EP1765137B1 - Pick-up absorbent tissue paper - Google Patents
Pick-up absorbent tissue paper Download PDFInfo
- Publication number
- EP1765137B1 EP1765137B1 EP04739433A EP04739433A EP1765137B1 EP 1765137 B1 EP1765137 B1 EP 1765137B1 EP 04739433 A EP04739433 A EP 04739433A EP 04739433 A EP04739433 A EP 04739433A EP 1765137 B1 EP1765137 B1 EP 1765137B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tissue paper
- adhesive
- absorbent tissue
- absorbent
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
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Images
Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L25/00—Domestic cleaning devices not provided for in other groups of this subclass
- A47L25/005—Domestic cleaning devices not provided for in other groups of this subclass using adhesive or tacky surfaces to remove dirt, e.g. lint removers
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L13/00—Implements for cleaning floors, carpets, furniture, walls, or wall coverings
- A47L13/10—Scrubbing; Scouring; Cleaning; Polishing
- A47L13/16—Cloths; Pads; Sponges
Definitions
- the present invention relates to an absorbent tissue paper comprising an adhesive applied to at least a part of one surface of the tissue paper. However, it should cover not more than 80 % of such surface area which can be used to pick up particles from a smooth surface, especially in but not limited to the household area.
- the technical problem underlying the present invention is to provide an absorbent tissue paper improved in its ability to pick up particles from a smooth surface, but still providing the advantages of known absorbent tissue papers, in particular in view of liquid absorbency, such absorbent tissue papers still being storable as a roll or stacked one upon the other.
- Absorbent tissue papers such as household towels commonly available today are very well suited for the removal of drops or smaller wet areas on smooth surfaces such as boards or tables. However, the uptake of smaller solid particles such as sugar, bread crumbs or bits of paper is almost impossible.
- tissue paper In contrast to liquid substances, the absorption of solid particles into the absorbent tissue papers does not work. The only possibility for uptake into the tissue paper is mechanical, whereby the user tries to get a hold of the particles using the tissue paper.
- DE-A 199 55 795 discloses an adhesive cleaning wipe comprising a water soluble sheet developing an adhesive force when water is applied.
- this document does not disclose that an adhesive is applied to one surface of such cleaning wipe covering not more than 80 % of such surface area in order to enable storage of such cleaning wipes as a roll or by stacking one upon the other.
- US-A 3 981 741 relates to a fibrous cleaning material impregnated with a latex mixture, which, after addition of water, develops a significant ability to absorb dirt on the surface. This document is silent on teaching that not more than 80 % of the surface area of such cleaning material should be covered with an adhesive to enable storage of such cleaning material as a roll or by stacking.
- EP-B 829 222 discloses a web material comprising a tackifier, wherein the web is of non-woven material and the tackifier is applied within a range from 100 to 200 g/m 2 .
- the consistency of the adhesive layer or tackifier, respectively, is not suitable for use as absorbent tissue papers stacked one upon the other or, preferably, in rolls.
- US-A 5 198 292 also relates to a cleaning cloth of a non-woven, woven or knitted type containing an adhesive and a tackifier which are effective to remove dust from a wide variety of surfaces.
- this document does not relate to absorbent tissue papers like household towels, which are stacked or preferably rolled for storage, so that also this document does not provide hints regarding the quantity or type of adhesive layer.
- US-A-4 990 192 discloses absorbent paper towels onto which discrete adherent globules are sprayed without forming a continuous coating on the surface.
- cloth may be used instead of a paper towel, whereas face or toilet tissue is not desirable.
- absorbent tissue paper relates to a one, two or three ply absorbent tissue paper and also includes an absorbent tissue paper consisting of four, five, six or more plies being bonded together. Such absorbent tissue papers are normally used as household towels, facials, handkerchiefs or toilet papers.
- a tissue paper is defined as a soft absorbent paper having a low basis weight.
- the total basis weight of tissue products is preferably equal to a maximum of 70 g/m 2 , more preferably to a maximum of 65 g/m 2 .
- Its density is typically below 0.6 g/cm 3 , preferably below 0.30 g/cm 3 and more preferably between 0.08 and 0.20 g/cm 3 .
- tissue is distinguished from paper production by its lower basis weight and its much higher tensile energy absorption index (see DIN EN 12625-4 and DIN EN 12625-5). 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 ("rush transfer") 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.
- Moist tissue paper webs are usually dried by the so-called Yankee drying, the through air drying (TAD) or the impulse drying method.
- the starting material for the production of the tissue paper usually is a fibrous cellulosic material, in particular pulp. If, however, linters or cotton is used as raw material for the production of tissue paper, usually no further pulping steps are needed. Due to the morphological structure, the cellulose already exists in an open state.
- the starting pulps used may relate to primary fibrous materials (raw pulps) or to secondary fibrous materials, whereby a secondary fibrous material is defined as a fibrous raw material recovered from a recycling process.
- the primary fibrous materials may relate both to a chemically digested pulp and to mechanical pulp such as thermorefiner mechanical pulp (TMP), chemothermorefiner mechanical pulp (CTMP) or high temperature chemothermomechanical pulp (HTCTMP).
- TMP thermorefiner mechanical pulp
- CMP chemothermorefiner mechanical pulp
- HTCTMP high temperature chemothermomechanical pulp
- Synthetic cellulose-containing fibres can also be used. Preference is nevertheless given to the use of pulp from plant material, particularly wood-forming plants. Fibers of softwood (usually originating from conifers), hardwood (usually originating from deciduous trees) or from cotton linters can be used for example.
- Fibres from esparto (alfa) grass, bagasse (cereal straw, rice straw, bamboo, hemp), kemp fibers, flax, and other woody and cellulosic fiber sources can also be used as raw materials.
- the corresponding fiber source is chosen in accordance with the desired properties of the end products in a manner known from the prior art. For example, the fibers present in hardwood, which are shorter than those of softwood, lend the final product a higher stability on account of the higher diameter/length ratio. If softness of the product is to be promoted, which is important e.g. for tissue paper, eucalyptus wood is particularly suitable as a fiber source.
- chemical raw pulps are also preferred, whereby it is possible to use completely bleached, partially bleached, and unbleached fibers.
- the chemical raw pulps suitable according to the invention include inter alia, suphite pulps, kraft pulps (sulphate process).
- tissue paper it is also possible to use regenerated cellulosic fibers or synthetic fibers such as polyolefine fibers, polyester fibers or polyamide fibers, as a starting material for the production of tissue paper, enhancing for instance, strength, absorption, smoothness or softness of the tissue paper.
- the tissue paper according to the invention may also comprise a minor amount of non-wovens.
- the fibers can be treated with additives - such as fillers, softeners, such as quaternary ammonium compounds and binders, such as conventional dry-strength agents or wet-strength agents used to facilitate the original paper making or to adjust the properties thereof.
- additives such as fillers, softeners, such as quaternary ammonium compounds and binders, such as conventional dry-strength agents or wet-strength agents used to facilitate the original paper making or to adjust the properties thereof.
- the tissue manufacture process essentially comprises
- Paper can be formed by placing ("wet-laying") the fibers, 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 12 and 3 5 % are obtained.
- 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 %.
- tissue making 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 paper product or tissue paper product according to the invention.
- the invention also relates to the use of a modified technique in which an improvement in specific volume is achieved by a special kind of drying with process section b) 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 (like a nonwoven) that leaves the sheet making stage is pre-dried to a dry-solids content of 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.
- 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 mechanical (embossing, knurling) and/or chemical (adhesive) 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 multi-ply 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.
- the present invention can be employed for all different types of tissue paper products known in the art, such as handkerchiefs, facials, toilet paper, household towels or napkins, however household towels and napkins are preferably used.
- the absorbent tissue paper contains an adhesive applied to at least a part of its surface.
- an adhesive should be non-toxic.
- Compounds suitable as adhesives of the present invention include, but are not limited to, commonly available glue, e.g. based on starch or modified starch such as methyl cellulose, carboxylic methyl cellulose and adhesive polymers and polymers of synthetic resins, rubbers, polypropylene, polyisobutylene, polyurethane, polyacrylics, polyvinyl acetate and polyvinyl alcohol.
- Suitable adhesive polymers include, but are not limited to, block co-polymers containing polystyrene endblocks, and polyisoprene, polybutadiene, and/or poly ethylene-butylene midblocks: polyolefins such as polyethylene, polypropylene, amorphous polypropylene, polyisoprene, polyisobutylene and polyethylene propylene, ethylene-vinylacetate copolymers; poly(vinylethylene-co-1,4-butadiene); natural rubber (poly cis-isoprene); polyacrylic acids, preferably 2-ethylhexylacrylate and isooctylacrylate, and polymethacrylic acid or their salts; polydimethylsiloxane, polydiphenylsiloxane, poly methyl phenyl siloxane; polyvinyl acetate, polyvinyl alcohol; and mixtures thereof.
- polyolefins such as polyethylene,
- Adhesive polymers useful for the present invention can further include thermoplastic polymers such as A-B-A triblock copolymers, A-B diblock copolymers, A-B-A-B-A-B multiblock copolymers, radial block copolymers and grafted versions thereof; homopolymers, copolymers and terpolymers of ethylene; and homopolymers, copolymers and terpolymers of propylene; and mixtures thereof.
- Radial block copolymers include Y-block and star polymers as well as other configurations.
- the A-B-A block copolymers useful herein are those described in U.S. Pat. No. 4,136,699 , which is incorporated herein by reference.
- Examples include those polymers available under the Kraton TM G series from Shell Chemical Co. There are various grades available including Kraton TM G-1726, Kraton TM G-1650, Kraton TM G-1651, Kraton TM G-1652, Kraton TM G-1657, all saturated A-B diblock/A-B-A triblock mixtures with ethylene/butylenes midblocks; Kraton TM D-1112 a high percent A-B diblock linear styrene-isoprene-styrene polymer; Kraton TM D-1107 and Kraton TM D-1111, primarily A-B-A triblock linear styrene-isoprene-styrene block copolymers; Kraton TM D4433X, a linear styrene-isoprene-styrene "SIS" block copolymer with an oil content of 30% by weight and Kraton TM D1184, a high molecular weight
- Adhesive polymers include a substantially linear copolymer having the general configuration A-B-A wherein the A block can be polystyrene and the B block can be ethylene-butylene, ethylene-propylene, isoprene, butadiene or mixtures thereof, and preferably the B block is ethylene-butylene or ethylene-propylene.
- Adhesive polymers of this type such as Kraton TM G- from Shell Chemical Co., from Elf Atochem North America under the tradename of Lotryl TM including 35 BA 900 and 35 BA 1000; from Exxon Chemical Co. under the tradename of Escorene TM including XW-23.AH and XW-22.
- These adhesive polymers can also have to be used in small concentrations with some of the block copolymers such as Kraton TM G-1651.
- adhesive polymers include polyamides, polyesters, polyvinyl alcohol, polyvinyl pyrrolidone and copolymers thereof, polyurethanes; polystyrenes, polyepoxides; graft copolymers of vinyl monomers and polyalkylene oxide polymers and; aldehyde containing resins such as phenol-aldehyde, urea-aldehyde, melamine-aldehyde and the like.
- adhesive polymers are based on polymers having units derived from vinylamine compounds.
- adhesives are conventional adhesive components soluble and dispersable in water such as glutine, casein, starch (also in modified form), dextrine, or mixtures thereof.
- Suitable adhesives can also be formulated with so-called synthetic resins.
- resins include, among other materials, (a) natural and modified resins, (b) polyterpene resins, (c) phenolic modified hydrocarbon resins, (d) coumarone-indene resins, (e) aliphatic and aromatic petroleum hydrocarbon resins, (f) phthalate esters and (g) hydrogenated hydrocarbons, hydrogenated rosins, and hydrogenated rosin esters.
- the adhesive is being applied on the surface by initiating penetration of such adhesive from an inner layer through one outer ply to the surface of such outer ply under the influence of mechanical force, it is preferred to use a pressure sensitive adhesive.
- the pressure sensitive adhesive comprises an adhesive polymer that is an acrylic adhesive polymer selected from a wide variety of polymers and copolymers derived from acrylic and/or methacrylic acid, or ester, amide and nitrile derivatives thereof. Mixtures of different polymers and copolymers can be used.
- These polymers and copolymers preferably have a glass transition temperature (Tg) of less than about 0 so that the mass of polymer is tacky at ambient temperatures.
- Tg glass transition temperature
- acrylate-based adhesive polymers examples include homopolymers and copolymers comprising isooctylacrylate, 2-ethylhexylacrylate, isoamylacrylate, nonylacrylate and butylacrylate and their copolymers or terpolymers with acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile. It is also possible to incorporate nonpolar acrylic monomers whose homopolymers have a relatively high Tg such as, for example, isobornylacrylate (see, e. g., WO 95/13,331 and WO 95/13,328 ).
- Suitable pressure sensitive adhesives can optionally be formulated with synthetic resins in order to improve adhesion and introduce tack into the pressure sensitive adhesive, to achieve the adhesive characteristics desired herein.
- the adhesive is applied to at least a part of one surface of the absorbent tissue paper.
- the adhesive does cover not more than 80% , especially not more than 70%, preferably not more than 60 %, more preferably not more than 50% of such surface to enable storage of such absorbent tissue paper as a roll or by stacking.
- Such adhesives can be applied to the absorbent tissue paper e. g. as a so-called "hot melt", whereby the adhesive has to be heated up to its melt temperature or as an aqueous dispersion.
- Suitable aqueous dispersions comprising among others adhesives, surfactants, emulsifiers, humectants, stabilizers and other chemical agents.
- the adhesive to be applied on the surface of the absorbent tissue paper is used in an amount of up to 150 g/m 2 , especially in an amount of up to 120 g/m 2 preferably in an amount of up to 100 g/m 2 and more preferably in an amount of up to 80 g/m 2 .
- tissue paper it is possible to apply the adhesive to the surface of the tissue paper at any suitable point in time and place during or after manufacturing of such tissue paper.
- the adhesive after drying (and creping) on the Yankee cylinder in a paper machine.
- the application may take place during the doubling process of single tissue paper webs to multiply webs, as a process step in the converting machine, or as an extra step between doubling and converting.
- the adhesive can be applied on the surface of the tissue paper either by spraying or by coating wherein the term coating also includes applying one or a few tapes which are being coated with adhesives.
- the adhesive is either heated up to the melting point so that it will be transferred into a so called "hot melt” or the adhesive is applied in the form of an aqueous solution.
- the adhesive it is preferred that the finished tissue paper should be treated with the adhesive.
- the delivery of the adhesive by means of a spraying device should be adjusted to the product flow speed to ensure that a selected amount of adhesive is applied at the selected part of the tissue paper. This can be achieved e. g. by using a photo-eye detection of a certain area of the tissue paper whereby at a certain line a signal will be transferred to the spraying device thereby initiating a shot of a certain amount of adhesive.
- Applying the adhesive to the tissue paper can also be achieved by coating during of after manufacturing of such tissue paper using an offset-roll system. It is clearly preferred that applying the adhesive by means of an offset-roll system should be carried out after manufacturing of the tissue paper. In order to ensure that a selected amount of adhesive is placed in the desired area of the tissue paper, a photo-eye detection system controlling the drive of the offset rolls should be used.
- the adhesive is applied on a limited surface area of the tissue paper, whereby one part of such surface would be free from any adhesive, the other part would be covered by the adhesive and both parts would be separated from each other by a line.
- the surface area being covered with adhesive should comprise not more than 80% especially not more than 70%, preferably not more than 60%, and more preferably not more than 50% of the total surface area.
- the adhesive instead of applying the adhesive to a limited surface area of the tissue paper, the adhesive also can be applied in the form of discrete spots covering one surface of such tissue paper.
- discrete means that each adhesive spot would be clearly distinctable from other spots even though it may overlap with other adhesive spots.
- all adhesive spots should cover not more than 80%, especially not more than 60% and more preferably not more than 50% of the whole surface area of one outer ply.
- Such adhesive spots may be present on the surface in form of a grid or they may form an irregular pattern.
- the individual adhesive spots preferably have an area of 0.01 to 30 mm, more preferably 0.02 to 15 mm 2 , even more preferably 0.02 to 10 mm 2 , in particular 0.02 to 6 mm 2 .
- a process for the manufacture of such an absorbent tissue paper comprises the step of applying an adhesive to at least a part of one surface of the absorbent tissue paper.
- Such process is characterized by the fact that not more than 80% of such surface area is covered with the adhesive and that the adhesive is applied on the surface either by spraying or by coating or by printing during or after manufacturing of such absorbent tissue paper.
- the adhesive used should be sticky enough to enable picking up of larger crumbs when the tissue paper is placed on the smooth surface.
- the adhesive strength should be not too large so that the consumer can easily remove the tissue paper from the smooth surface and that the tissue paper can still be stored as a roll or stacked upon one another and subsequently be separated for use.
- the absorbent tissue paper according to the present invention is especially useful for picking up solid particles such as sugar, bread crumbs, bits of paper or other solid wastes.
- the present invention is a very interesting alternative for table vacuum cleaners and brushes, it makes shaking out of table cloth unnecessary and thus contributes to making household work easier.
- tissue papers developed according to the present invention can be used inter alia as handkerchiefs, napkins, facials or toilet papers. However there is a clear preference that these tissue papers are specially useful as household towels.
- the bottom side (b) of a household towel is coated with adhesive spots, thereby forming a grid-like pattern.
- (a) relates to the top side of the household towel.
- Figure 4 relates to a spraying device for applying an adhesive to a tissue paper according to the present invention comprising a photo-eye detector (a), a hot-melt applicator (b) and several rolls (c).
- (d) represents the product flow
- (e) indicates the adhesive areas of the tissue papers
- (f) represents the perforation lines of the tissue papers.
- Figure 5 shows a so-called contact application device for applying an adhesive to a tissue paper according to the present invention comprising an offset-roll system (a), a photo-eye detector (b) and several rolls (c).
- the product flow is represented by (d) and (e) indicates the adhesive areas of the tissue papers.
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Abstract
Description
- The present invention relates to an absorbent tissue paper comprising an adhesive applied to at least a part of one surface of the tissue paper. However, it should cover not more than 80 % of such surface area which can be used to pick up particles from a smooth surface, especially in but not limited to the household area.
- The technical problem underlying the present invention is to provide an absorbent tissue paper improved in its ability to pick up particles from a smooth surface, but still providing the advantages of known absorbent tissue papers, in particular in view of liquid absorbency, such absorbent tissue papers still being storable as a roll or stacked one upon the other.
- Absorbent tissue papers such as household towels commonly available today are very well suited for the removal of drops or smaller wet areas on smooth surfaces such as boards or tables. However, the uptake of smaller solid particles such as sugar, bread crumbs or bits of paper is almost impossible.
- In contrast to liquid substances, the absorption of solid particles into the absorbent tissue papers does not work. The only possibility for uptake into the tissue paper is mechanical, whereby the user tries to get a hold of the particles using the tissue paper.
- In case of several bread crumbs distributed across a table, however, there is a considerable risk that the particles picked up first will fall out again. Sometimes, the desired effect is achieved using a moist tissue paper. However, there is no guarantee for this and the outcome will not be perfect in most cases. Some materials will stick to the tissue paper owing to the moisture, but the adhesive force is often not sufficient.
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DE-A 199 55 795 discloses an adhesive cleaning wipe comprising a water soluble sheet developing an adhesive force when water is applied. However, this document does not disclose that an adhesive is applied to one surface of such cleaning wipe covering not more than 80 % of such surface area in order to enable storage of such cleaning wipes as a roll or by stacking one upon the other. -
US-A 3 981 741 relates to a fibrous cleaning material impregnated with a latex mixture, which, after addition of water, develops a significant ability to absorb dirt on the surface. This document is silent on teaching that not more than 80 % of the surface area of such cleaning material should be covered with an adhesive to enable storage of such cleaning material as a roll or by stacking. -
EP-B 829 222 - However, in order to stack the cut web material, a liner material is necessary, which is placed between two pads so as to prevent the pads adhering to each other.
- Consequently, the consistency of the adhesive layer or tackifier, respectively, is not suitable for use as absorbent tissue papers stacked one upon the other or, preferably, in rolls.
-
US-A 5 198 292 also relates to a cleaning cloth of a non-woven, woven or knitted type containing an adhesive and a tackifier which are effective to remove dust from a wide variety of surfaces. However, this document does not relate to absorbent tissue papers like household towels, which are stacked or preferably rolled for storage, so that also this document does not provide hints regarding the quantity or type of adhesive layer. -
US-A-4 990 192 discloses absorbent paper towels onto which discrete adherent globules are sprayed without forming a continuous coating on the surface. Alternatively cloth may used instead of a paper towel, whereas face or toilet tissue is not desirable. - It is one object of the present invention to provide an absorbent tissue paper, especially an absorbent household paper, capable of picking up small solid particles such as sugar, bread crumbs or bits of paper.
- It is a further technical object of the present invention to enable that such absorbent tissue papers capable of picking up small solid particles can be stored as a roll or stacked one upon the other.
- The above-mentioned technical objects are solved by an absorbent tissue paper comprising the features of claim 1. Embodiments are named in the dependent claims.
- The term "absorbent tissue paper" relates to a one, two or three ply absorbent tissue paper and also includes an absorbent tissue paper consisting of four, five, six or more plies being bonded together. Such absorbent tissue papers are normally used as household towels, facials, handkerchiefs or toilet papers.
- A tissue paper is defined as a soft absorbent paper having a low basis weight. One generally selects a basis weight of 8 to 40 g/m2, preferably 8 to 30 g/m2, especially 10 to 25 g/m2 per ply. The total basis weight of tissue products is preferably equal to a maximum of 70 g/m2, more preferably to a maximum of 65 g/m2. Its density is typically below 0.6 g/cm3, preferably below 0.30 g/cm3 and more preferably between 0.08 and 0.20 g/cm3 .
- The production of tissue is distinguished from paper production by its lower basis weight and its much higher tensile energy absorption index (see DIN EN 12625-4 and DIN EN 12625-5). 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 ("rush transfer") 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. Moist tissue paper webs are usually dried by the so-called Yankee drying, the through air drying (TAD) or the impulse drying method.
- The starting material for the production of the tissue paper usually is a fibrous cellulosic material, in particular pulp. If, however, linters or cotton is used as raw material for the production of tissue paper, usually no further pulping steps are needed. Due to the morphological structure, the cellulose already exists in an open state.
- The starting pulps used may relate to primary fibrous materials (raw pulps) or to secondary fibrous materials, whereby a secondary fibrous material is defined as a fibrous raw material recovered from a recycling process. The primary fibrous materials may relate both to a chemically digested pulp and to mechanical pulp such as thermorefiner mechanical pulp (TMP), chemothermorefiner mechanical pulp (CTMP) or high temperature chemothermomechanical pulp (HTCTMP). Synthetic cellulose-containing fibres can also be used. Preference is nevertheless given to the use of pulp from plant material, particularly wood-forming plants. Fibers of softwood (usually originating from conifers), hardwood (usually originating from deciduous trees) or from cotton linters can be used for example. Fibres from esparto (alfa) grass, bagasse (cereal straw, rice straw, bamboo, hemp), kemp fibers, flax, and other woody and cellulosic fiber sources can also be used as raw materials. The corresponding fiber source is chosen in accordance with the desired properties of the end products in a manner known from the prior art. For example, the fibers present in hardwood, which are shorter than those of softwood, lend the final product a higher stability on account of the higher diameter/length ratio. If softness of the product is to be promoted, which is important e.g. for tissue paper, eucalyptus wood is particularly suitable as a fiber source.
- With regard to softness of the products, the use of chemical raw pulps is also preferred, whereby it is possible to use completely bleached, partially bleached, and unbleached fibers. The chemical raw pulps suitable according to the invention include inter alia, suphite pulps, kraft pulps (sulphate process).
- It is also possible to use regenerated cellulosic fibers or synthetic fibers such as polyolefine fibers, polyester fibers or polyamide fibers, as a starting material for the production of tissue paper, enhancing for instance, strength, absorption, smoothness or softness of the tissue paper. The tissue paper according to the invention may also comprise a minor amount of non-wovens.
- The fibers can be treated with additives - such as fillers, softeners, such as quaternary ammonium compounds and binders, such as conventional dry-strength agents or wet-strength agents used to facilitate the original paper making or to adjust the properties thereof.
- The tissue manufacture process essentially comprises
- a) forming that includes the headbox and the wire portion,
- b) the drying portion (TAD (through air drying)) or conventional drying on the yankee cylinder) that also usually includes the crepe process essential for tissues,
- c) typically the monitoring and winding area.
- Paper can be formed by placing ("wet-laying") the fibers, 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 12 and 3 5 % are obtained.
- 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 %. In the case of tissue making, 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 paper product or tissue paper product according to the invention.
- Instead of the conventional tissue making process described above, the invention also relates to the use of a modified technique in which an improvement in specific volume is achieved by a special kind of drying with process section b) 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 (like a nonwoven) that leaves the sheet making stage is pre-dried to a dry-solids content of 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.
- 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. When processing the raw fibrous web or raw tissue paper into the final product ("converting"), 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 mechanical (embossing, knurling) and/or chemical (adhesive) ply adhesion, volumetric and structural embossing, folding, imprinting, perforating, application of lotions, smoothing, stacking, rolling up.
- To produce multi-ply tissue paper products, such as handkerchiefs, toilet paper, facials, towels or household towels, 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 multi-ply 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.
- The present invention can be employed for all different types of tissue paper products known in the art, such as handkerchiefs, facials, toilet paper, household towels or napkins, however household towels and napkins are preferably used.
- According to the present invention the absorbent tissue paper contains an adhesive applied to at least a part of its surface. Such an adhesive should be non-toxic. Compounds suitable as adhesives of the present invention include, but are not limited to, commonly available glue, e.g. based on starch or modified starch such as methyl cellulose, carboxylic methyl cellulose and adhesive polymers and polymers of synthetic resins, rubbers, polypropylene, polyisobutylene, polyurethane, polyacrylics, polyvinyl acetate and polyvinyl alcohol.
- Suitable adhesive polymers include, but are not limited to, block co-polymers containing polystyrene endblocks, and polyisoprene, polybutadiene, and/or poly ethylene-butylene midblocks: polyolefins such as polyethylene, polypropylene, amorphous polypropylene, polyisoprene, polyisobutylene and polyethylene propylene, ethylene-vinylacetate copolymers; poly(vinylethylene-co-1,4-butadiene); natural rubber (poly cis-isoprene); polyacrylic acids, preferably 2-ethylhexylacrylate and isooctylacrylate, and polymethacrylic acid or their salts; polydimethylsiloxane, polydiphenylsiloxane, poly methyl phenyl siloxane; polyvinyl acetate, polyvinyl alcohol; and mixtures thereof.
- Adhesive polymers useful for the present invention can further include thermoplastic polymers such as A-B-A triblock copolymers, A-B diblock copolymers, A-B-A-B-A-B multiblock copolymers, radial block copolymers and grafted versions thereof; homopolymers, copolymers and terpolymers of ethylene; and homopolymers, copolymers and terpolymers of propylene; and mixtures thereof. Radial block copolymers include Y-block and star polymers as well as other configurations. The A-B-A block copolymers useful herein are those described in
U.S. Pat. No. 4,136,699 , which is incorporated herein by reference. Examples include those polymers available under the Kraton™ G series from Shell Chemical Co. There are various grades available including Kraton™ G-1726, Kraton™ G-1650, Kraton™ G-1651, Kraton ™ G-1652, Kraton™ G-1657, all saturated A-B diblock/A-B-A triblock mixtures with ethylene/butylenes midblocks; Kraton™ D-1112 a high percent A-B diblock linear styrene-isoprene-styrene polymer; Kraton™ D-1107 and Kraton™ D-1111, primarily A-B-A triblock linear styrene-isoprene-styrene block copolymers; Kraton™ D4433X, a linear styrene-isoprene-styrene "SIS" block copolymer with an oil content of 30% by weight and Kraton™ D1184, a high molecular weight styrene-butadienestyrene "SBS" block copolymer both available from Shell Chemical Co.; Stereon™ 840A and Stereon™ 841A, A-B-A-B-A-B multiblock SBS block copolymers available from Firestone; Europrene™ Sol T-193B, a linear SIS block copolymer available from Enichem Elastomers; Europrene™ Sol T-190, a linear styrene-isoprene-styrene block copolymer and Europrene™ Sol T-163, a radial SBS block copolymer both also available from Enichem Elastomers; VectorTM 4461-D, a linear SBS block copolymer available from Exxon Chemical Co.; VectorTM 4111, 4211 and 4411, fully coupled linear SIS block copolymers containing different weight percentages of styrene endblock; and VectorTM 4113, a highly coupled linear SIS block copolymer also available from Exxon Chemical Co.; and DPX-550, DPX-551 and DPX-552 radial SIS block copolymers available from Dexco Polymers. This list is not exclusive and there are numerous grades of block copolymers available from various sources for such adhesives, especially so called hot melt adhesives. These polymers may be used alone, or in any combinations. - Other adhesive polymers include a substantially linear copolymer having the general configuration A-B-A wherein the A block can be polystyrene and the B block can be ethylene-butylene, ethylene-propylene, isoprene, butadiene or mixtures thereof, and preferably the B block is ethylene-butylene or ethylene-propylene. Adhesive polymers of this type, such as Kraton ™ G- from Shell Chemical Co., from Elf Atochem North America under the tradename of Lotryl™ including 35 BA 900 and 35 BA 1000; from Exxon Chemical Co. under the tradename of Escorene™ including XW-23.AH and XW-22. These adhesive polymers can also have to be used in small concentrations with some of the block copolymers such as Kraton™ G-1651.
- Other adhesive polymers include polyamides, polyesters, polyvinyl alcohol, polyvinyl pyrrolidone and copolymers thereof, polyurethanes; polystyrenes, polyepoxides; graft copolymers of vinyl monomers and polyalkylene oxide polymers and; aldehyde containing resins such as phenol-aldehyde, urea-aldehyde, melamine-aldehyde and the like.
- Further suitable adhesive polymers are based on polymers having units derived from vinylamine compounds.
- Other components which can be used as adhesives are conventional adhesive components soluble and dispersable in water such as glutine, casein, starch (also in modified form), dextrine, or mixtures thereof.
- Suitable adhesives can also be formulated with so-called synthetic resins. Such resins include, among other materials, (a) natural and modified resins, (b) polyterpene resins, (c) phenolic modified hydrocarbon resins, (d) coumarone-indene resins, (e) aliphatic and aromatic petroleum hydrocarbon resins, (f) phthalate esters and (g) hydrogenated hydrocarbons, hydrogenated rosins, and hydrogenated rosin esters.
- In case that the adhesive is being applied on the surface by initiating penetration of such adhesive from an inner layer through one outer ply to the surface of such outer ply under the influence of mechanical force, it is preferred to use a pressure sensitive adhesive.
- In a preferred embodiment, the pressure sensitive adhesive comprises an adhesive polymer that is an acrylic adhesive polymer selected from a wide variety of polymers and copolymers derived from acrylic and/or methacrylic acid, or ester, amide and nitrile derivatives thereof. Mixtures of different polymers and copolymers can be used.
- These polymers and copolymers preferably have a glass transition temperature (Tg) of less than about 0 so that the mass of polymer is tacky at ambient temperatures.
- Examples of useful acrylate-based adhesive polymers include homopolymers and copolymers comprising isooctylacrylate, 2-ethylhexylacrylate, isoamylacrylate, nonylacrylate and butylacrylate and their copolymers or terpolymers with acrylic acid, methacrylic acid, acrylamide, methacrylamide, acrylonitrile and methacrylonitrile. It is also possible to incorporate nonpolar acrylic monomers whose homopolymers have a relatively high Tg such as, for example, isobornylacrylate (see, e. g.,
WO 95/13,331 WO 95/13,328 - Suitable pressure sensitive adhesives can optionally be formulated with synthetic resins in order to improve adhesion and introduce tack into the pressure sensitive adhesive, to achieve the adhesive characteristics desired herein.
- According to the present invention, the adhesive is applied to at least a part of one surface of the absorbent tissue paper. However, the adhesive does cover not more than 80% , especially not more than 70%, preferably not more than 60 %, more preferably not more than 50% of such surface to enable storage of such absorbent tissue paper as a roll or by stacking.
- Such adhesives can be applied to the absorbent tissue paper e. g. as a so-called "hot melt", whereby the adhesive has to be heated up to its melt temperature or as an aqueous dispersion. Suitable aqueous dispersions comprising among others adhesives, surfactants, emulsifiers, humectants, stabilizers and other chemical agents.
- The adhesive to be applied on the surface of the absorbent tissue paper is used in an amount of up to 150 g/m2, especially in an amount of up to 120 g/m2 preferably in an amount of up to 100 g/m2 and more preferably in an amount of up to 80 g/m2.
- Generally it is possible to apply the adhesive to the surface of the tissue paper at any suitable point in time and place during or after manufacturing of such tissue paper.
- However it is clearly preferred to apply the adhesive after drying (and creping) on the Yankee cylinder in a paper machine. Thus, the application may take place during the doubling process of single tissue paper webs to multiply webs, as a process step in the converting machine, or as an extra step between doubling and converting.
- The adhesive can be applied on the surface of the tissue paper either by spraying or by coating wherein the term coating also includes applying one or a few tapes which are being coated with adhesives.
- However, it is also possible to use printing techniques such as the rotogravure printing technique or the flexographic printing technique for applying the adhesive to the tissue paper.
- In case that the spraying technique is used the adhesive is either heated up to the melting point so that it will be transferred into a so called "hot melt" or the adhesive is applied in the form of an aqueous solution. Although it is possible to apply the adhesive during manufacturing of the tissue paper, it is preferred that the finished tissue paper should be treated with the adhesive. The delivery of the adhesive by means of a spraying device should be adjusted to the product flow speed to ensure that a selected amount of adhesive is applied at the selected part of the tissue paper. This can be achieved e. g. by using a photo-eye detection of a certain area of the tissue paper whereby at a certain line a signal will be transferred to the spraying device thereby initiating a shot of a certain amount of adhesive.
- Applying the adhesive to the tissue paper can also be achieved by coating during of after manufacturing of such tissue paper using an offset-roll system. It is clearly preferred that applying the adhesive by means of an offset-roll system should be carried out after manufacturing of the tissue paper. In order to ensure that a selected amount of adhesive is placed in the desired area of the tissue paper, a photo-eye detection system controlling the drive of the offset rolls should be used.
- According to the present invention, it is possible that the adhesive is applied on a limited surface area of the tissue paper, whereby one part of such surface would be free from any adhesive, the other part would be covered by the adhesive and both parts would be separated from each other by a line. In order to ensure that the consumer can easily remove such tissue paper from the smooth area, the surface area being covered with adhesive should comprise not more than 80% especially not more than 70%, preferably not more than 60%, and more preferably not more than 50% of the total surface area.
- Instead of applying the adhesive to a limited surface area of the tissue paper, the adhesive also can be applied in the form of discrete spots covering one surface of such tissue paper. The term "discrete" means that each adhesive spot would be clearly distinctable from other spots even though it may overlap with other adhesive spots.
- Preferably all adhesive spots, if taken together, should cover not more than 80%, especially not more than 60% and more preferably not more than 50% of the whole surface area of one outer ply. Such adhesive spots may be present on the surface in form of a grid or they may form an irregular pattern. The individual adhesive spots preferably have an area of 0.01 to 30 mm, more preferably 0.02 to 15 mm2, even more preferably 0.02 to 10 mm2, in particular 0.02 to 6 mm2.
- A process for the manufacture of such an absorbent tissue paper comprises the step of applying an adhesive to at least a part of one surface of the absorbent tissue paper. Such process is characterized by the fact that not more than 80% of such surface area is covered with the adhesive and that the adhesive is applied on the surface either by spraying or by coating or by printing during or after manufacturing of such absorbent tissue paper.
- It is important that the adhesive used should be sticky enough to enable picking up of larger crumbs when the tissue paper is placed on the smooth surface. However, the adhesive strength should be not too large so that the consumer can easily remove the tissue paper from the smooth surface and that the tissue paper can still be stored as a roll or stacked upon one another and subsequently be separated for use.
- The absorbent tissue paper according to the present invention is especially useful for picking up solid particles such as sugar, bread crumbs, bits of paper or other solid wastes.
- An uptake of solid particles is now possible without detrimentally affecting the ability of the tissue paper to absorb liquid substances. Moreover, due to the fact that only one surface of the tissue paper is covered with adhesives, the other non-sticky surface can still be used for subsequent cleaning after the solid particles have been removed. The present invention is a very interesting alternative for table vacuum cleaners and brushes, it makes shaking out of table cloth unnecessary and thus contributes to making household work easier.
- The improved tissue papers developed according to the present invention can be used inter alia as handkerchiefs, napkins, facials or toilet papers. However there is a clear preference that these tissue papers are specially useful as household towels.
-
- Fig.
- 1 shows a schematic view of a double-side household towel according to a first embodiment of the present invention;
- Fig. 2
- shows a schematic view of a double-side household towel according to a second embodiment of the present invention;
- Fig. 3
- shows a schematic view of a household towel according to a third embodiment of the present invention;
- Fig. 4
- shows a schematic view of a spraying device for applying adhesive to a tissue paper in accordance with the present invention; and
- Fig. 5
- shows a schematic view of a contact application device for applying adhesive to a tissue paper according to the present invention.
- Examples of various embodiments of the present invention are shown in the drawings and described in more detail in the following.
-
Figure 1 shows a double-side household towel according to one embodiment of the present invention which is structured, printed and embossed on the top side (a) and which is coated with adhesives on the bottom side (b). -
Figure 2 relates a double-side household towel according to another embodiment of the present invention having a special adhesive area (a) at the rear part of the bottom side of the household towel. Such adhesive area is placed perpendicular to the wiping direction (b). - As can be seen from
Figure 3 , it is also possible according to the present invention that the bottom side (b) of a household towel is coated with adhesive spots, thereby forming a grid-like pattern. (a) relates to the top side of the household towel. -
Figure 4 relates to a spraying device for applying an adhesive to a tissue paper according to the present invention comprising a photo-eye detector (a), a hot-melt applicator (b) and several rolls (c). (d) represents the product flow, (e) indicates the adhesive areas of the tissue papers and (f) represents the perforation lines of the tissue papers. -
Figure 5 shows a so-called contact application device for applying an adhesive to a tissue paper according to the present invention comprising an offset-roll system (a), a photo-eye detector (b) and several rolls (c). The product flow is represented by (d) and (e) indicates the adhesive areas of the tissue papers.
Claims (7)
- Absorbent tissue papers stacked one upon the other or rolled, each absorbent tissue paper comprising an adhesive applied to at least a part of one surface (b; a) of the absorbent tissue paper so as to enable picking up of solid particles, but covering not more than 80% of such surface area and being applied in an amount of up to 150 g/m2,
wherein the adhesive is applied on the surface either by spraying or coating or printing during or after manufacturing of the absorbent tissue papers. - Absorbent tissue paper according to claim 1, wherein the adhesive covers not more than 50% of one surface area (b; a) of the absorbent tissue paper.
- Absorbent tissue paper according to any of claims 1 to 2, wherein the adhesive is applied on a certain limited area of one surface (a) of the absorbent tissue paper.
- Absorbent tissue paper according to any of claims 1 to 3, wherein the adhesive is applied in the form of discrete spots covering one surface (b) of the absorbent tissue paper.
- Absorbent tissue paper according to claim 4, wherein the average area of the discrete spots ranges from 0.01 mm2 to 30 mm2 .
- Absorbent tissue paper according to any of claim 1 to 5, wherein the adhesive is applied on the surface either by spraying or by coating or by printing during or after manufacturing of such absorbent tissue paper.
- Absorbent tissue paper according to any of claims 1 to 6, wherein the total basis weight of such absorbent tissue paper is equal to a maximum of 70 g/m2.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2004/005790 WO2005117681A1 (en) | 2004-05-28 | 2004-05-28 | Pick-up absorbent tissue paper |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1765137A1 EP1765137A1 (en) | 2007-03-28 |
EP1765137B1 true EP1765137B1 (en) | 2011-07-13 |
Family
ID=34957821
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04739433A Expired - Lifetime EP1765137B1 (en) | 2004-05-28 | 2004-05-28 | Pick-up absorbent tissue paper |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1765137B1 (en) |
AT (1) | ATE515972T1 (en) |
ES (1) | ES2366616T3 (en) |
WO (1) | WO2005117681A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10801163B2 (en) | 2016-04-15 | 2020-10-13 | H.B. Fuller Company | Polyacrylic adhesive for use in tissue paper laminating |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1239079A1 (en) * | 2001-03-09 | 2002-09-11 | Georgia-Pacific France | Paper sheet with small cushions |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2474619A (en) * | 1944-01-22 | 1949-06-28 | Marathon Paper Mills Co | Heat-sealable sheet material |
US2838421A (en) * | 1956-11-28 | 1958-06-10 | Minnesota Mining & Mfg | Adhesives and adhesive tapes |
US5198292A (en) * | 1988-06-15 | 1993-03-30 | International Paper Company | Tack cloth for removing solid particles from solid surfaces and method for its manufacture |
US4990192A (en) * | 1989-10-16 | 1991-02-05 | Alberto-Culver Company | Method of removing lint, hair and other particulate matter from fabric |
JPH09140655A (en) * | 1995-11-20 | 1997-06-03 | T C F:Kk | Portable dust remover |
-
2004
- 2004-05-28 WO PCT/EP2004/005790 patent/WO2005117681A1/en not_active Application Discontinuation
- 2004-05-28 AT AT04739433T patent/ATE515972T1/en not_active IP Right Cessation
- 2004-05-28 ES ES04739433T patent/ES2366616T3/en not_active Expired - Lifetime
- 2004-05-28 EP EP04739433A patent/EP1765137B1/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1239079A1 (en) * | 2001-03-09 | 2002-09-11 | Georgia-Pacific France | Paper sheet with small cushions |
Non-Patent Citations (1)
Title |
---|
"Ullmann's Encyclopedia of Industrial Chemistry", vol. 25, 2003, WILEY-VCH, Weinheim, pages: 125 * |
Also Published As
Publication number | Publication date |
---|---|
ES2366616T3 (en) | 2011-10-21 |
EP1765137A1 (en) | 2007-03-28 |
WO2005117681A1 (en) | 2005-12-15 |
ATE515972T1 (en) | 2011-07-15 |
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