprinted between the TAD-fabric and the Yankee-cylinder.
  • Creping may be conducted also during transfer of the paper sheet from the forming wire directly to the TAD-fabric or via a transfer fabric. For this creping the forming fabric runs faster than the following fabric receiving the sheet (rush transfer).
  • the so-called inner sheet-forming screen can thus be operated at a speed that is up to 40% faster than that of the next fabric or that of the subsequent felt, the initially formed and already pre-drained paper web being transferred to the next TAD fabric.
  • Another possible influence on the softness and strength of the raw tissue lies in the production of a layering in which the primary fibrous web to be formed is built up by a specially constructed headbox in the form of physically different layers of fibrous material, these layers being jointly supplied as a pulp strand to the sheet making stage.
  • the following procedural steps are normally used individually or in combination: cutting to size (longitudinally and/or cross cutting), producing a plurality of plies, producing chemical and/or mechanical (e.g. by embossing) ply adhesion, volumetric and structural embossing, folding, imprinting, perforating, application of lotions, smoothing, stacking, rolling up.
  • cutting to size longitudinally and/or cross cutting
  • producing a plurality of plies producing chemical and/or mechanical (e.g. by embossing) ply adhesion, volumetric and structural embossing, folding, imprinting, perforating, application of lotions, smoothing, stacking, rolling up.
  • an intermediate step preferably occurs with so-called doubling in which the raw tissue in the finished product's desired number of plies is usually gathered on a common multiply master roll.
  • the processing step from the raw tissue that has already been optionally wound up in several plies to the finished tissue product occurs in processing machines which include operations such as repeated smoothing of the tissue, edge embossing, to an extent combined with full area and/or local application of adhesive to produce ply adhesion of the individual plies (raw tissue) to be combined together, as well as longitudinal cut, folding, cross cut, placement and bringing together a plurality of individual tissues and their packaging as well as bringing them together to form larger surrounding packaging or bundles.
  • the individual paper ply webs can also be pre-embossed and then combined in a roll gap according to the foot-to-foot or nested methods.
  • test samples were conditioned over 12 hours at 50% relative humidity and 23 °C prior to testing.
  • the basis weight was determined according to DIN EN 12625-6.
  • the anisotropy was determined by dividing the dry breaking load value in machine direction(MD) through the dry breaking load value in cross direction (CD) as determined according to item 3.4 below.
  • the measurement is made by a precision micrometer (precision 0.001mm) according to a modified method based on EN 12625, part 3.
  • precision micrometer precision 0.001mm
  • the diameter of the pressure foot is 35,7 ⁇ 0.1 mm (10,0 cm 2 nominal area).
  • the pressure applied is 2,0 kPa ⁇ 0,1 kPa.
  • the pressure foot is movable at a speed rate of 2,0 ⁇ 0.2 mm/s.
  • a usable apparatus is a thickness meter type L & W 51D20 (available from Lorentzen & Wettre, US).
  • the paper to be measured i.e. two sheets of a single-ply or multi-ply paper are cut into pieces of 20x25 cm and conditioned in an atmosphere of 23°C, 50 % RH (Relative Humidity) for at least 18 hours.
  • the sheets are placed beneath the pressure plate which is then lowered.
  • the thickness value for the sheet is then read off 5 sec after the pressure value has stabilised.
  • the thickness measurement is then repeated four times with further samples treated in the same manner.
  • the mean value of the 5 values obtained is taken as thickness of the two sheets measured.
  • the dry strength was determined according to prEN 12625-4: 2001, Tissue Paper and Tissue Products, Part 4: Determination of width-related breaking strength, elongation at break and tensile energy absorption.
  • the wet strength was determined according to prEN ISO/FDIS 12625-5:2001(E) Tissue Paper and Tissue Products, Part 5: determination of wet tensile strength (CEN TC 172).
  • the samples to be tested were always artificially aged before conducting the tensile test. Aging was effected by heating the samples in an air-circulating drying cabinet to (125 ⁇ 1) °C for a period of 10 min.
  • the dry weight was determined according to DIN EN 20638 Pulp: determination of the dry-solids content (ISO 638: 1978); German version EN 20638:1993.
  • weight proportions (Kg/t) always refer to the amount of treated cellulosic fibres (dry weight).
  • a pilot scale TAD tissue paper making machine was used in the practice of the present invention.
  • an aqueous slurry of pine sulfate pulp (Grapho Celeste, available from SCA ⁇ strand) was refined at a consistency of 3 weight % to a freeness value of 35°SR in a conical refiner (available from Sunds Defibrator) operating at 78kWh/t.
  • Both furnish streams were further diluted at the fan pump to a consistency of about 0.1 weight %.
  • the highly refined furnish stream (35°SR) was treated with 0.9 Kg/t Berocell 596, a quaternary ammonium surfactant available from Akzo Nobel Chemicals GmbH, which was added to the inlet of the fan pump being installed shortly before the headbox.
  • the individually treated furnish streams were kept separate through the headbox and deposited onto a Fourdrinier wire to form a two layer embryonic web containing 70 weight % of the refined and treated pine sulfate pulp and 30 weight % of the unrefined treated sulfite pulp, respectively.
  • the web was adhered to the surface of the Yankee Cylinder by means of commercially available creping adhesives with the layer formed by sulfite pulp. After drying and creping, a single ply two layer raw tissue paper was obtained which has the properties shown in Table 1 below.
  • a single ply two layer tissue paper was produced in the same manner as set forth in example 1 apart from the following two differences.
  • the pine sulfate pulp was refined to a freeness value of 26°SR only. Further, no softener (Berocell 596) was added to the refined pine sulfate pulp and unrefined spruce sulfite pulp, respectively.
EP02028783A 2002-12-23 2002-12-23 Feste und weiche Tissue- oder Vliesstoff- Bahnen aus hochgemahlenen zellulosischen Fasern Withdrawn EP1433898A1 (de)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP02028783A EP1433898A1 (de) 2002-12-23 2002-12-23 Feste und weiche Tissue- oder Vliesstoff- Bahnen aus hochgemahlenen zellulosischen Fasern
ES03813562T ES2300661T3 (es) 2002-12-23 2003-12-08 Tejido suave y fuerte de fibras celulosicas altamente refinadas.
EP03813562A EP1583869B1 (de) 2002-12-23 2003-12-08 Weiche und belastbare vliese aus hochraffinierten cellulosefasern
AU2003296627A AU2003296627A1 (en) 2002-12-23 2003-12-08 Soft and strong webs from highly refined cellulosic fibres
AT03813562T ATE387541T1 (de) 2002-12-23 2003-12-08 Weiche und belastbare vliese aus hochraffinierten cellulosefasern
DE60319434T DE60319434T2 (de) 2002-12-23 2003-12-08 Weiche und belastbare vliese aus hochraffinierten cellulosefasern
PL03376004A PL376004A1 (en) 2002-12-23 2003-12-08 Soft and strong webs from highly refined cellulosic fibres
PCT/EP2003/013904 WO2004057109A1 (en) 2002-12-23 2003-12-08 Soft and strong webs from highly refined cellulosic fibres

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EP02028783A EP1433898A1 (de) 2002-12-23 2002-12-23 Feste und weiche Tissue- oder Vliesstoff- Bahnen aus hochgemahlenen zellulosischen Fasern

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EP03813562A Expired - Lifetime EP1583869B1 (de) 2002-12-23 2003-12-08 Weiche und belastbare vliese aus hochraffinierten cellulosefasern

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AU (1) AU2003296627A1 (de)
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CN101451330B (zh) * 2007-12-05 2010-12-15 杭州杭化播磨造纸化学品有限公司 无甲醛瓦楞纸板耐水增强剂及其制备工艺和应用
US20110048661A1 (en) * 2009-09-01 2011-03-03 Armstrong World Industries, Inc. Cellulosic product forming process and wet formed cellulosic product
WO2015070012A1 (en) * 2013-11-08 2015-05-14 Solenis Technologies, L.P. Surfactant based brown stock wash aid treatment for papermachine drainage and dry strength agents
WO2016027006A1 (en) * 2014-08-18 2016-02-25 Kemira Oyj Strength agent, its use and method for increasing strength properties of paper
WO2017103335A1 (en) * 2015-12-15 2017-06-22 Kemira Oyj Method for producing paper, board or the like
CN109891020A (zh) * 2016-10-27 2019-06-14 凯尔海姆纤维制品有限责任公司 人造纤维素纤维和包含纤维素纤维的非织造产品或织物
CN113529479A (zh) * 2014-10-06 2021-10-22 艺康美国股份有限公司 通过在含有淀粉的施胶压榨制剂中使用二烯丙基胺丙烯酰胺共聚物来提高纸块体强度的方法

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US9206555B2 (en) 2013-01-31 2015-12-08 Kimberly-Clark Worldwide, Inc. Tissue having high strength and low modulus
US8702905B1 (en) 2013-01-31 2014-04-22 Kimberly-Clark Worldwide, Inc. Tissue having high strength and low modulus
US8753751B1 (en) 2013-01-31 2014-06-17 Kimberly-Clark Worldwide, Inc. Absorbent tissue
US8834677B2 (en) 2013-01-31 2014-09-16 Kimberly-Clark Worldwide, Inc. Tissue having high improved cross-direction stretch
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CN106337313A (zh) * 2015-07-10 2017-01-18 谈旻轩 转印纸制造方法
JP6626375B2 (ja) * 2016-03-07 2019-12-25 花王株式会社 クレープ紙及びその製造方法、並びに吸収性物品の製造方法
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US10724173B2 (en) 2016-07-01 2020-07-28 Mercer International, Inc. Multi-density tissue towel products comprising high-aspect-ratio cellulose filaments
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CN101451330B (zh) * 2007-12-05 2010-12-15 杭州杭化播磨造纸化学品有限公司 无甲醛瓦楞纸板耐水增强剂及其制备工艺和应用
US20110048661A1 (en) * 2009-09-01 2011-03-03 Armstrong World Industries, Inc. Cellulosic product forming process and wet formed cellulosic product
US8741105B2 (en) * 2009-09-01 2014-06-03 Awi Licensing Company Cellulosic product forming process and wet formed cellulosic product
US9365977B2 (en) 2009-09-01 2016-06-14 Awi Licensing Llc Cellulosic product forming process and wet formed cellulosic product
US9598819B2 (en) 2013-11-08 2017-03-21 Solenis Technologies, L.P. Surfactant based brown stock wash aid treatment for papermachine drainage and dry strength agents
WO2015070012A1 (en) * 2013-11-08 2015-05-14 Solenis Technologies, L.P. Surfactant based brown stock wash aid treatment for papermachine drainage and dry strength agents
CN106574444B (zh) * 2014-08-18 2019-10-25 凯米罗总公司 强度剂以及其用于增强纸的强度性质的用途和方法
WO2016027006A1 (en) * 2014-08-18 2016-02-25 Kemira Oyj Strength agent, its use and method for increasing strength properties of paper
JP2017530264A (ja) * 2014-08-18 2017-10-12 ケミラ ユルキネン オサケイティエＫｅｍｉｒａ Ｏｙｊ 紙力剤、その使用方法及び紙の強度特性を高める方法
CN106574444A (zh) * 2014-08-18 2017-04-19 凯米罗总公司 强度剂以及其用于增强纸的强度性质的用途和方法
AU2015305047B2 (en) * 2014-08-18 2018-11-08 Kemira Oyj Strength agent, its use and method for increasing strength properties of paper
US10273634B2 (en) 2014-08-18 2019-04-30 Kemira Oyj Strength agent, its use and method for increasing strength properties of paper
RU2690362C2 (ru) * 2014-08-18 2019-05-31 Кемира Ойй Упрочняющее вещество, его применение и способ улучшения прочностных свойств бумаги
CN113529479A (zh) * 2014-10-06 2021-10-22 艺康美国股份有限公司 通过在含有淀粉的施胶压榨制剂中使用二烯丙基胺丙烯酰胺共聚物来提高纸块体强度的方法
CN108474181A (zh) * 2015-12-15 2018-08-31 凯米罗总公司 用于生产纸、纸板或类似物的方法
US10767312B2 (en) 2015-12-15 2020-09-08 Kemira Oyj Method for producing paper, board or the like
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WO2017103335A1 (en) * 2015-12-15 2017-06-22 Kemira Oyj Method for producing paper, board or the like
CN109891020A (zh) * 2016-10-27 2019-06-14 凯尔海姆纤维制品有限责任公司 人造纤维素纤维和包含纤维素纤维的非织造产品或织物
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EP1583869B1 (de) 2008-02-27
WO2004057109A1 (en) 2004-07-08
AU2003296627A1 (en) 2004-07-14
DE60319434D1 (de) 2008-04-10
DE60319434T2 (de) 2009-02-26
PL376004A1 (en) 2005-12-12
EP1583869A1 (de) 2005-10-12
ATE387541T1 (de) 2008-03-15
ES2300661T3 (es) 2008-06-16

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Effective date: 20041231