EP0372388A2 - Feuille nettoyante dispersible dans l'eau - Google Patents

Feuille nettoyante dispersible dans l'eau Download PDF

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Publication number
EP0372388A2
EP0372388A2 EP89122081A EP89122081A EP0372388A2 EP 0372388 A2 EP0372388 A2 EP 0372388A2 EP 89122081 A EP89122081 A EP 89122081A EP 89122081 A EP89122081 A EP 89122081A EP 0372388 A2 EP0372388 A2 EP 0372388A2
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EP
European Patent Office
Prior art keywords
water
paper
disintegrable
cleaning sheet
sheet
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.)
Granted
Application number
EP89122081A
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German (de)
English (en)
Other versions
EP0372388A3 (fr
EP0372388B1 (fr
Inventor
Shusuke Kakiuchi
Makoto Ishii
Atsuo Nakae
Seiko Ekuseruin Higashi Shukugo 307 Ikoma
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Kao Corp
Original Assignee
Kao Corp
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Filing date
Publication date
Priority claimed from JP63303159A external-priority patent/JPH0724636B2/ja
Priority claimed from JP63303160A external-priority patent/JP2549159B2/ja
Priority claimed from JP1047534A external-priority patent/JP2584508B2/ja
Application filed by Kao Corp filed Critical Kao Corp
Priority to AT89122081T priority Critical patent/ATE101670T1/de
Publication of EP0372388A2 publication Critical patent/EP0372388A2/fr
Publication of EP0372388A3 publication Critical patent/EP0372388A3/fr
Application granted granted Critical
Publication of EP0372388B1 publication Critical patent/EP0372388B1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • D21H17/43—Carboxyl groups or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid compositions
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/25—Cellulose
    • D21H17/26—Ethers thereof

Definitions

  • This invention relates to a water-disintegrable cleaning sheet, and more particularly to a water-disintegrable cleaning sheet comprising a specific water disintegrable paper having incorporated or impregnated there into an aqueous cleaning agent containing an organic solvent, which is suitable for cleaning or sterilization of floors or walls of rooms or toilet rooms, furniture, toilet seats, toilet basins, etc. or useful as toilet paper, and can be thrown into flushing water.
  • Water-disintegrable papers or cleaning goods made of a chemical-containing water-disintegrable paper which can be thrown into water have been used as toilet paper or for cleaning a toilet room or toilet equipment.
  • Conventional water-disintegrable paper usually contains a dry strength agent such as polyvinyl alcohol, carboxymethyl cellulose, and cationic starch, for enhancing dry paper strength without impairing water disintegrability.
  • a paper sheet containing a dry strength agent undergoes serious reduction of strength when impregnated with water. Therefore, where a water-disintegrable paper is combined with a cleaning agent for cleaning or sterilization of floors, walls, furniture, and toilet equipment or for use as toilet paper, the cleaning agent to be combined with has been limited to liquid substances or chemicals having no or very low water content.
  • the cleaning agent In using a cleaning agent of high water content, it has been necessary that the cleaning agent should be foamed and sprayed on a water-disintegrable paper immediately before use and be used without delay in order to suppress water absorption into paper and to prevent strength reduction.
  • Polyacrylamide or the like dry strength agent endows paper with strength enough to withstand use even with a small amount of water being impregnated in the paper sheet, but tends to impair water disintegrability of the sheet.
  • the conventional dry strength agents could not provide a strength enough to withstand cleaning use even when combined with a cleaning agent of high water content in good balance with water disintegrability.
  • JP-A-47-­9486 JP-A-47-­9486
  • JP-A-61-­296159 discloses a water-disintegrable paper in which an aqueous solution containing salts such as potassium salt, calcium salt and barium salt, is impregnated into a fibrous sheet containing carrageenan as a binder, which is used for a wetting tissue paper.
  • JP-A-55-103393 discloses a method for preparing a paper having high strength in a dry state while low in wet state, which comprises treating paper surface with alkali metal and/or alkali earth metal salt of polyacrylic acid polymers, and that the paper can be used for writing paper, printing paper, wrapping paper, etc.
  • An object of the present invention is to provide a water-disintegrable cleaning sheet containing a cleaning agent, which has strength enough for cleaning use under a mechanical force while retaining satisfactory water disintegrability.
  • the inventors have found that the above object of the present invention is accomplished by incorporating a water-soluble binder having a carboxyl group and at least one metallic ion selected from the group consisting of ions of an alkaline earth metal, manganese, zinc, cobalt and nickel, and an aqueous cleaning agent containg an organic solvent into a web composed of water-dispersible fibers.
  • the present invention provides a water-disintegrable cleaning sheet comprising a web of water-dispersible fibers having incorporated thereinto a water-soluble binder having a carboxyl group; at least one polyvalent metallic ion selected from the group consisting of ions of alkaline earth metals, zinc; cobalt and nickel; and an aqueous cleaning agent containing an organic solvent.
  • Water-dispersible fibers which constitute a water-­disintegrable cleaning sheet of the present invention are not particularly restricted as long as they are fibrous materials substantially dispersible in water.
  • suitable water-dispersible fibers are wood pulp fibers, non-wood vegetable fibers, and synthetic fibers such as rayon fibers and polyester fibers.
  • Water-soluble binders having a carboxyl group which can be used in the present invention include polysaccharide derivatives, synthetic high polymers, and naturally-occurring substances.
  • Suitable polysaccharide derivatives include carboxymethyl cellulose, carboxyethyl cellulose, and carboxymethylated starch, with carboxymethyl cellulose being preferred.
  • suitable synthetic high polymers include homopolymers of an unsaturated carboxylic acid, copolymers of two or more unsaturated carboxylic acids, and copolymers of an unsaturated carboxylic acid and other copolymerizable monomer.
  • suitable unsaturated carboxylic acids are acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, maleic acid, and fumaric acid.
  • Monomers copolymerizable with the unsaturated carboxylic acid include esters of these unsaturated carboxylic acids, vinyl acetate, olefins (e.g., ethylene), acrylamide, and vinyl ether.
  • Preferred of these high polymers are those containing an acrylic acid and/or methacrylic acid unit, e.g., polyacrylic acid, polymethacrylic acid, an acrylic acid-methacrylic acid copolymer, and an acrylic acid (or methacrylic acid)-alkyl acrylate (or alkyl methacrylate) copolymer.
  • an acrylic acid and/or methacrylic acid unit e.g., polyacrylic acid, polymethacrylic acid, an acrylic acid-methacrylic acid copolymer, and an acrylic acid (or methacrylic acid)-alkyl acrylate (or alkyl methacrylate) copolymer.
  • Suitable naturally-occurring water-­soluble binders are alginic acid, xanthan gum, arabic gum, tragacanth gum, and pectin.
  • carboxymethyl cellulose is particularly preferred.
  • the water-soluble binder is usually used in an amount of from 0.1 to 30% by weight, preferably from 1 to 15% by weight, and more preferably form 1 to 10% by weight, based on an amount of a dry web.
  • a metallic ion which is incorporated into the water-­disintegrable cleaning sheet of the present invention is at least one selected from the group consisting of ions of alkaline earth metals such as magnesium, calcium, strontium and barium; manganese; zinc; cobalt; and nickel.
  • metallic ions as described above, calcium, strontium, barium, zinc, cobalt, and nickel ions are preferred from the standpoint of sufficient strength for cleaning work of the cleaning sheet of the present invention.
  • Monovalent metallic ions other than those described above satisfy water disintegrability but cannot afford strength withstanding cleaning work.
  • the essential metallic ion is preferably used in an amount of at least 1/4 mol, more preferably at least 1/2 mol, per mol of carboxyl group of the water-soluble binder.
  • the essential metallic ion is incorporated into the water-disintegrable cleaning sheet of the present invention in the forms:
  • a molar ratio of (a)/(b) is in the range of from 1/0.01 to 1/10, preferably from 1/0.05 to 1/3.
  • an alkali metal salt of the binder which formed a salt between the carboxyl group and an alkali metal such as sodium and potassium, is preferably used as a water-soluble binder.
  • the water-disintegrable cleaning sheet of the present invention can be produced by incorporating water-disintegrable paper composed of the above-mentioned components with an aqueous cleaning agent containing an organic solvent.
  • Processes for producing the water-disintegrable paper which constitute the water-disintegrable cleaning sheet of the present invention are not particularly restricted and include conventionally known wet process and dry process.
  • the water-­disintegrable paper can be obtained by spraying or coating an aqueous solution of the water-soluble salt of at least one selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt and nickel, to a dry web containing carboxyl-containing water-soluble binder, and then drying.
  • the paper containing carboxyl-containing water-soluble binder is obtained by adding a carboxyl-containing water-soluble binder into an aqueous dispersion of water-dispersible fibers and then subjecting paper making, or by spraying or coating a carboxyl-­containing water-soluble binder to a web composed of water-­dispersible fibers, and then drying. Further, it can be obtained by spraying or coating a carboxyl-containing water-­soluble binder and an aqueous solution containing water-soluble salt of at least one selected from the group consisting of an alkaline earth metal, manganese, zinc, cobalt and nickel, and then drying.
  • the water-disintegrable paper is obtained by adding the intermolecular mixed salt binder into an aqueous dispersion of water-dispersible fibers and then subjecting paper making, or by spraying or coating a solution of the intermolecular mixed salt binder to a web composed of water-dispersible fibers and then drying.
  • Processes for producing the water-disintegrable cleaning sheet of the present invention are not particularly restricted, and it can be produced, for example, by incorporating or impregnating an aqueous cleaning agent into the water-disintegrable paper as described above, or adding an aqueous cleaning agent into the water-disintegrable paper at any step of the above-mentioned production procedure of the water-disintegrable paper. Further, the water-disintegrable cleaning sheet can be produced by incorporating an aqueous cleanig agent together with the essential metallic ion of the present invention.
  • the essential metallic ion is, for example, incorporated into the water-disintegrable cleaning sheet by dissolving at least one of water-soluble salt of the essential metallic ion, namely the form (B) as mentioned above, into an aqueous cleaning agent containing an organic solvent, and impregnating or spraying the resulting aqueous cleaning agent into the web containing calboxyl-containing water-soluble binder, and then drying.
  • the aqueous cleaning agent which is incorporated in the cleaning sheet essentially contains an organic solvent for obtaining high strength withstanding cleaning work.
  • Suitable organic solvents are water-compatible (or water-soluble) solvents typically including monohydric lower alcohols such as ethanol, methanol, and propanol; glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, buthylene glycol and hexylene glycol; mono- or diethers of the aforementioned glycols and lower alcohols such as methanol, ethanol and butanol; esters of the aforementioned glycols and lower fatty acids; and polyhydric alcohols such as glycerine and sorbitol.
  • water-insoluble solvents they are added in the form of an emulsion.
  • the aqueous cleaning agent is usually used in an amount about 0.5 to 5 times, preferably 1 to 2.5 times the weight of water-disintegrable paper.
  • the content of the organic solvent in the aqueous cleaning agent ranges from 95 to 5% by weight, preferably from 8 to 92% by weight, and that of water ranges from 5 to 95% by weight, preferably from 92 to 8% by weight.
  • cleaning agents rich in organic solvent e.g., ethanol and isopropyl alcohol, are employed.
  • aqueous cleaning agents rich in water are employed.
  • the water content ranges from 30 to 95% by weight, preferably from 40 to 92% by weight, more preferably from 60 to 90% by weight
  • the organic solvent content ranges from 5 to 70% by weight, preferably from 8 to 60% by weight, more preferably from 10 to 40% by weight.
  • the aqueous cleaning agents may further contain surfactants, sterilizers, deodorizers; perfumes, and the like.
  • anionic surfactants nonionic surfactants, cationic surfactants and amphoteric surfactants are include.
  • Preferred examples thereof include amine oxides having one or two of alkyl group containing 8 to 22 carbon atoms or lower alkyl group, sulfobetaines or hydroxysulfobetaines having alkyl group containing 8 to 22 carbon atoms, and carbobetaines having alkyl group containing 8 to 22 carbon atoms, as amphoteric surfactants; alkylsulfates containing 8 to 22 carbon atoms, alkyl ether sulfates adding 1 to 30 mol of ethylene oxide and having alkyl group containing 8 to 22 carbon atoms, alkylbenzene sulfonic acid salts having alkyl group containing 8 to 22 carbon atoms, ⁇ -sulfofatty acid ester salts containing 8 to 22 carbon atoms, alkyl (or
  • a cleaning sheet prepared by simply impregnating water-disintegrable paper containing a carboxyl-containing water-soluble binder with an aqueous solution having dissolved therein the above-described metallic ion, or by simply incorporating the web composed of water-dispersible fibers with an intermolecular mixed salt of the water-soluble binder fails to exhibit sufficient strength enough to carry out cleaning. It is considered that a combined use of an organic solvent markedly accelerates formation of an insolubilized crosslinked complex of the water-soluble binder and the metallic ion to thereby afford sufficient strength for cleaning work even in using an aqueous cleaning agent having a very high water content.
  • the water-disintegrable cleaning sheet of the present invention even when using a cleaning agent of high water content, exhibits strength withstanding cleaning work and satisfactory water disintegrability in good balance and produces great effects as cleaning sheet.
  • a toilet paper-like water-disintegrable paper sheet having a basis weight of 25 g/m2 was produced from a bleached kraft pulp of conifer beaten to a CSF (Canadian Standard Freeness) of 680 cc using an ordinary paper machine.
  • the water-disintegrable paper sheet was sprayed with 3% (corresponding to 0.75 g/m2) of a sodium carboxymethyl cellulose "CMC 2200" (produced by Daisel Kagaku K.K.) in the form of a 1% aqueous solution and dried to obtain a CMC-­containing sheet.
  • CMC 2200 sodium carboxymethyl cellulose
  • the CMC-containing sheet was impregnated with 1.7 times the sheet weight of a 1% solution of calcium chloride in an ethanol/water mixed solvent having a ratio of 50/50, 20/80, 10/90 or 0/100 to obtain a water-disintegrable cleaning sheet.
  • a strip 25 mm wide and 100 mm long was cut out of the cleaning sheet, and breaking strength of the strip in the machine direction (MD) and cross direction (CD) was measured using a universal testing machine "RTM-25" (manufactured by Orientic K.K.) under conditions of 300 mm/min in rate of pulling and 50 mm in grip distance.
  • the cleaning sheet was used for wiping black tiles inclusive of the joints for 5 minutes. Dusting on the tiles and fuzzing of the sheet are observed and evaluated according to the following rating system. o: Neither substantial dusting nor fuzzing was observed. ⁇ : Slight dusting was observed, but fuzzing was not observed. ⁇ : Dusting and fuzzing were observed.
  • the cleaning sheet was cut to pieces of 50 mm ⁇ 50 mm and put into the water under stirring. After 90 seconds, the disintegrated and dispersed state of the sheet was observed and evaluated according to the following rating system, taking commercially available toilet paper as a standard having satisfactory dispersibility. o: Satisfactory dispersion ⁇ : Slightly poor dispersion ⁇ : Poor dispersion
  • Example 1 A cleaning sheet was produced in the same manner as in Example 1, except for using an impregnating solution containing no calcium chloride. The resulting cleaning sheet was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 1 below.
  • Example 1 50/50 20/80 10/90 0/100 Wet Tensile Strength (g/25mm) MD 1020 CD 620 MD 480 CD 310 MD 370 CD 220 MD 40 CD 28 Dusting and Fuzzing ⁇ ⁇ ⁇ ⁇ Water-Disintegrability ⁇ ⁇ ⁇ ⁇ Comparative Example 1 Wet tensile Strength (g/25mm) MD 350 CD 200 MD 90 CD 50 MD 35 CD 20 MD 30 CD 17 Dusting and Fuzzing ⁇ ⁇ ⁇ ⁇ Water-Disintegrability ⁇ ⁇ ⁇ ⁇ ⁇
  • Each of calcium chloride, barium chloride, strontium nitrate, chromium chloride, manganese sulfate, zinc chloride, cobalt chloride, nickel nitrate, and lead sulfate was dissolved in a 2/8 mixed solvent of ethanol and water to prepare a 1% impregnating solution.
  • the CMC-containing sheet as prepared in Example 1 was impregnated with a 1.7 times the sheet weight of the impregnating solution.
  • a cleaning sheet was produced in the same manner as in Example 2, except for replacing the metallic salt as used in Example 2 with potassium chloride, copper sulfate, ferrous chloride, ferric chloride, stannous chloride, or aluminum sulfate.
  • Example 2 Metallic Ion in Solution Wet Tensile Strength (g/25mm) Dusting and Fuzzing Water-Disintegrability MD CD
  • Example 2 Ca2+ 480 310 ⁇ ⁇ Sr2+ 492 322 ⁇ ⁇ Ba2+ 524 340 ⁇ ⁇ Mn2+ 273 163 ⁇ ⁇ Zn2+ 472 302 ⁇ ⁇ Co2+ 396 194 ⁇ ⁇ Ni2+ 440 276 ⁇ ⁇ Comparative Example 2 K+ 42 19 ⁇ ⁇ Cu2+ 540 348 ⁇ ⁇ Fe2+ 442 283 ⁇ ⁇ Sn2+ 480 320 ⁇ ⁇ Fe3+ 686 390 ⁇ ⁇ Al3+ 760 411 ⁇ ⁇ ⁇
  • Example 2 Calcium chloride was dissolved in a 2/8 mixed solvent of ethanol and water in a prescribed concentration, and the resulting impregnating solution was impregnated into the CMC-containing sheet as prepared in Example 1 in an amount of 1.7 times the weight of the sheet to obtain a water-­disintegrable cleaning sheet containing a Ca2+ ion at a molar ratio of 1/4, 1/2, or 1/1 to the carboxylate ion of CMC.
  • a web of split and deposited fibers of a conifer fluff pulp (basis weight: 30 g/m2) was sprayed with 15% of a sodium salt of an acrylic acid-2-ethylhexyl acrylate copolymer (7/3 by mol), followed by drying to obtain a water-soluble binder-­containing water-disintegrable sheet.
  • Crepe paper having a basis weight of 25 g/m2 was produced from a raw material comprising 100 parts of parts of NBKP (softwood kraft pulp) and 10 part of CMC2200 using a cylindrical net-Yankee machine.
  • the resulting CMC-containing sheet was sprayed with 1 part of a 2% calcium chloride aqueous solution per part of the sheet and dried to obtain a water-disintegrable sheet.
  • the sheet was impregnated with 1.5 times the sheet weight of a cleaning agent comprising a surfactant (Softanol 70), ethanol, and water (1/20/79).
  • a cleaning agent comprising a surfactant (Softanol 70), ethanol, and water (1/20/79).
  • Softanol 70 a surfactant
  • ethanol a surfactant for ethanol
  • water a surfactant for ethanol
  • Table 5 the results obtained are shown in Table 5 below.
  • Example 5 Comparative Example 4 Wet Tensile Strength (g/25 mm): MD 520 50 CD 300 30 Dusting ⁇ ⁇ Water Disintegrability ⁇ ⁇
  • Toilet paper-like crepe paper having a basis weight of 20 g/m2 (crepe ratio: 10%) was produced from a raw material comprising 60 parts of NBKP and 40 parts of LBKP (broad-leaved tree kraft pulp) using a cylindrical net-Yankee machine.
  • the crepe paper was coated with 3% the paper weight of CMC2200 with a gravure coater followed by drying to obtain CMC-­containing paper.
  • the CMC-containing paper was uniformly sprayed with part of a 2% aqueous solution of zinc sulfate per part of the paper and dried to obtain water-disintegrable paper.
  • the CMC-containing paper as prepared in Example 6 was impregnated with the same cleaning agent as used in Example 6.
  • the impregnated paper was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 6 below.
  • the crepe paper as described in Example 6 was coated with 3% the paper weight of a 3:1 mixture of CMC2200 and calcium chloride with a gravure coater and dried to obtain water-disintegrable paper.
  • Example 6 Comparative Example 5 Wet Tensile Strength (g/25mm): MD 480 420 55 CD 350 300 40 Dusting ⁇ ⁇ ⁇ Water Disintegrability ⁇ ⁇ ⁇
  • a web of split and deposited fibers of conifer fluff pulp (basis weight: 40 g/m2) was sprayed with 15% the weight of a 3:2 mixture of CMC1330 (produced by Daisel K.K.) and calcium chloride and dried to obtain water-disintegrable paper.
  • Example 8 The web as described in Example 8 was sprayed with 10% the web weight of CMC1330 and dried. The resulting CMC-­containing paper was impregnated with a cleaning agent in the same manner as in Example 8. The properties of the impregnated paper are shown in Table 7. TABLE 7 Example 8 Comparative Example 6 Wet Tensile Strength (g/25 mm): MD 320 18 CD 310 20 Dusting ⁇ ⁇ Water Disintegrability ⁇ ⁇
  • the crepe paper as described in Example 6 was coated with 3% the paper weight of a monoethanolamine salt of a methacrylic acid-lauryl methacrylate copolymer (7/3 by mol) with a gravure coater and dried to obtain water-soluble binder-­containing paper.
  • the paper was uniformly sprayed with 1 part of a 2% calcium chloride aqueous solution per part of the paper and dried to obtain water-disintegrable paper.
  • the water-disintegrable paper was impregnated with 1.5 times the paper weight of a cleaning agent comprising a surfactant (dodecyldimethylamine oxide), polyethylene glycol 400 and water (1/20/79). Properties of the impregnated paper were evaluated in the same manner as in Example 1, and the results obtained are shown in Table 8 below.
  • a cleaning agent comprising a surfactant (dodecyldimethylamine oxide), polyethylene glycol 400 and water (1/20/79).
  • Example 9 The water-soluble binder-containing paper as obtained in Example 9 was impregnated with a cleaning agent in the same manner as in Example 9. Properties of the impregnated paper are shown in Table 8 below. TABLE 8 Example 9 Comparative Example 7 Wet Tensile Strength (g/25 mm): MD 450 48 CD 310 40 Dusting ⁇ ⁇ Water Disintegrability ⁇ ⁇
  • the water-disintegrable paper was impregnated with 1.7 times the paper weight of a cleaning agent comprising a surfactant (Softanol 90), ethanol and water (1/15/84), and the impregnated paper was evaluated in the same manner as in Example 1. The results obtained are shown in Table 9 below.
  • Water-disintegrable crepe paper having a basis weight of 25 g/m2 (crepe ratio: 15%) was produced from a raw material comprising 100 parts of NBKP and 10 parts of a water-soluble sodium carboxymethyl cellulose (produced by Daisel K.K.) using a cylindrical net-Yankee machine.
  • Example 10 The water-disintegrable paper was impregnated with a cleaning agent in the same manner as in Example 10. Properties of the impregnated paper are shown in Table 9. TABLE 9 Example 10 Comparative Example 8 Wet Tensile Strength (g/25 mm): MD 300 45 CD 250 25 Dusting ⁇ ⁇ Water Disintegrability ⁇ ⁇
  • Toilet paper-like crepe paper having a basis weight of 20 g/m2 (crepe ratio: 10%) was produced from a raw material comprising 70 parts of NBKP and 30 parts of LBKP using a cylindrical net-Yankee machine.
  • the impregnated paper was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 10 below.
  • the crepe paper as described in Example 11 was coated with 3% the paper weight of a water-soluble sodium corboxymethyl cellulose with a gravure coater and dried to obtain water-disintegrable paper.
  • the water-disintegrable paper was impregnated with a cleaning agent in the same manner as in Example 11. Properties of the impregnated paper are shown in Table 10.
  • Example 11 Example 12 Comparative Example 9 Wet Tensile Strength (g/25 mm): MD 320 470 40 CD 250 350 20 Dusting ⁇ ⁇ ⁇ Water Disintegrability ⁇ ⁇ ⁇
  • the impregnated paper was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 11 below.
  • Example 13 The web as described in Example 13 was sprayed with 10% the web weight of a water-soluble sodium carboxymethyl cellulose and dried to obtain water-disintegrable paper.
  • Example 13 The water-disintegrable paper was impregnated with a cleaning agent in the same manner as in Example 13. Properties of the impregnated paper are shown in Table 11. TABLE 11 Example 13 Comparative Example 10 Wet Tensile Strength (g/25 mm): MD 310 10 CD 280 15 Dusting ⁇ ⁇ Water Disintegrability ⁇ ⁇
  • the water-disintegrable paper was impregnated with 1.5 times the paper weight of a cleaning agent comprising a surfactant (dodecyldimethylamine oxide), polyethylene glycol 400 and water (1/19/80), and the impregnated paper was evaluated in the same manner as in Example 1. The results obtained are shown in Table 12 below.
  • the crepe paper as described in Example 11 was coated with 3% of a methacrylic acid-lauryl methacrylate copolymer (7/3 by mol) sodium salt and dried to obtain water-soluble binder-containing paper.
  • Example 14 The water-soluble binder-containing paper was impregnated with a cleaning agent in the same manner as in Example 14. Properties of the impregnated paper are shown in Table 12 below. TABLE 12 Example 14 Comparative Example 11 Wet Tensile Strength (g/25 mm): MD 410 36 CD 280 25 Dusting ⁇ ⁇ Water Disintegrability ⁇ ⁇
  • a water-disintegrable paper sheet having a basis weight of 25 g/m2 was produced from a bleached kraft pulp of conifer beaten to a CSF (Canadian Standard Freeness) of 680 cc using an ordinary paper machine.
  • the water-disintegrable paper sheet was sprayed with 3% the paper weight (corresponding to 0.75 g/m2) of a sodium carboxymethyl cellulose "CMC 1330" (produced by Daisel Kagaku K.K.) in the form of a 1% aqueous solution and dried to obtain a CMC-containing sheet.
  • CMC 1330 sodium carboxymethyl cellulose
  • the water-disintegrable paper sheet was sprayed with 3% the paper weight (corresponding to 0.75 g/m2) of a sodium polyacrylate having a mean molecular weight of 135,000 (produced by Aldrich Chemical Company, Inc.) in the form of a 1% aqueous solution and dried to obtain a polyacrylate-containing sheet.
  • the cleaning sheet was cut to pieces of 50 mm x 50 mm and put into the water under stirring. The time required for collapse (water disintegration) of the sheet in water was measured.
  • the water-disintegrable paper sheet as described in Example 15 was sprayed with 3% the paper weight (corresponding to 0.75 g/m2) of carrageenan having a mean molecular weight of 300,000 (produced by Tokyo Kasei K.K.) in the form of a 1% aqueous solution and dried to obtain a carrageenan-containing sheet.
  • the carrageenan-containing sheet was impregnated with a cleaning agent in the same manner as in Example 15. Properties of the impregnated paper are shown in Table 13 below. TABLE 13 Wet Tensile Strength (g/25mm) Dusting and Fuzzing Water Disintegrability (sec.) MD CD Example 15 CMC-containing Sheet 430 270 ⁇ 14 Polyacrylic acid-containing Sheet 620 390 ⁇ 45 Comparative Example 12 Carrageenan-containing Sheet 78 46 ⁇ 17

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Paper (AREA)
  • Detergent Compositions (AREA)
EP19890122081 1988-11-30 1989-11-30 Feuille nettoyante dispersible dans l'eau Expired - Lifetime EP0372388B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT89122081T ATE101670T1 (de) 1988-11-30 1989-11-30 Im wasser abbaubares reinigungsblatt.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP63303159A JPH0724636B2 (ja) 1988-11-30 1988-11-30 水解性清掃物品
JP63303160A JP2549159B2 (ja) 1988-11-30 1988-11-30 水解紙
JP303160/88 1988-11-30
JP303159/88 1988-11-30
JP1047534A JP2584508B2 (ja) 1989-02-28 1989-02-28 清掃用品用水解紙
JP47534/89 1989-02-28

Publications (3)

Publication Number Publication Date
EP0372388A2 true EP0372388A2 (fr) 1990-06-13
EP0372388A3 EP0372388A3 (fr) 1991-12-18
EP0372388B1 EP0372388B1 (fr) 1994-02-16

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Application Number Title Priority Date Filing Date
EP19890122081 Expired - Lifetime EP0372388B1 (fr) 1988-11-30 1989-11-30 Feuille nettoyante dispersible dans l'eau

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EP (1) EP0372388B1 (fr)
CA (1) CA2004296A1 (fr)
DE (1) DE68913161T2 (fr)
ES (1) ES2051344T3 (fr)
HK (1) HK121294A (fr)

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EP0926299A2 (fr) * 1997-12-26 1999-06-30 Uni-Charm Corporation Feuille de nettoyage désintégrable dans l'eau et contenant de l'alkylcellulose
EP0904933A3 (fr) * 1997-09-24 2000-05-17 Uni-Charm Corporation Feuille fibreuse laminée désintégrable dans l'eau et feuille essuie-tout la contenant
EP1090983A2 (fr) * 1999-10-05 2001-04-11 Uni-Charm Corporation Feuille fibreuse décomposable dans l'eau et contenant un composé de gel
EP1167510A1 (fr) * 2000-06-23 2002-01-02 The Procter & Gamble Company Lingette humide, jetable pour le nettoyage des surfaces dures
EP1630288A1 (fr) * 2004-08-20 2006-03-01 Kao Corporation Article pour le nettoyage désintegrable et à haut gonflant ainsi qu' un procédé pour la fabrication d'un papier désintegrable
EP1681003A2 (fr) 2005-01-18 2006-07-19 Kanfer, Joseph S. Serviettes décomposables par dissolution pour déposer une solution sur une surface
WO2010069988A2 (fr) * 2008-12-18 2010-06-24 Georgia-Pacific France Feuille de papier delitable dans l'eau, mandrin pour rouleau de papier constitue d'une telle feuille
WO2013081911A1 (fr) * 2011-11-30 2013-06-06 Dow Global Technologies Llc Feuille fibreuse non tissée désintégrable dans l'eau
WO2014170348A1 (fr) * 2013-04-15 2014-10-23 Welland Medical Limited Lingette jetable dans les toilettes
US9034478B2 (en) 2008-12-18 2015-05-19 Sca Tissue France Method for making a sheet of degradable paper, use of said sheet for making a mandrel defining a roll carrier, degradable paper sheet, and mandrel including at least one of said sheets
US9039651B2 (en) 2009-08-03 2015-05-26 Sca Tissue France Fibrous sheet that disintegrates in water, process for manufacturing said fibrous sheet, core consisting of strips of said fibrous sheet
EP3330436A1 (fr) 2016-11-30 2018-06-06 CheM&P GmbH & Co KG Substrat fibreux, anti-hygroscopique avec résistance à l'humidité réglable et procédé de fabrication
WO2019011728A1 (fr) * 2017-07-14 2019-01-17 Chem&P Gmbh & Co. Kg Composite renforcé par des fibres résistant à l'humidité et susceptible de se désagréger dans l'eau
CN109790688A (zh) * 2016-09-30 2019-05-21 大王制纸株式会社 水解性片材及该水解性片材的制造方法
EP3575466A1 (fr) * 2018-05-29 2019-12-04 Intervisa Beteiligung und Verwaltung GmbH Matériau composite fibreux pouvant être dissout dans l'eau
US20230167608A1 (en) * 2020-05-29 2023-06-01 Daio Paper Corporation Water dispersible sheet and method to manufacture water dispersible sheet

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US5264269A (en) * 1989-09-21 1993-11-23 Kao Corporation Water-disintegratable cleaning article in laminated sheet form
WO1992013032A1 (fr) * 1991-01-25 1992-08-06 Battelle Memorial Institute Composition polymere dispersible dans une base et articles dispersibles
US5905046A (en) * 1995-10-13 1999-05-18 Uni-Charm Corporation Biodegradable and hydrolyzable sheet
US6127593A (en) * 1997-11-25 2000-10-03 The Procter & Gamble Company Flushable fibrous structures
US6579570B1 (en) 2000-05-04 2003-06-17 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6423804B1 (en) 1998-12-31 2002-07-23 Kimberly-Clark Worldwide, Inc. Ion-sensitive hard water dispersible polymers and applications therefor
US6713414B1 (en) 2000-05-04 2004-03-30 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6653406B1 (en) 2000-05-04 2003-11-25 Kimberly Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6835678B2 (en) 2000-05-04 2004-12-28 Kimberly-Clark Worldwide, Inc. Ion sensitive, water-dispersible fabrics, a method of making same and items using same
US6548592B1 (en) 2000-05-04 2003-04-15 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6815502B1 (en) 2000-05-04 2004-11-09 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersable polymers, a method of making same and items using same
US6444214B1 (en) 2000-05-04 2002-09-03 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6599848B1 (en) 2000-05-04 2003-07-29 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6683143B1 (en) 2000-05-04 2004-01-27 Kimberly Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6429261B1 (en) 2000-05-04 2002-08-06 Kimberly-Clark Worldwide, Inc. Ion-sensitive, water-dispersible polymers, a method of making same and items using same
US6586529B2 (en) 2001-02-01 2003-07-01 Kimberly-Clark Worldwide, Inc. Water-dispersible polymers, a method of making same and items using same
US6828014B2 (en) 2001-03-22 2004-12-07 Kimberly-Clark Worldwide, Inc. Water-dispersible, cationic polymers, a method of making same and items using same
ES2560354B1 (es) * 2015-11-18 2016-11-22 Juan SALVADOR VALERO Microfibra higiénica hidrodispersable
ES2613889B1 (es) * 2015-11-25 2018-03-12 Juan SALVADOR VALERO Microfibra higiénica hidrodispersable, perfeccionada
WO2020087079A1 (fr) 2018-10-26 2020-04-30 Monosol, Llc Articles multicouches dispersibles dans l'eau
WO2021081475A1 (fr) 2019-10-25 2021-04-29 Monosol, Llc Articles multicouches dispersibles dans l'eau

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JPS55103393A (en) 1979-01-27 1980-08-07 Basf Ag Production of paper with high dry strength and low wet strength
JPS61296159A (ja) 1985-06-19 1986-12-26 ア−ス製薬株式会社 水解性不織布

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JPS55103393A (en) 1979-01-27 1980-08-07 Basf Ag Production of paper with high dry strength and low wet strength
JPS61296159A (ja) 1985-06-19 1986-12-26 ア−ス製薬株式会社 水解性不織布

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CN1117659C (zh) * 1997-09-24 2003-08-13 尤妮佳股份有限公司 水崩解性纤维薄片及将其重叠后形成的擦试用薄片
EP0904933A3 (fr) * 1997-09-24 2000-05-17 Uni-Charm Corporation Feuille fibreuse laminée désintégrable dans l'eau et feuille essuie-tout la contenant
EP0926299A3 (fr) * 1997-12-26 2000-05-24 Uni-Charm Corporation Feuille de nettoyage désintégrable dans l'eau et contenant de l'alkylcellulose
EP0926299A2 (fr) * 1997-12-26 1999-06-30 Uni-Charm Corporation Feuille de nettoyage désintégrable dans l'eau et contenant de l'alkylcellulose
EP1090983A2 (fr) * 1999-10-05 2001-04-11 Uni-Charm Corporation Feuille fibreuse décomposable dans l'eau et contenant un composé de gel
EP1090983A3 (fr) * 1999-10-05 2003-12-03 Uni-Charm Corporation Feuille fibreuse décomposable dans l'eau et contenant un composé de gel
WO2002000084A3 (fr) * 2000-06-23 2002-04-04 Procter & Gamble Chiffons humides jetables dans les toilettes pour surfaces dures
EP1167510A1 (fr) * 2000-06-23 2002-01-02 The Procter & Gamble Company Lingette humide, jetable pour le nettoyage des surfaces dures
EP1630288A1 (fr) * 2004-08-20 2006-03-01 Kao Corporation Article pour le nettoyage désintegrable et à haut gonflant ainsi qu' un procédé pour la fabrication d'un papier désintegrable
US7758724B2 (en) 2004-08-20 2010-07-20 Kao Corporation Bulky water-disintegratable cleaning article and process for producing water-disintegratable paper
EP1681003A2 (fr) 2005-01-18 2006-07-19 Kanfer, Joseph S. Serviettes décomposables par dissolution pour déposer une solution sur une surface
EP1681003A3 (fr) * 2005-01-18 2007-11-14 Kanfer, Joseph S. Serviettes décomposables par dissolution pour déposer une solution sur une surface
US8197830B2 (en) 2005-01-18 2012-06-12 Gojo Industries, Inc. Dissolvable pads for solution delivery to a surface
US9034478B2 (en) 2008-12-18 2015-05-19 Sca Tissue France Method for making a sheet of degradable paper, use of said sheet for making a mandrel defining a roll carrier, degradable paper sheet, and mandrel including at least one of said sheets
WO2010069988A2 (fr) * 2008-12-18 2010-06-24 Georgia-Pacific France Feuille de papier delitable dans l'eau, mandrin pour rouleau de papier constitue d'une telle feuille
FR2940330A1 (fr) * 2008-12-18 2010-06-25 Georgia Pacific France Feuille de papier delitable dans l'eau, mandrin pour rouleau de papier constitue d'une telle feuille
WO2010069988A3 (fr) * 2008-12-18 2010-09-02 Georgia-Pacific France Feuille de papier delitable dans l'eau, mandrin pour rouleau de papier constitue d'une telle feuille
US8758564B2 (en) 2008-12-18 2014-06-24 Sca Tissue France Water-degradable paper sheet, and tube for a paper roll consisting of such a sheet
US9353482B2 (en) 2008-12-18 2016-05-31 Sca Tissue France Water-degradable paper sheet, and tube for a paper roll consisting of such a sheet
RU2539336C2 (ru) * 2008-12-18 2015-01-20 Джорджия-Пасифик Франс Бумажный лист, распадающийся в воде, и трубчатый сердечник для бумажного рулона, состоящий из такого листа
US9896803B2 (en) 2009-08-03 2018-02-20 Sca Tissue France Fibrous sheet that disintegrates in water, process for manufacturing said fibrous sheet, core consisting of strips of said fibrous sheet
US9139957B2 (en) 2009-08-03 2015-09-22 Sca Tissue France Fibrous sheet disintegrating in water, process for manufacturing said fibrous sheet, use of said fibrous sheet for the manufacture of a core
US9518360B2 (en) 2009-08-03 2016-12-13 Sca Tissue France Fibrous sheet disintegrating in water, process for manufacturing said fibrous sheet, use of said fibrous sheet for the manufacture of a core
US10626557B2 (en) 2009-08-03 2020-04-21 Essity Operations France Fibrous sheet that disintegrates in water, process for manufacturing said fibrous sheet, core consisting of strips of said fibrous sheet
US9039651B2 (en) 2009-08-03 2015-05-26 Sca Tissue France Fibrous sheet that disintegrates in water, process for manufacturing said fibrous sheet, core consisting of strips of said fibrous sheet
US9303358B2 (en) 2011-11-30 2016-04-05 Dow Global Technologies Llc Water-disintegratable non-woven fibrous sheet
WO2013081911A1 (fr) * 2011-11-30 2013-06-06 Dow Global Technologies Llc Feuille fibreuse non tissée désintégrable dans l'eau
WO2014170348A1 (fr) * 2013-04-15 2014-10-23 Welland Medical Limited Lingette jetable dans les toilettes
AU2014255777B2 (en) * 2013-04-15 2018-11-08 Welland Medical Limited Flushable wipe
CN109790688A (zh) * 2016-09-30 2019-05-21 大王制纸株式会社 水解性片材及该水解性片材的制造方法
CN109790688B (zh) * 2016-09-30 2021-10-08 大王制纸株式会社 水解性片材及该水解性片材的制造方法
WO2018099724A1 (fr) 2016-11-30 2018-06-07 Chem&P Gmbh & Co. Kg Substrat fibreux résistant à l'humidité présentant une résistance variable à l'humidité et à l'état mouillé et son procédé de fabrication
RU2716449C1 (ru) * 2016-11-30 2020-03-11 Чем&П Гмбх & Цо. Кг Влагопрочная волокнистая основа с регулируемой влагопрочностью и стойкостью к увлажнению и способ ее изготовления
WO2018099623A1 (fr) 2016-11-30 2018-06-07 Chem&P Gmbh & Co. Kg Substrat fibreux résistant à l'humidité présentant une résistance variable à l'humidité et à l'état mouillé et son procédé de fabrication
US11136720B2 (en) 2016-11-30 2021-10-05 Chem&P Gmbh & Co. Kg Moisture-proof, fibrous substrate having adjustable moisture and wet strength, and method for production thereof
EP3330436A1 (fr) 2016-11-30 2018-06-06 CheM&P GmbH & Co KG Substrat fibreux, anti-hygroscopique avec résistance à l'humidité réglable et procédé de fabrication
WO2019011728A1 (fr) * 2017-07-14 2019-01-17 Chem&P Gmbh & Co. Kg Composite renforcé par des fibres résistant à l'humidité et susceptible de se désagréger dans l'eau
EP3575466A1 (fr) * 2018-05-29 2019-12-04 Intervisa Beteiligung und Verwaltung GmbH Matériau composite fibreux pouvant être dissout dans l'eau
WO2019228920A1 (fr) * 2018-05-29 2019-12-05 Intervisa Beteiligung Und Verwaltung Gmbh Matériau composite renforcé par des fibres susceptible de se désagréger dans l'eau
US20230167608A1 (en) * 2020-05-29 2023-06-01 Daio Paper Corporation Water dispersible sheet and method to manufacture water dispersible sheet

Also Published As

Publication number Publication date
DE68913161T2 (de) 1994-07-07
EP0372388A3 (fr) 1991-12-18
HK121294A (en) 1994-11-11
DE68913161D1 (de) 1994-03-24
ES2051344T3 (es) 1994-06-16
EP0372388B1 (fr) 1994-02-16
CA2004296A1 (fr) 1990-05-31

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