WO2016203809A1 - Feuille hydrolysable - Google Patents

Feuille hydrolysable Download PDF

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Publication number
WO2016203809A1
WO2016203809A1 PCT/JP2016/060518 JP2016060518W WO2016203809A1 WO 2016203809 A1 WO2016203809 A1 WO 2016203809A1 JP 2016060518 W JP2016060518 W JP 2016060518W WO 2016203809 A1 WO2016203809 A1 WO 2016203809A1
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WO
WIPO (PCT)
Prior art keywords
water
sheet
paper
toilet cleaner
ply
Prior art date
Application number
PCT/JP2016/060518
Other languages
English (en)
Japanese (ja)
Inventor
慎也 和泉
朝子 田中
敦子 長谷澤
真平 向山
孝介 山崎
Original Assignee
大王製紙株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2015121313A external-priority patent/JP2017006157A/ja
Priority claimed from JP2015131770A external-priority patent/JP6193310B2/ja
Application filed by 大王製紙株式会社 filed Critical 大王製紙株式会社
Publication of WO2016203809A1 publication Critical patent/WO2016203809A1/fr

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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K10/00—Body-drying implements; Toilet paper; Holders therefor
    • A47K10/16—Paper towels; Toilet paper; Holders therefor
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K11/00—Closets without flushing; Urinals without flushing; Chamber pots; Chairs with toilet conveniences or specially adapted for use with toilets
    • A47K11/10—Hand tools for cleaning the toilet bowl, seat or cover, e.g. toilet brushes
    • 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
    • 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
    • A47L13/17—Cloths; Pads; Sponges containing cleaning agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/34—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising cellulose or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply

Definitions

  • the present invention relates to a water disintegratable sheet.
  • the conventional wet sheet may be broken if the edge of the toilet is rubbed strongly. Therefore, it has been a problem to improve the resistance to tearing when rubbed strongly while ensuring water disintegration.
  • the suppleness is lowered, so that it is difficult to place the wet sheet on the curved surface such as the edge of the toilet bowl, and there is a problem that the wiping property is lowered.
  • the present invention has been made in view of the above problems, and a first object of the present invention is to provide a water-decomposable sheet having improved resistance to tearing when strongly rubbed while ensuring water-decomposability. Another object of the present invention is to provide a water-decomposable sheet that improves the resistance to tearing when rubbed strongly and suppresses a decrease in flexibility.
  • the water-decomposable sheet according to claim 1 is A substantially water-dispersible multi-ply base paper sheet containing pulp and a water-soluble binder is impregnated with an aqueous agent;
  • the basis weight of the multiple plies is 30 to 150 gsm,
  • a wear resistance test with a Gakushin type friction fastness tester using a PP band as a Gakuden pendulum was performed 3 times each in the MD direction and the CD direction, and the average of the measured values for each 3 times was calculated. The value is 40 times or more.
  • the invention according to claim 2 is the invention according to claim 1,
  • the bending resistance test by the cantilever method is performed three times each, the average of the measured values of each three times is calculated, and the average value is 33 mm or less.
  • the invention according to claim 3 is the invention according to claim 1 or 2
  • the average value in the wear resistance test is 45 times or more in the MD direction and 50 times or more in the CD direction.
  • the invention according to claim 4 is the invention according to any one of claims 1 to 3,
  • the content of the water-soluble binder is increased as it goes to the front surface and / or the back surface.
  • the present invention it is possible to provide a water-decomposable sheet having improved resistance to tearing when rubbed strongly while ensuring water-decomposability.
  • FIG. 10 is an enlarged view of a portion AA in FIG. 9.
  • FIG. 11 is an end view of the BB cutting part of FIG. 10.
  • FIG. 11 is an end view of the CC cut portion of FIG. 10. It is the schematic which shows an example of a papermaking apparatus.
  • the water-decomposable sheet according to the present invention will be described using the toilet cleaner 100 as an example, but the water-decomposable sheet according to the present invention is a wet tissue impregnated with a chemical solution for wiping purposes other than the toilet cleaner. Is also included. Further, the paper conveyance direction at the time of manufacturing the toilet cleaner 100 will be described as the Y direction (vertical direction), and the direction orthogonal to the conveyance direction will be described as the X direction (lateral direction).
  • the toilet cleaner 100 is obtained by plying (stacking) a plurality of (for example, two) base paper sheets, and is impregnated with a predetermined chemical solution. Moreover, as shown in FIG. 1, two types of embossing EM11 and EM12 are given to the whole sheet
  • the contact area between the two embossing EM11 and such cleaning object caused by EM12 is, 100 mm 2 per is preferably 15 mm 2 ⁇ 30 mm 2 approximately.
  • the embossed EM11 by arranging the embossed EM11 to be a rhombus lattice, it is possible to reduce wiping unevenness as compared with the case where the embossed EM11 is disposed in a square lattice or a rectangular lattice. Further, the embossing EM12 is disposed between the embossing EM11.
  • the toilet cleaner 100 is folded in half at the center in the Y direction by being folded. Then, it is stored in a folded plastic case, packaging film, etc. in a folded state, and is expanded and used as needed during use. Note that the method of folding the toilet cleaner 100 is not limited to two, and may be, for example, four or eight.
  • the base paper sheet of the toilet cleaner 100 is composed of a water-decomposable fiber assembly so that it can be discarded as it is in the toilet puddle after cleaning the toilet.
  • mixed fibers of hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP) are used.
  • LLKP hardwood bleached kraft pulp
  • NNKP softwood bleached kraft pulp
  • the component ratio of the hardwood bleached kraft pulp exceeds 50% by weight, that is, the blending ratio of the softwood bleached kraft pulp to the hardwood bleached kraft pulp is less than 1/1.
  • By increasing the compounding ratio of hardwood bleached kraft pulp to softwood bleached kraft pulp gaps between fibers are reduced and moisture transpiration is suppressed, so that the difficulty of drying can be improved.
  • a solution containing carboxymethyl cellulose (CMC) is applied to the base paper sheet from the front and back as a binder solution for enhancing paper strength.
  • the toilet cleaner 100 is in a state in which the content of CMC increases from the center in the thickness direction toward the front and back surfaces. As a result, the toilet cleaner 100 is less likely to be broken even if the edge of the toilet bowl is rubbed more strongly than a conventional product that is uniformly impregnated with a water-soluble binder.
  • Toilet cleaner 100 performs a wear resistance test with a Gakushin type friction fastness tester using PP band as a Gakuden pendulum three times each in the MD direction and CD direction, and calculates the average of the measured values for each three times. Each average value is 40 times or more.
  • the above-mentioned abrasion resistance test is performed by folding the toilet cleaner 100 in three, rubbing the measurement part with a Gakushin type friction fastness tester, and measuring the number of times when damage such as fluffing or tearing is visually confirmed on the paper surface. To do.
  • a PP band with a mesh pattern on the surface is assumed assuming that the toilet cleaner is actually used, that is, the edge of the toilet bowl is rough due to dirt.
  • the condition that the toilet cleaner can endure during actual use is 40 times or more, but it is more than 45 times in the MD direction and 50 times or more in the CD direction. preferable.
  • the toilet cleaner 100 is a cantilever method (JIS L1913: 2010).
  • the bending resistance test is carried out three times, and the average of the measured values (distance from which the test piece is pushed out) is calculated three times so that the average value is 33 mm or less.
  • the average value is 33 mm or less as a measure of the suppleness that allows the toilet cleaner to follow a curved surface such as the edge of a toilet bowl. Yes.
  • the ratio of vertical and horizontal fiber orientation is preferably 0.8 to 2.0, and more preferably 1.0.
  • the paper making process which is a paper manufacturing process
  • the vertical and horizontal fiber orientation ratio of the toilet cleaner 100 is set to 0.8 to 2.0, preferably 1.0, so that it can be wiped from any direction.
  • a toilet cleaner 100 that is not easily torn can be provided.
  • the ratio of the vertical and horizontal fiber orientations can be determined by the ratio of the wet strength in the MD and CD directions.
  • the toilet cleaner 100 of the present embodiment is impregnated with a predetermined chemical solution (aqueous drug).
  • a predetermined chemical solution aqueous drug
  • a fragrance e.g., a fragrance, an antiseptic, a disinfectant, a paper strength enhancer
  • a predetermined chemical solution containing an auxiliary agent such as an organic solvent is impregnated.
  • the chemical solution is preferably impregnated in an amount of 150 to 300% by weight based on the weight of the base paper sheet that is the base material of the toilet cleaner 100.
  • aqueous cleaning agent a surfactant or a lower or higher (aliphatic) alcohol can be used.
  • flavor 1 type or several types can be suitably selected and used out of oil-based fragrance
  • preservative for example, parabens such as methyl paraben, ethyl paraben, propyl paraben and the like can be used.
  • benzalkonium chloride for example, benzalkonium chloride, chlorhexidine gluconate, popidone iodine, ethanol, benzilium cetyl oxide, triclosan, chlorxylenol, isopropylmethylphenol and the like can be used.
  • the paper strength enhancer crosslinking agent
  • boric acid various metal ions, and the like can be used.
  • organic solvent polyhydric alcohols such as glycol (divalent), glycerin (trivalent), and sorbitol (tetravalent) can be used.
  • the above-mentioned adjuvants for the components of the chemical solution can be appropriately selected, and components that perform other functions may be included in the chemical solution as necessary.
  • the bulging portion PR21 has a curved shape.
  • the embossed EM12 has a bulged portion PR22 having a planar shape.
  • the embossing EM12 is arrange
  • the two types of embosses EM11 and EM12 formed in this way can increase the contact area with the object to be cleaned, the hardness of the toilet cleaner 100 is reduced and the wiping performance is improved.
  • the toilet cleaner 100 is powered during wiping work.
  • the contact area is increased for the first time. Therefore, the contact area is increased, and the flexibility is improved due to the deformation of each emboss.
  • the contact area CN31 generated by the deformation of the emboss EM11 due to the force applied to the toilet cleaner 100 during the wiping operation is discretely generated in the vicinity of the emboss EM11.
  • the contact area CN32 generated by the deformation of the embossing EM11 and EM12 due to the force applied to the toilet cleaner 100 during the wiping operation is It can be seen that the contact area CN31 in FIG. 4A increases.
  • embossing EM11 and EM12 can obtain the effect of normal embossing similarly, and can improve the texture, absorbability, bulkiness, etc. of a toilet cleaner. Furthermore, the continuous embossing EM21 can also obtain the effect of the appearance by giving embossing similarly to normal embossing.
  • FIG. 5 is a flowchart showing a method for manufacturing the toilet cleaner 100.
  • FIG. 6 is a schematic diagram of a solution application facility for applying a binder solution to the base paper sheet of the toilet cleaner 100.
  • FIG. 7 is a schematic diagram of processing equipment for processing a base paper sheet to which a binder solution has been applied by the solution application equipment shown in FIG.
  • a paper making process (S1) for making a paper as a base paper with a paper machine (not shown) is performed.
  • continuous dry base paper 1 ⁇ / b> A fed out from a plurality of (for example, two) primary raw rolls 1, 1 each wound up the base paper that has been made.
  • a drying process (S4) and a slit / winding process (S5) for slitting and winding the dried continuous water-decomposable sheet 1D are performed.
  • the number of primary rolls can be changed as long as there are two or more. However, in the following description, an example of using two primary rolls will be described.
  • the continuous water-decomposable sheet 1 ⁇ / b> D fed from the secondary raw roll 11 wound in the slit / winding step (S ⁇ b> 5) is embossed.
  • An embossing process (S6) and a finishing process (S7) for finishing the embossed sheet 1E that has been embossed are performed. Details of each process will be described later.
  • a papermaking raw material is made by a known wet papermaking technique to form a base paper sheet. That is, after making the papermaking raw material into a wet paper state, it is dried by a dryer or the like to form a base paper sheet such as thin paper or crepe paper.
  • a raw material of the base paper sheet for example, known virgin pulp, waste paper pulp and the like can be used, and at least pulp fibers are included.
  • a blend of LBKP and NBKP in an appropriate ratio is particularly suitable.
  • the base paper sheet of the present invention contains an anionic acrylamide polymer (hereinafter referred to as “anionic PAM”) as a flocculant.
  • anionic PAM is a polymer obtained by copolymerizing an acrylamide monomer and an anionic monomer. Examples of the acrylamide monomer include acrylamide alone or a mixture of acrylamide and the following nonionic monomer copolymerizable with acrylamide.
  • Nonionic monomers copolymerizable with acrylamide include methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, N-isopropylacrylamide, N-hydroxyethylacrylamide, diacetone.
  • Examples include acrylamide, acryloylmorpholine, N-acryloylpyrrolidine, N-acryloylpiperidine, N-vinylrolidone, N-vinylformamide, and N-vinylacetamide. These may be used alone or in combination of two or more.
  • anionic monomer examples include acrylic acid, methacrylic acid, acrylamido-2-methylpropanesulfonic acid, itaconic acid, maleic acid, fumaric acid, and neutralized salts thereof.
  • a monomer such as styrene, acrylonitrile, (meth) acrylic acid ester, or the like may be blended as long as the water solubility of the anionic PAM is not impaired.
  • the addition amount of the anionic PAM is preferably about 10 to 1000 ppm.
  • papermaking chemicals such as a wet paper strength agent, an adhesive, and a release agent may be appropriately used for the base paper sheet.
  • a binder solution is provided in the solution provision process of the solution provision equipment mentioned later, you may make it provide a binder solution in the step of a papermaking process.
  • the strength of the entire water-decomposable sheet can be increased, and by further applying a binder solution in the solution-applying process in the subsequent process, the surface strength of the water-decomposable sheet is further increased. Can be raised.
  • a water-soluble binder and a fixing agent to the pulp fiber of the water-soluble binder are added to a dispersion liquid containing pulp as a papermaking raw material, and this is used as a raw material.
  • a paper making method is known (Japanese Patent Laid-Open No. 3-193996). That is, it is a method of internally adding a water-soluble binder.
  • a sheet made from a pulp-containing dispersion may be wet-papered, press dehydrated or semi-dried, and then a water-soluble binder may be spray-dried or coated and dried to produce a fiber sheet containing a predetermined amount of the water-soluble binder.
  • a fiber sheet having a lower density and better water disintegration can be obtained by using a pre-drying system such as a hot-air passing dryer than performing press dewatering.
  • a pre-drying system such as a hot-air passing dryer than performing press dewatering.
  • FIG. 12 shows a schematic view of an example of a production apparatus preferably used for producing a fiber sheet when a water-soluble binder is used as the binder.
  • the manufacturing apparatus (wet papermaking machine) shown in FIG. 12 includes a former 14, a wire part, a first dry part 17, a spray part, and a second dry part 24.
  • the former 14 adjusts the furnish supplied from a preparation device (not shown) to a predetermined concentration and supplies it to the wire part.
  • a preparation device includes a device that beats and beats raw materials such as pulp fibers, and an addition device that adds additives such as sizing agents, pigments, paper strength enhancers, bleaching agents, and flocculants to the beaten and beaten raw materials.
  • additives such as sizing agents, pigments, paper strength enhancers, bleaching agents, and flocculants to the beaten and beaten raw materials.
  • a stock made of a raw material having a predetermined concentration according to the characteristics of hydrolyzed paper is prepared as a finished stock. It is also possible to mix a binder with the pulp slurry.
  • the wire part is a wet paper that forms the paper stock supplied from the former as a wet paper.
  • the first dry part 17 dries the wet paper formed in the wire part.
  • the spray part sprays the binder onto the paper dried by the first dry
  • the furnish supplied from the former 14 is made in the wire part, and a wet paper is formed on the wire 15. Water is removed from the wet paper by suction by a suction box 16 installed in the wire part, and the wet paper has a predetermined moisture content.
  • the wet paper is introduced into the first dry part 17 and dried.
  • the first dry part 17 is composed of a through air dryer (hereinafter referred to as TAD).
  • the TAD includes a rotating drum 18 having a breathable peripheral surface, and a hood 19 that covers the rotating drum 18 almost airtightly.
  • air heated to a predetermined temperature is supplied into the hood 19. The heated air flows from the outside of the rotating drum 18 toward the inside.
  • the wet paper web is transported while being held on the peripheral surface of the rotating drum 18 rotating in the direction of the arrow in FIG. While being transported in the TAD, the heated paper penetrates the wet paper in the thickness direction, whereby the wet paper is dried to become paper.
  • the paper obtained in the first dry part 17 is sprayed with an aqueous solution (binder solution) containing a binder in the spray part.
  • the spray part is a position between the first and second dry parts 17 and 24. Both dry parts 17 and 24 are connected via a conveyor.
  • the conveyor includes an upper conveyor belt 20 and a lower conveyor belt 21 that rotate in the directions indicated by the arrows.
  • the conveyor 20 is configured to convey paper to the second dry part 24 while being dried by the TAD of the first dry part 17 and sandwiching the paper between the belts 20 and 21.
  • a vacuum roll 22 is disposed at the folded end on the downstream side of the upper conveyor belt 20. The vacuum roll 22 adsorbs paper on the back surface of the upper conveyor belt 20 and conveys the upper conveyor belt 20 under the adsorbed state.
  • the spray part includes a spray nozzle 23.
  • the spray nozzle 23 is disposed below the second dry part 24 and so as to face the vacuum roll 22.
  • the spray nozzle 23 sprays a spray liquid containing a binder toward the vacuum roll 22 and adds (externally adds) the spray liquid to paper.
  • the paper is conveyed to the second dryer part 24.
  • the second dryer part 24 is composed of a Yankee dryer.
  • the paper that has been sprayed with the spray liquid and is in a wet state is conveyed while being held on the peripheral surface of the rotary drum 25 of the Yankee dryer installed in the hood 26.
  • the paper is dried while being held by the rotary drum 25 and conveyed.
  • the position where the binder is supplied in the spray part may be a position between the first and second dry parts 17 and 24.
  • the position above the upper conveyor belt 20 the first and second dry parts shown in FIG. 12. You may make it spray a binder from the arrow position between 17 and 24). Further, the binder may be sprayed from above (the arrow position on the right side of the second dry part 24 shown in FIG. 12) on the paper after being dried by the second dry part 24.
  • the direction in which the binder is sprayed between the first and second dry parts 17 and 24 and after the second dry part 24 is not limited to the upper direction, and may be from the lower side or from the upper and lower sides.
  • the fiber orientation in the paper making process, adjustment is performed so that the ratio of vertical and horizontal fiber orientation (vertical / horizontal) of the base paper sheet is 0.8 to 2.0, preferably 1.0.
  • the fiber orientation can be adjusted, for example, by adjusting the angle at which the papermaking raw material is supplied to the wire part in a paper machine.
  • the angle at which the papermaking raw material is supplied can be determined, for example, by adjusting the slice opening degree of the head box. Or it is good also as adjusting fiber orientation by giving a vibration in the direction orthogonal to the conveyance direction (running direction) of a paper machine.
  • the basis weight is preferably about 15 to 75 gsm.
  • the basis weight of the ply-processed sheet containing the water-soluble binder (continuous water-decomposable sheet 1D) is about 30 to 150 gsm.
  • the basis weight is based on JIS P 8124.
  • the continuous dry base paper 1A becomes a ply-processed hydrolyzed paper through a ply processing step (S2), a solution application step (S3), a drying step (S4), and a slit / winding step (S5), which will be described later.
  • the toilet cleaner 100 is processed through an embossing process (S6) and a finishing process (S7).
  • the ply processing step (S2) of this embodiment will be described.
  • the continuous dry base papers 1A and 1A continuously fed from the raw roll 1 are ply processed along the continuous direction to form a ply continuous sheet 1B. It is supplied to the mating unit 2.
  • the overlapping portion 2 is composed of a pair of rolls, and plies each continuous base paper 1A, 1A to form a ply continuous sheet 1B subjected to ply processing.
  • the continuous dry base papers 1A and 1A may be lightly fastened with pin embossing (contact embossing) so that they are not easily displaced.
  • the binder solution contains carboxymethyl cellulose (CMC) as a water-soluble binder.
  • CMC carboxymethyl cellulose
  • the concentration of carboxymethylcellulose in the binder solution is 1 to 30% by weight, preferably 1% by weight or more and less than 4% by weight.
  • the degree of etherification of CMC is desirably 0.6 to 2.0, particularly 0.9 to 1.8, and more preferably 1.0 to 1.5.
  • the expression of water disintegration and wet paper strength is very good.
  • CMC can use a water swelling thing. This demonstrates the function of tying together the fibers constituting the sheet while remaining unswelled by crosslinking of specific metal ions in the chemical solution, and can exhibit strength as a wiping sheet that can withstand cleaning and wiping operations.
  • Ingredients other than carboxymethylcellulose in the binder solution include polyvinyl alcohol, starch or derivatives thereof, hydroxypropylcellulose, sodium alginate, tolton gum, guar gum, xanthan gum, gum arabic, carrageenan, galactomannan, gelatin, casein, albumin, pull plan, poly Examples thereof include binder components such as ethylene oxide, viscose, polyvinyl ethyl ether, polyacrylic acid soda, polymethacrylic acid soda, polyacrylamide, hydroxylated derivatives of polyacrylic acid, and polyvinylpyrrolidone / vinylpyrrolidone vinyl acetate copolymer.
  • binder components such as ethylene oxide, viscose, polyvinyl ethyl ether, polyacrylic acid soda, polymethacrylic acid soda, polyacrylamide, hydroxylated derivatives of polyacrylic acid, and polyvinylpyrrolidone / vinylpyrrolidone vinyl acetate copolymer.
  • a water-soluble binder having a carboxyl group is an anionic water-soluble binder that easily forms a carboxylate in water.
  • examples thereof include polysaccharide derivatives, synthetic polymers, and natural products.
  • the polysaccharide derivative include a salt of carboxymethyl cellulose, carboxyethyl cellulose or a salt thereof, carboxymethylated denven or a salt thereof, and an alkali metal salt of carboxymethyl cellulose is particularly preferable.
  • Examples of the synthetic polymer include a polymer or copolymer salt of an unsaturated carboxylic acid, a salt of a copolymer of an unsaturated carboxylic acid and a monomer copolymerizable with the unsaturated carboxylic acid, and the like.
  • Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, maleic acid, and fumaric acid.
  • Examples of monomers that can be copolymerized with these include esters of these unsaturated carboxylic acids, vinyl acetate, ethylene, acrylamide, and vinyl ether.
  • Particularly preferred synthetic polymers are those using acrylic acid or methacrylic acid as the unsaturated carboxylic acid.
  • polyacrylic acid polymethacrylic acid, acrylic acid-methacrylic acid copolymer salt, acrylic acid or methacrylic acid.
  • examples thereof include a salt of a copolymer of an acid and an alkyl acrylate or an alkyl methacrylate.
  • natural products include sodium alginate, xanthan gum, gellan gum, tarragant gum, pectin and the like.
  • the solution application step (S3) of this embodiment will be described.
  • the solution application step (S3) as shown in FIG. 6, two fluids are formed on both outer surfaces of the ply continuous sheet 1B (the surfaces on which the continuous dry base papers 1A and 1A do not face each other when the continuous dry base papers 1A and 1A are plyed).
  • the above-mentioned binder solution is sprayed by the spray nozzles 3 and 3 of the system or the one-fluid system to generate the continuous sheet 1C.
  • the ply continuous sheet 1B immediately after the ply processing in the ply processing step is merely overlapped with the continuous dry base papers 1A and 1A.
  • the binder solution is sprayed from both sides of the ply continuous sheet 1B.
  • 3 is substantially the same as the case where the binder solution is applied in a state where the continuous dry base papers 1A and 1A are separated, the binder solution penetrates in the thickness direction, and the sheets adhere to each other during conveyance. It penetrates further during crimping in the slit and winding process.
  • a spraying method of a binder solution you may make it spray the above-mentioned binder solution on the one outer surface of the ply continuous sheet 1B.
  • the above-described primary raw rolls 1 and 1 are fed from the two-fluid type spray nozzle to the outer surface (the surface where the sheets do not face each other) of at least one of the continuous dry base papers 1A and 1A fed from the primary raw rolls 1 and 1 respectively.
  • the two-fluid spray nozzle 3 is a spray nozzle that mixes and sprays compressed air and liquid divided into two systems, compared to a one-fluid spray nozzle that sprays compressed liquid alone, The liquid can be sprayed finely and uniformly.
  • a binder solution viscosity 400 to 1200 MPa.s
  • injection pressure 1.5 MPa or more
  • a binder solution (viscosity 400 to 1200 MPa.s) is applied to the outer surface of each ply-processed ply continuous sheet 1B at an injection pressure of 1.5 MPa or less.
  • the binder solution is easily impregnated in the thickness direction of the sheet, and the binder solution is easily applied uniformly on the sheet surface.
  • the toilet cleaner 100 is centered in the thickness direction (when applied on both sides) or non-coated with the binder solution (when applied on one side). Since the content of the water-soluble binder increases as it goes from the surface to the application surface of the binder solution, the surface strength can be improved while ensuring water disintegration, and the toilet cleaner 100 is less likely to be damaged even when rubbed strongly. Can be manufactured.
  • the drying step (S4) of this embodiment will be described.
  • the insoluble liquid in the binder solution of the continuous sheet 1C is evaporated to fix the active ingredient, particularly CMC, to the fibers.
  • the fixing amount of CMC decreases toward the inside in the thickness direction. Therefore, when the chemical solution is impregnated in the finishing step (S7) described later, the cross-linking reaction is less likely to occur toward the inner side in the thickness direction, and since there are many voids, the surface strength of the sheet is improved while being flexible. Can be suppressed.
  • the drying equipment 4 a hooded dryer equipment that blows hot air on the continuous sheet 1C to dry it can be used.
  • a press roll or a turn roll may be installed, and the continuous sheet 1C may be passed through the press roll or the turn roll before the drying step (S4).
  • an infrared irradiation facility may be used as the drying facility.
  • a plurality of infrared irradiation units are arranged in parallel in the conveying direction of the continuous sheet 1C, and drying is performed by irradiating the continuous sheet 1C to be conveyed with infrared rays. Since moisture is generated by infrared rays and dried, uniform drying is possible as compared with a dryer using hot air, and wrinkles can be prevented from occurring in the subsequent slit / winding process.
  • the slit / winding step (S5) of this embodiment will be described.
  • the slit / winding step (S5) in order to use the ply-processed continuous water-decomposable sheet 1D with an off-line processing machine, it is dried in the drying step (S4) and the CMC is fixed.
  • the illustrated continuous water-decomposable sheet 1D is slit to a predetermined width by the slitter 5 while adjusting the tension, and wound by the winder facility 6.
  • the winding speed is appropriately determined in consideration of the ply processing step (S2), the solution application step (S3), and the drying step (S4).
  • the continuous water-decomposable sheet 1D subjected to the ply process is pressure-bonded, whereby the continuous water-decomposable sheet 1D is more integrated and becomes a sheet corresponding to one sheet.
  • the embossing process (S6) of this embodiment will be described.
  • the embossing roll 12 has an embossing process that forms a predetermined shape on the entire surface of the continuous water-decomposable sheet 1D fed from the secondary raw roll 11 by the embossing roll 12. Applied. This embossing is performed for the purpose of improving the strength, bulkiness, wiping property and the like of the sheet, as well as the design.
  • the finishing process (S7) of this embodiment will be described.
  • the finishing process (S7) as shown in FIG. 7, in the finishing equipment 13, the embossed sheet 1E is cut, the cut sheets are folded, and the chemicals are applied to the folded sheets. Impregnation and packaging of each sheet impregnated with the chemical solution are performed in a series of flows.
  • the cross-linking agent contained in the chemical solution is preferably a polyvalent metal ion.
  • the use of one or more polyvalent metal ions selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt, and nickel allows the fibers to be sufficiently bonded to withstand use.
  • the toilet cleaner 100 is manufactured through the above steps.
  • a ply processing step of plying a plurality of base papers not containing a water-soluble binder A solution application step of applying a binder solution to the ply-processed sheet; A drying step of drying the sheet provided with the binder solution; A winding step of slitting and winding the sheet dried in the drying step to a predetermined width; Including
  • the binder solution is sprayed to the corresponding outer surface from spray nozzles provided corresponding to both outer surfaces of the ply-processed sheet.
  • a plurality of base papers that do not contain a water-soluble binder may be ply-processed, and a plurality of base papers that contain a water-soluble binder may be ply-processed.
  • Example Material of base paper 100% pulp Weighing: 45 g / m 2 Number of plies: 2 plies Water-soluble binder and its content: CMC 1.2 g / m 2 (spray coating) Chemical liquid components: surfactant, glycol ether, disinfectant, fragrance, water, etc. Chemical liquid impregnation rate: 200% Embossing: Comparative Example 1 Base material: 100% pulp Weighing: about 45 g / m 2 Number of plies: 2 Water-soluble binder and its content: CMC 1.0 g / m 2 Chemical liquid components: surfactant, glycol ether, fragrance, water, etc.
  • Chemical liquid impregnation rate 200% Embossing: Comparative example 2 Base material: 100% pulp Weighing: 30 g / m 2 Number of plies: 3 Water-soluble binder and its content: PVA 1.5 g / m 2 Chemical solution components: surfactant, ethanol, disinfectant, fragrance, water, etc. Chemical solution impregnation rate: 200% Embossing: Yes
  • the test piece (toilet cleaner) is 75 mm wide x 240 mm long without peeling off the ply, and is cut in the MD and CD directions, folded in three so that both end regions in the width direction overlap, and the measurement part is a Gakushin friction Rub with a fastness tester, and measure the number of times when damage such as fluffing or tearing is confirmed on the paper surface. This measurement is performed three times each in the MD direction and the CD direction, and the average of the measured values for each three times is calculated.
  • the test conditions with the Gakushin type friction fastness tester are as follows.
  • Friction element Shape ⁇ 20mm ⁇ R50mm Load 200gf (including white cotton cloth stopper and arm) Load per unit area 50 gf / cm 2 (load 200 gf / contact area 4.0 cm 2 ) PP band (Sekisui Jushi Corporation part number 19K) (Width 15mm x Length 60mm)) Fix one piece to the friction element with screws so that no gaps or wrinkles occur.
  • Test piece (toilet cleaner): width 25mm (ply is not peeled off and width 75mm) Folded in three) x length 240mm (sample stage side)
  • Test procedure (1) Mount the test piece on the sample stage so as not to loosen. (2) Gently lower the friction element onto the sample table. (3) Start test by pressing start SW. -Judgment method: The state of the test piece was confirmed by swaying 10 times each, and the number of times when damage such as fluffing and tearing was visually confirmed on the paper surface was measured.
  • Test piece for bending resistance
  • the test piece (toilet cleaner) is cut in the MD direction with a width of 25 mm and a length of 120 mm without peeling off the ply, and is extruded in the direction of the slope of the cantilever type tester based on the cantilever method (JIS L1913: 2010). Measure the distance that was pushed out when one end of the contacted with the slope. This measurement is performed three times, and the average of the three measurement values is calculated.
  • Test procedure (1) Place the short side of the test piece on the base of the scale on a smooth horizontal surface with a 45 ° bevel at one end. (2) Gently slide the test piece in the direction of the slope, and read the position of the other end with a scale when the center point of one end of the test piece touches the slope.
  • the examples have a stronger surface strength than Comparative Examples 1 and 2, and damage such as fuzz and tear when rubbed strongly in an environment assuming actual use. It turned out that it is hard to occur.
  • the average value in both the MD direction and the CD direction exceeds the numerical value (40 times) that is a measure of whether or not the toilet cleaner can withstand during actual use. I knew that I could endure it.
  • Comparative Examples 1 and 2 the average value in both the MD direction and the CD direction was lower than the numerical value that is the standard, and it was found that the comparative examples 1 and 2 could not withstand the actual use.
  • the toilet cleaner is wiped by allowing the user to determine which direction the CD direction of the toilet cleaner is (for example, an arrow indicating the CD direction is attached to the toilet cleaner paper). At this time, the user can use the toilet cleaner by matching the stroke direction of the hand with the CD direction, so that the toilet cleaner can be further prevented from being broken during the cleaning.
  • the toilet cleaner has a water decomposability by setting the surface strength value that is a measure of whether or not the toilet cleaner can withstand actual use to 40 times or more in the above test. It is proved that it is difficult to tear even if rubbed strongly while ensuring.
  • the numerical value corresponding to each use evaluation shown in Table 1 displays the ratio of the user who performed the said evaluation in percentage.
  • the average shown in Table 1 is 5 points for “satisfied”, 4 points for “slightly satisfied”, 3 points for “neither”, 2 points for “slightly dissatisfied”, and 1 point for “satisfied”. It is the value obtained by multiplying the score corresponding to the evaluation by the number of responses of the evaluation and dividing the sum by the number of respondents.
  • Example 1 The conditions of Example 1 were as follows: raw material 100% pulp, weighed 45 g / m 2 , ply number 2 plies, water-soluble binder CMC, CMC content 1.2 g / m 2 ( According to a doctor chamber method), the chemical component is surfactant, glycol ether, disinfectant, fragrance, water, etc., the chemical solution impregnation rate is 200%, and embossing is present.
  • Example 2 The execution conditions of Example 2 were as follows: raw material 100% pulp, weighing 45 g / m 2 , ply number 2 plies, water-soluble binder CMC, CMC content 1.0 g / m 2 (spray coating) ),
  • the chemical component is a surfactant, glycol ether, disinfectant, fragrance, water, etc., the impregnation rate is 200%, and embossing is present.
  • Example 3 The working conditions of Example 3 were as follows: raw material 100% pulp, weighed 45 g / m 2 , ply number 2 plies, water-soluble binder CMC, CMC content 1.0 g / m 2 (doctor chamber (Depending on the system), the chemical component is a surfactant, glycol ether, disinfectant, fragrance, water, etc., the impregnation rate is 200%, and embossing is present.
  • Example 4 The conditions of Example 4 were as follows: raw material 100% pulp, weighed 45 g / m 2 , ply number 3 plies, water-soluble binder CMC, CMC content 1.2 g / m 2 (spray coating) ),
  • the chemical component is a surfactant, glycol ether, disinfectant, fragrance, water, etc., the impregnation rate is 200%, and embossing is present.
  • Example 5 The execution conditions of Example 5 were as follows: raw material 100% pulp, weighed 30 g / m 2 , ply number 3 plies, water-soluble binder CMC, CMC content 1.2 g / m 2 (spray coating) ),
  • the chemical component is a surfactant, glycol ether, disinfectant, fragrance, water, etc., the impregnation rate is 200%, and embossing is present.
  • the test results regarding the abrasion resistance of Examples 1 to 5 described above are 53 times for the average value in the MD direction of Example 1, 56 times for the average value in the CD direction, and 45 times for the average value in the MD direction of Example 2.
  • the average value in the CD direction is 48 times
  • the average value in the MD direction in Example 3 is 50 times
  • the average value in the CD direction is 53 times
  • the average value in the MD direction in Example 4 is 50 times
  • the average value in the MD direction of Example 5 was 50 times
  • Examples 1 to 5 have a surface strength stronger than that of Comparative Examples 1 and 2 as in the above-described Examples, such as fuzz and tear when rubbed strongly in an environment assumed for actual use. It was found that damage was difficult to occur.
  • the above-mentioned test results regarding the bending resistance of Examples 1 to 5 were 30 mm for Example 1, 28 mm for Example 2, 28 mm for Example 3, 33 mm for Example 4, and 28 mm for Example 5. That is, it was found that in Examples 1 to 5, the length of the test piece moved was shorter than that of Comparative Example 1 and was more flexible than Comparative Example 1 as in the above Examples.
  • the embossed EM11 in which the bulging part PR21 has a curved shape and the embossing EM12 in which the bulging part PR22 has a flat shape are illustrated. It is not necessarily limited to this shape, for example, the bulging part of embossing EM11 and embossing EM12 may be a planar shape from which height differs. Further, for example, the bulging portion of the emboss EM 11 may be a flat shape, and the bulging portion of the emboss EM 12 may be a curved shape.
  • first embossing and second embossing there are two types of embossing (first embossing and second embossing) in which the shape of the bulging part is not the same shape, and the second embossing is arranged around the first embossing. If it exists, the shape of the bulging portion of each emboss may be any shape.
  • the embossed EM12 having a flat bulge is disposed between the embossed EM11 having a curved bulge, but the embossed EM11 intersects each other. Also good.
  • all the embosses EM11 and EM12 are convex in the front direction of the drawing in FIG. 1, but the embossments EM11 and EM12 that are convex in the front direction of the drawing and the front direction of the drawing.
  • the concave embosses EM11 and EM12 may be alternately arranged.
  • embosses EM11 and EM12 solid line portions convex in the front direction of FIG. 8 and embossments EM11 and EM12 (broken line portions) concave in the front direction of FIG.
  • embossments EM11 and EM12 broken line portions concave in the front direction of FIG.
  • the bulging portion PR21 of the emboss EM11 and the bulging portion PR22 of the EM12 are formed as a continuous embossing EM21 by closely adhering to each other.
  • the bulging portion PR21 and the bulging portion PR22 of the EM 12 may be close to each other but not closely attached.
  • the shape of the emboss EM 11 is exemplified as a circular shape or an elliptical shape, but the emboss shape may be any shape such as a square or a polygon.
  • the heights HT21 and HT22 of the bulging portions of the embosses EM11 and EM12 in FIG. 3 are preferably 0.40 mm to 0.75 mm, for example.
  • the height of the bulging portion of the emboss can be measured by measuring the surface in 3D with a Keyence digital microscope.
  • the height is less than 0.40 mm, the friction at the time of wiping becomes strong and difficult to wipe, and if the height exceeds 0.75 mm, the shapes of the embosses EM11 and EM12 are liable to break during packaging. It looks bad.
  • the embossing pattern of the toilet cleaner is not limited to the above pattern.
  • 9 is a plan view of the toilet cleaner 101 in which only the embossing pattern of the toilet cleaner 100 is changed
  • FIG. 10 is an enlarged view of a portion AA of FIG. 9
  • FIG. 11A is an end view of a cut section BB of FIG.
  • FIG. 11B is an end view taken along the line CC of FIG.
  • the concave portion e2 has a shape obtained by inverting the convex portion e1.
  • the convex portions e1 and the concave portions e2 are alternately arranged as an example, and this row forms an emboss pattern in which the rows are arranged in multiple rows and the convex portions e1 and the concave portions e2 in adjacent rows are shifted from each other by a half pitch.
  • the convex portions e1 and the concave portions e2 are alternately formed both in the vertical direction and in the horizontal direction, so that the wiping property of dirt is improved compared to the embossed pattern in which the convex portions and the concave portions are arranged in a line. Can be made.
  • the shape of the convex part e1 and the recessed part e2 is not specifically limited, Circular, an ellipse, a polygon etc. are used. It is good also as what combined each shape.
  • the binder solution is applied by a spray method.
  • the doctor chamber method for the continuous dry base paper 1A continuously fed from the primary original roll 1 ( Transfer equipment comprising two printing plate rolls paired with one backup roll, an anilox roll paired with each printing plate roll, and a doctor chamber for applying a chemical to each anilox roll), and / or 3 roll system (two printing rolls paired with one backup roll, anilox roll paired with each printing roll, dip roll for applying chemicals to each anilox roll, and dip roll
  • the binder solution may be applied by a transfer facility equipped with a pan for applying a chemical solution to .
  • the binder solution is transferred from the provided printing machine to the corresponding base paper.
  • the binder solution is applied to at least one surface of the base paper as the front and back surfaces of the water-decomposable sheet, and the water-soluble binder is water-soluble. You may make it provide a binder solution with respect to at least any one surface of the base paper used as the surface of a water-decomposable sheet and a back surface among several base paper containing a binder.
  • the chemical solution is applied by the doctor chamber method because the chemical solution can be transferred more uniformly and stably in the width direction than the three-roll method. Furthermore, it has the drying process which dries the continuous paper to which the chemical
  • the doctor chamber method will be described in detail below as an example.
  • the coating processing speed when applying the binder solution is 30 to 100 m / min, more preferably 50 to 80 m / min. If it is less than 30 m / min, the crepe stretches before being dried, and there is a problem that it is difficult to process in a subsequent process. On the other hand, when the amount exceeds 100 m / min, a sufficient transfer amount cannot be obtained, or variation in wet strength and water disintegration occurs due to variation in the coating amount in the width direction.
  • the diameter of the backup roll is suitably 250 to 420 mm.
  • the diameter is less than 250 mm, the contact area between the printing plate roll and the backup roll is reduced, and stable coating cannot be performed. Even if the diameter exceeds 420 mm, there is no problem in manufacturing, but it is not preferable because the equipment cost is excessive.
  • the printing plate roll is provided with an anilox roll for delivering a binder solution thereto, and a doctor chamber for delivering the binder solution to the anilox roll for application thereto is provided.
  • a snake pump that delivers the binder solution to the doctor chamber is installed on both the feed and return to feed the anilox roll solution pan. High binder solution transfer is possible.
  • the continuous dry base paper 1A fed out from the primary raw roll 1 is wound around a backup roll through an appropriate guide roll, and given appropriate tension and surface stability. Then, the binder solution is roll-transferred by the printing plate roll to the continuous dry base paper 1A wound around the backup roll.
  • the printing plate roll is a solid roll with no concave grooves, and a binder solution is applied to the entire continuous dry base paper 1A as in solid printing.
  • the seamless roll used as the printing plate roll is formed by winding a rubber plate around a sleeve of a type roll, putting it in a kettle, performing overheating welding, and polishing.
  • the rubber plate used as the material can be selected in material, hardness, color and the like according to a predetermined purpose.
  • the number of lines and the cell capacity of the anilox roll delivering the binder solution to the printing plate roll are 60 to 120 lines / inch and the cell capacity is 40 to 90 ml / m 2 depending on the concentration of the binder solution. Is desirable. If the number of lines is less than 60 lines / inch, an excessive binder solution is transferred to the printing plate roll, and as a result, the binder solution may be applied to the continuous dry base paper 1A with unevenness from the printing plate roll. Rise. On the other hand, when the number of lines exceeds 120 lines / inch, it becomes difficult to deliver a sufficient amount of the binder solution to the entire peripheral surface of the printing plate roll.
  • the continuous dry base paper 1A to which the binder solution is applied (transferred) as described above targets only the base paper that is the uppermost layer or the lowermost layer when plying. That is, for example, in the case of three-ply processing, the binder solution is not applied (transferred) to the continuous dry base paper 1A serving as the middle layer.
  • the binder solution is transferred to the continuous dry base paper 1A, that is, the binder solution is transferred to the continuous dry base paper 1A before the ply processing step. Thereafter, the binder solution may be transferred to the ply continuous ply sheet 1B.
  • a ply processing step of plying a plurality of base papers not containing a water-soluble binder, and a ply-processed sheet A solution application step for applying (transferring) the binder solution to the sheet, a drying step for drying the sheet provided with the binder solution, and a winding step for slitting and winding the sheet dried in the drying step to a predetermined width. And the solution applying step transfers the binder solution to a corresponding outer surface from a printing machine provided corresponding to the outer surface of at least one of the ply-processed sheets.
  • a plurality of base papers that do not contain a water-soluble binder may be ply-processed, and a plurality of base papers that contain a water-soluble binder may be ply-processed.
  • a binder solution with high viscosity can be apply
  • the binder surface may be coated on the sheet surface by a coater for hot melt resin coating. In such a case, it is possible to fix the CMC only on the sheet surface.
  • the binder solution is applied in the solution application process of the solution application equipment shown in FIG. 6, but the binder solution may be applied in the paper making process.
  • the paper making process includes making a plurality of base papers, and the paper making process is performed on wet paper being made. To apply a binder solution.
  • the wet paper formed by the paper making net is transported on the felt, and the wet paper on the felt is transferred to the Yankee dryer via the touch roll.
  • the wet paper is dried to obtain a base paper in the process of being attached and conveyed, and the binder solution is sprayed from the spray nozzle onto the wet paper immediately after being transferred onto the above-mentioned Yankee dryer.
  • the binder solution is applied even in the paper making process, the strength of the entire water-decomposable sheet obtained can be increased, and the surface of the water-decomposable sheet can be obtained by further applying the binder solution in the subsequent solution applying process. The strength can be further increased.
  • CMC is used as the water-soluble binder, but polyvinyl alcohol (PVA) may be used.
  • PVA polyvinyl alcohol
  • the present invention can be suitably used in the field of manufacturing a water-decomposable sheet.

Landscapes

  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Paper (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Abstract

Selon l'invention, dans un dispositif de nettoyage de toilettes (100), une feuille de papier de base multicouche sensiblement dispersible dans l'eau contenant une pulpe et un liant soluble dans l'eau est imprégnée d'un agent chimique aqueux, le poids de base de la multicouche étant de 30 à 150 gsm. Ledit dispositif de nettoyage de toilettes (100) est configuré de telle sorte que, lorsqu'un test de résistance à l'abrasion est réalisé trois fois, chacun dans la direction MD et la direction CD, à l'aide d'un testeur de résistance au frottement de type oscillant dans lequel une bande PP est utilisée comme oscillateur, et les moyennes des valeurs de mesure provenant de chacun des tests sont calculées, chacune des valeurs moyennes est égale ou supérieure à 40 fois.
PCT/JP2016/060518 2015-06-16 2016-03-30 Feuille hydrolysable WO2016203809A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015121313A JP2017006157A (ja) 2015-06-16 2015-06-16 水解性シート
JP2015-121313 2015-06-16
JP2015-131770 2015-06-30
JP2015131770A JP6193310B2 (ja) 2015-06-30 2015-06-30 水解性シート

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WO2016203809A1 true WO2016203809A1 (fr) 2016-12-22

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003183971A (ja) * 2001-12-12 2003-07-03 Asahi Kasei Corp 複合シートおよびこれを用いた清拭用部材
JP2011030793A (ja) * 2009-07-31 2011-02-17 Daio Paper Corp 清掃用水解性ウェットシート

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003183971A (ja) * 2001-12-12 2003-07-03 Asahi Kasei Corp 複合シートおよびこれを用いた清拭用部材
JP2011030793A (ja) * 2009-07-31 2011-02-17 Daio Paper Corp 清掃用水解性ウェットシート

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