CA2004296A1 - Water-disintegrable cleaning sheet - Google Patents
Water-disintegrable cleaning sheetInfo
- Publication number
- CA2004296A1 CA2004296A1 CA 2004296 CA2004296A CA2004296A1 CA 2004296 A1 CA2004296 A1 CA 2004296A1 CA 2004296 CA2004296 CA 2004296 CA 2004296 A CA2004296 A CA 2004296A CA 2004296 A1 CA2004296 A1 CA 2004296A1
- Authority
- CA
- Canada
- 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.)
- Abandoned
Links
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
Landscapes
- 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)
Abstract
ABSTRACT OF THE DISCLOSURE
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 metallic ion selected from the group consisting of ions of alkaline earth metals, manganese, zinc, cobalt, and nickel; and an aqueous cleaning agent containing an organic solvent, is disclosed. The sheet satisfies both water disintegrability and strength even when cotained a cleaning agent of high water content.
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 metallic ion selected from the group consisting of ions of alkaline earth metals, manganese, zinc, cobalt, and nickel; and an aqueous cleaning agent containing an organic solvent, is disclosed. The sheet satisfies both water disintegrability and strength even when cotained a cleaning agent of high water content.
Description
;~0 ~9~;
WATER-DISINTEGRABLE CL~ANING S~EET
FIELD OF THE ~i2NTION
Th s inven_ion relates to a water-disintegrable _leaning sheet, and more particularly to a water-dislntegrable cleaning sheet comprising a specific water disintes-able paDer having incorporated or impregnated thereinto an a~ueous cleaning agent containing an organic solvent, which is suitable for cleaning or sterilization o. floors or walls Oî rooms or toilet rooms, furniture, toilet seats, toilQt basins, etc. or useful as toilet paper, and can be thrown into flushing water.
B~CXGROUND OE THE_INVENTION
Water-disintegrable papers or cleaning goods made of a chemicai-&or.taining wa.er-disintegrable paper which can be ~hrown into water have been used as toilet paper or for cleaning a toilet room or toilet equipment. Conventio~a water-disintegrable paper usually contains a dry s~rength agent such as polyvinyl alcohol, carboxymethyl cellulose, and cationic starch, for enhancing dry paper strength without impairing water d:isintegrability.
However, 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 w th a cleaning asent for cleaning or sterilization of floors, walls, furniture, and toilet equipment or for use as ~0~296 toilet paper, the cleaning agent to be combined with has been limiteà to liquid substances or chemicals having no or very low wa~er content.
In using z cleaning agenL cS high water content, it has beer necessary that the cleaning agent should be foamed and sp~ayQd on a water-disintegrable pa?er i.~ediately befo-e use and be used without delay in order to suppress water absorption iII ~0 paper and to pr2vent strength reduction.
Polyacrylamiàe or the like dry strength agent endows paper with strength enough lo withstand use even with a small amount of water being impregnated in the paper sheet, but tends to impair water di~inteyrability of the sheet.
Hence, 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.
It has been proposed to spray a binder solution containing polyvinyl alcohol and borax on a paper sheet followed by drying by heat whereby polyvinyl alcohol and borax are reacted to provide water-disintegrable paper having temporary water resistance, which is useful as absorbent materials such as napkin or diaper, as disclosed in JP-A-47 9486 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"3. Further, JP-A-61-296159 discloses a water-disintegrable paper in which an 200 ~296 aqueous solution containing salts such as potassium salt, calciu~ salt nd barium sa't, is impregnated into a fiorous sheet contain ng carrageenan as a bin~er, which is used for a wetting tissue p~per. F~rthermore, JP-A-55-lQ3393 ~isclGses a method for preparing a paper having high strength in a dry state while lcw in we~ ctate~ wh ch comp~lsec tre~ting 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. These water-disintegrabl~ papers, however, does not withstand the mechanical force in cleaning work when impregnated with water.
S~Y OF THE INVENTION
An object of the present invention is to provide a wate--disinteg able cleaning sheet containing a claaning agent, which has strength enough for cleaning use under a mechanical forca while retaining satisfactory water disintegrability.
As a _esult of extensive invastigations, 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.
ZOO~X96 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 carboxyi group; at least one polyvalent metallic ion selected from the group consisting of io~s of al~zlina eart~ me'als, manganese, zirc, cobalt and nickel; and an a~ueous cleaning agent containing an organic solvent.
DETAILED DESC~IPTION OF THE INVENTION
Water-dispercible fibers which constitute a water-disintegrable cleaning sheet of the present invention are not particularly restricted as long as they ars fibrous materials substantially dispersible in water. Examples of suit~ble ~ater-dispersible fibers are wood pulp fibe,s, non-wood vegetable fibers, and synthecic fibers such as rayon fibers and polyester fibers.
Water-soluble binders having a carbo~yl group which can be used in the present invention include polysaccharide derivatives, synthetic high polymers, and naturally-occurring substances.
Examples of suitable polysaccharide derivatives include carboxymethyl cellulose, carboxyethyl cellulose, and carboxymethylated starch, with carboxymethyl cellulose being preferred.
Examples of suitable synthetic high polymers include homopolymers of an unsaturated carboxylic acid, copolymers of Z1)0~96 two or more unsatura,ed carboxylic acids, and copolymers of an unsaturated carboxylic acid and other copolymeriæable monomer.
Specific examples of suitable Insaturated carboxylis acids are acrylic acid, methacrylic ac~d, itaconic acid, crotonic acid, maleic anhydride, maleic acid, ~nd fumaric acid. Monomers copolymerizable with the unsa~urated carboxylic acid include esters of these ur.saturated carbox-fllc acids, vinyl aceta~e, olefins (e.g., etilylene~, acrylamide, and vinyl ether.
Preferred of these high polymers are those contain~ng an acryl c 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.
Examples of suitable naturally-occurring water solub'e binders are alginic acid, xan~han g-~., arabic gum, tragacanth aum, and pectin.
Among these water-soluble binders, carboxy~ethyl cellulose is particl1larly 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 cleanin~ sheet of the present in-~ention (hereinafter refexred to as an 'essential metallic ion-) is at 29~
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.
Of ~he metal'ic ions as desc_ibed abo-ve, calcium, strontium, barium, zinc, cobalt, and nickei ions are preferred -rom the standpoi~t of ,ufficient st ength fcr clearing ~-ork of the cleaning sheet of the present invention.
Monovalent metallic ions other than Ihose described above satisfy water disintegrability but cannot arford strength withstanding cleaning work. Divalent metallic ions other than those described above, e.g., Cu2', Fe2+ or Sn2+, and trivalent metailic ions other than those described above, e.g., Fe~ or A~3+, afford strength enough for cleaning work but do not sa~isfy water disintegrability.
The essential metallic ion is preferably used in an amount of al least 1/4 mol, more preferably at least 1/2 mol, per mol of carboxyl group of the water-soluble binder.
The essential metallic i~n is incorporate~ into the water-disintegrable cleaning sheet of the present invention in the forms:
(A) an intermolecular mixed salt of the water-soluble binder formed between the carboxyl group thereof and (a) an alkali metal and (b) at least one selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt and nickel; and/or ;~0~296 (B) at least one of water-soluble salts such as hydroxides, chlorides, sulfates, nitrates, carbonates, formates and acetales, of at least one selected from the group consist~ng of an alkaline earth metal, mangznes~, zinc, cobal and nickel.
In the inter~olecu7~r rrlixe-~ sal~ zs ment-oned abov2 as form (A), a molar ratio of (a)~(b) is in the range of from l/0.01 to 1/10, preferably from l/0.05 to 1~3.
When the metal ion is incorporated into the cleaning sheet of the present invention in the form (B) above, an alkali metal salt of the binder which formed a salt between the carboxyl group and an alkali metal such as sodium and po~assium, is preferably used as a water-soluble binder.
The above forms (A) and (B) of th~ essential metallic ion are used each aione, or combination thereof to incorporate the essential metallic ion into the cieaning sheet of the present inv2ntion.
The wzter-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. For example, 2C0~29~
when the essential metallic ion is incorporated in the water-disintegrable paper in the form (B) above, the water-disintegrable pape- can be obtained by spraying or coating an aqueou~ solution of the waEer-soluble salt of at least one selected from the group consistins of alkaline earth metals, man~anese, zinc, ccbal~ and nickei, to a dry web conlzini..g carboxyl-containing water-soluble binder, and then drying. The paper containing carboxyl-cont2ining water-~oluble binder is obtained by adding a carboxyl-con~aining water-soluble binder into an aqueous dispersion of water-dispersible fibers and then sub~ecting 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 ODtaine~ by spraying or coating a carboxyl-cont2ining water-soluble b nder and an aqueous solution containing water-soluble salt of at least one selected from the g-oup consisting of an alkaline earth metal, manganes , zinc, cobalt and nickel, and then drying.
When the essential metallic ion is incorporated in the water-disintegrable paper iIl the form (A) above, namely a form of an intermolecular mixed salt of the water-soluble binder, 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 2(~0 ~296 salt binder to a web composed of water-dispersible fibers and then drying.
Further, when the essential metallic ion is incorporated in the water-disintegrable paper in combination of forms (~ and (~) above, the above-ment-oned incorporating prGcesscs are optionally comb1ned to obtain _he paper.
Processes for producir.g the water-disintegrable cleaning sheet of the present invention aIe not particularly restric'ed, and it can be produced, for ex2mple, by incorporating or impregrating an aqueous cleaning agent into the water-disintegrab~e paper as described above, or adding an aqueous cleaning agent into the water-disintegrable pzper 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. In such production, 1he 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.
_ 9 _ Z(~O~Z96 The aqueous cleaning agent which is incorporated in the cleanir.g sheet essentially contains an organic solvent fo-obtainlng nigh strength withstanding cleaning ~-ork. Suitable organ-c solvents are watel-compatible (cr water-soluble) solvents typically including mor.ohydric lower alcohols such as e'hanol, meth_nol, and propar.ol; g]ycols such 2S 2thylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, buthylene glycol and hexylene glycol; mono- or dlethers of the aforementioned glycols and lower alcohols such as methanol, ethanol and butanol; esters of the aforementioned glycols and lower fatty acids; and poiyhydric alcohols such as glycerine and sorbitol. In using 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, prererably 1 to 2.5 times the weight of water-disintegrable paper.
The content of the organic solvent in th~ aqu20us 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. For sterilization of toilet equipment, etc., cleaning agents rich in organic solvent, e.g., ethanol and isopropyl alcohol, are employed.
For removal of hydrophilic dirt from living rooms, kitchens or toilet rooms, aqueous cleaning agents rich in water are 2(~ 29~
employed. In this case, the water content ranges from 30 to 9S~ by weight, preferably from 40 to 92% by weigh~, more preferably from O0 to 90~ by wei~ht, ard the organic solv~nt conter.t ransQs from 5 to 70% ~y ~eight, preferably fro~ 8 to 60% by weight, more preferably from 1~ to 40~ by weight.
Ir desired, the aqueous cle3r.ing ~gents may furtner contain surfactants, sterilizers, deodorizers, perf~es, and t he like ~ s the s-~rfactants which may be contained in the cleaning agent of the present invention, 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 ato~s or lower alkyl gr.up, sulfcbetaines or hydroxysulfobetaines having alkyl group containing 8 to 22 carbon aioms, and carbobetaines having alkyl group cont~ir.ing 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 alkenyl) succinates containing 6 to 22 carbon atoms, and paraffinsulfonates containing 8 to 22 carbon atoms, as anionic surfactants; polyoxyalkylenes (mainly, polyoxyethylene, 2~0~'36 polyoxypropylene, or a mixture of these), glycol ethers, polyoxyalkylene alkyl phenyl ethers, alkyl glycosides, and sucrose fa~ty acid esters, as nonionic sur actants; quatQrnary a.~monium salts having an aiky-l srcup con.air.ing ~ to 11 carbon atoms, 2S cationic surfactants. These surfactants a--e added into the cleanirg zgents to 're ircGr~C~atQ ir. o wa~er-disintegrable cleaning sheet in an amount of generally from C.i to 5~ by weight.
A cleaning sheet prepared by simply impregnatina water-disintegrable paper containing a carboxyl~containing water-soluble binder with an aqueous solution having dissolved therein the above-dsscribed metallic ion, or by simply incorporating the web composed of water-dispersible fibers with an intermolecular mi~ed 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 forma~ion 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. Further, when spent water-disintegrable paper is discarded into toilet flushing wa~er, etc., the metallic ion and organic solvent in the sheet are diluted with a large quantity of water to make the insolubilized binder water-soluble, thereby maintaining water disintegrability.
~ 3~j As described above, the water-disintegrable cleaning sheet of the present invention, e-~en when using a cleaning agent of high water content, exhibits strength withstanding cleaning work and satisfactory watcr disintegrability in good balance and proàuces great effects as cle~nin~ sheet.
The p~esent invention is now illustrated in greater detail by way of the following Examples, but it should be understood th~t the present invention is not construed as being limited thereto. All the percents, parts, and ratios are given on a wei~ht basLs unless otherwise indicated.
A toilet paper-like water-disint~grable paper sheet having a basis weight of 25 g/m2 was produced from a bleached ~raft pulp of coni,er beaten to a CS~ (Canadian Stand~rd Freeness) of fi80 cc using an ordinary paper machine.
The water-disintegrable paper sheet was sprayed with 3% (corresponding to 0.75 g/m2) of a sodium car~oxymethyl cellulose CMC 2200" (produced by Daisel ~agaku R.R.) in the form of a 1% aqueous solution and dried to obtain a CMC-containing sheet.
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-disinte~rable cleaning sheet.
Z~ Z96 Wet tensile strength, dusting and fuzzing on use, and water disintegrability of the resulting cleaning sheet were evaluated in a~cordance with the following test methods. The results ~btained are shown in Table 1 below.
l. We~ Ter.sile ~trenqth:
A s~rip 25 mm w~de and 100 mm long was cut 01t of the cleaning sheet, and breaXing strength of the strip in the machine direction (~D) 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.
2. Dustinq and Fuzzinq:
The cleaning sheet W2S used for wiping black tiles inclusive of the joints for 5 minutas. Dusti~g on the tiles and fuzzing of the sheet were observed and evaluated according to the following rating system.
o: ~either substantial dusting nor fuzzing was observed.
~: Sligh.t dusting was observed, but fuzzing was not observed.
x: Dusting and fuzzing were observed.
3. Water Disinteqrabilitv:
In l ~-volume beaker was put 500 m~ of water and agitated with a stirrer at 300 rpm.
The cleaning sheet was cut to pieces of 50 mm x 50 mm and put into the water under stirring. After 90 seconds, the ;~0~ 9~;
disintegrated and dispersed state of the sheet was observed and evaluated according to the following rating system, taking co~ercially available toilet paper as a standard having satisf2ctory dispersioility.
o: Satisfacto-y dispersion ~: Sligntly poor disrersion x: Door dispersion COMPARATI~/E ~:XAMPLE 1 A cleaning sheet was produced in the same manner as in Example l, except for using an impregnating solution containing no calcium chloride. The resulting cleaning sheet was ~valuated in the same manner as in Example 1, and -ths results obtained ar~ sho~n in Table l below.
XOO~X9~
Ethanol/hacer (w/w) Example 1 50/50 20/80 10/90 0/100 -Wet Tersile MD CDMD CD MD CD MD CD
StrengthlQ20 620 ~80 '10 370 22~ ~0 28 (g/25mm)`
Dusting and o c o x Fuz7ing Water- o o o o Disintegrability Comparative Example l Wet lensile MD CD MD CD MD CD MD CD
Strength 350 200 90 50 35 20 30 17 (gt25mm) Dusting and Q x x x Fuzzing Watsr- o o o o Disintegrability Each of calcium chloride, bari~m 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.
Each of the resulting water-disintegrable cleaning sheets was evaluat0d in the same manner as in Example 1, and the results obtained are shown in Table 2 below.
ZCi~ 36 COMPA~ATIVE EXAMPLE 2 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 potâssium cnloride, copper sulfGte, ferrous chloride, ferric chloride, stannouC chloride, or aluminum sulf2te.
Each of the resulting sheets was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 2 below.
Z0~ .Z9~, MetallicWet Tensile Dusting Water Ion inStrenqth (g/25mm! and Disinte-SolutionMD CD Fuzzinq Grabili~y Example 2_ Ca2+ 480 310 o o Sr7+ 492 322 o o Ba2 524 340 o o ~n2+ 273 163 o o Zn~+ 472 302 o o Co2+ 396 194 o o Ni2+ 440 276 o o Comparative Example 2 K 42 19 x o Cu2+ 540 348 o x Fe2+ 442 283 o x Sn2+ 480 320 o x Fe3+ 686 390 o x A~3 760 41i o x EXAMPLE_3 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 i.n 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 200~ZI'3~i ratio of 1/4, 1/2, or 1/1 to the carboxylate lon of CMC.
Each of the resulting cleaning sheets was evaluated in the same manner as ir. Example 1, and the rssults obtained are shown in Table 3 below.
~ Tensile Dustlng Ca2+/COO~ strength ~q/~5mm! ar.d Water Molar RatioMD CD Euzzinq Disintearability 1/1 560310 o o 1/2 490290 o o 1/4 345190 o o A web of split and deposited fibers of a conifer fluff pu]p (basis weight: 30 g/m2) was sprayed with ]5% of a sodium salt of an acrylic acid-2-etnylhexyl acrylate copolymer (~3 by mol~, followed by d-ying to obtain a water-soluble bir.der-containing water-disintegrable sheet.
The resl~lting sheet was impregnated with 1.5 t mes the sheet weight of an aqueous clear.ing agent comprising zinc sulfate, polyoxyethylene dodecyl ether (p=8), propylene glycol and water at a ratio of 1/1/15/83 to obtain a water-disintegrable cleaning sheet.
The resulting cleaning sheet was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4 below.
0~9~i COMPARATIVE ~XAMPL~ 3 Thewater-solublebinder-cor.taining-~G er-c sin~egr2ble shee~ as prepared in Example ~ was im2regnated with an a~ueous c1ean7ng ager.t comprising polyox~ethylene dcdecyl ether (p=8~, propylene glycol, and water at a ratio of 1/15/84 in the same manner as in Exampie 4.
The resulting cleaning sheet was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4 below.
T~BLE 4 Net Tensile Example Streng~h (q/2577.7~) Dusting and ~ater No. MD CD Fuzzinq Disintea-ability Example 12O0 280 o o Comparative 15 13 x o ~xample 3 EX~PLE 5 Crepe paper having a basis weight of 25 g/m2 (crepe ratio: 20%) 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 l 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 ~he sheet 20~) ~29~
weight of a cleaning agent comprising a surfactant (Softanol 70), ethanol, and water (1/20/79). The resul~ing cleanir.g sheet was evaluated in the same manne. as in Example 1, znd the results obtained ale shown in Table 5 below.
The C~C-containing crepe paper as described in Exa.~ple 5 was impregnated with 1.5 times the paper weight of the same clear,ing agent as used in Example 5. The resulting cleaning sheet was evaluated in the same manner as in Example 1, and ~he results obtained are shown in Table 5 below.
Compar~tive Example 5 Example 4 Wet Tensile Strength (g/25 mm):
Dusting o x Water Disintegrability o o 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.
~ ~ O~t~ ~
The CMC-containing paper was uniformly sprayed with 1 part of a 2% aqueous solution of zinc sulfate per part of the paper and dried to obt~in water-disintegrable paper.
The resulting water-disintegr2ble pa~er was iJmpregnated wi~h 2.0 times the paper weight of a cleaning agent comprising a surfactznt (polyoxyethylene dodecyl ether (p=12)), propylene glycol, and water (2/15/83), and the properties of the impregnated paper were evalua~ed in the same manner as in Example 1. The results obtained are shown in Table 6 below.
COMPARATIVE EXAMP_E 5 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 ev~luated in the same manner as in Example 1, and the -esu~ts obtained are shol~ ln Table 6 below.
E~MPLE 7 The crepe paper as descri'oed in Exampie 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.
The water disintegrable paper was impregnated with 2.0 times the paper weight of 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 are shown in Table 6 below.
~00 ~29~i Comparative Example 6 Example 7 Example 5 Wet Tensile Strength (g/25mm):
Dustir.g o o x Water Disintegrability o o o A web of spiit 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 payer.
The water-disinte~rable paper was impregnated with 3 times the paper weight of a clean.ng ~oent com~risins polyethylene dodecyl ether (p=10), ethylene glycol and water (1il9/80), and the properlies of the impregnated paper were evaluated in the same manner as in Example 1. The results ob'ained are shown in Table 7 below.
COMPARATIVE EX~MPLE_6 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.
200~296 TA~LE 7 Comparative Example 8 Example 6 ~et Tensile ~trength ~g/25 mm):
Dusting o x Water Disintegrability o o ~ he 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 spr2yed with l part Oc a 2 calcium chlori~e aqueous solution per par~ of the pape- and dried to o~tain water-dis~ntegrable paper.
The water-disintegr2ble paper was impregnated with 1.5 times the pape- weight of a cleaning agent comprising a surfactant (dodecyldimethylamine oxide), polyethylene glycol 400 and water (1/20/79). Prcperties of the impregnated paper were evaluated in the s~me manner as in Example 1, and the results obtained are shown in Table 8 below.
The water-soluble binder-containing paper as obtained in Example 9 was impregnated witn a cleaning agent in the same Z0~9~i manner as in Example 9. Properties of the impregnated paper are shown in Table 8 below.
Con,parative Example 9 Exam~le 7 Wet Tensile S-treng~h (g/25 mm):
Dusting o x ~ater ~isintegrability o o 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 carboxymethyl cellulcse scdium-calcium mixed salt (Na:Ca=l~l by mol; produced by Daisel K.K.) using a cylindrical net-Yankee machine.
The water-disintegrable paper was ~mpregnated 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/mZ (crepe ratio: 15~) was produced from a raw material comprising 100 parts of NBKP and 10 parts of a water-soluble - 2~ -~OO ~Z9~
sodium carboxymethyl cellulose (produced by Daisel X.K.) using a cylindrical net-Yankee machine.
The water-disintegrable paper was impregnated with a cleaning asen ir. the s2me m~nner 2S in Exampl2 10. ~-oper_ies of the impregnated paper are shown in Table 9.
T~PLE 9 Comparative Example 10 Example 8 Wet Tensile Strength (g/25 mm):
MD 300 ~5 Dusting o x Water Disintegrability o o Toilet paper-like crepe pap~r having a basis weight of 20 g/m2 (crepe ratio: 10%) was produced from a raw material comprising /0 parts of NBRP and 30 parts of LDKP using a cylindrical net-Yankee machine.
The crepe paper was coated with 3% the paper weight of a water-soluble carboxymethyl cellulose sodium-zinc mixed salt (Na:Zn=10/1 by mol; produced by Daisel K.K.) and dried to obtain water-disintegrable paper.
The water-disintegrable paper was impregnated with 2.0 times the paper weight of a cleaning agent comprising a surfartant (polyoxyethylene dodecyl ether (p=12)), propylene glycol and water (2/15/83). The impregnated paper was 9~i evaluated in the same manner as in Example 1, and the results obtained are shown in Table 10 below.
The crepe paper 2S described in E~ample 11 was coated witn 3% the paper weighi of a wa~er-soluble sodium corbo.Yymethyl cellulose with 2 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.
ZC~O,~X9G
EXA~PLE 12 The crepe paper as described in Example 11 was coated with 3% the paper weight of a water-soluble carboxymethyl cellulose sodium-calcium mixed salt (Na:Ca-10/1 by mol;
produced by Daisel X.~<.) and dried to obtaill water-disintegrable paper.
The water-disintegrable paper was impresnated wi~h 2.0 times the paper weight of a cleaning agent comprising surfactant, propylene glycol and water. The impregnated paper was evaluated in the same manner as in ~xample 1, and the results obtained are shown in Table 10 below.
Comparative Example 11 Exam?le l2 Example 9 Wet Tensile Strength (g/25 mm):
Dust ng o o x Water Disintegrability o o o A web of split and deposited fibers of conifer fluff pulp having a basis weight of 40 g/m2 was sprayed with 10% the web weight of a water-soluble carboxymethyl cellulose sodium-calcium mixed salt (Na:Ca=l/1 by mole) and dried to obtain water-disintegrable paper.
The water-disintegrable paper was impregnated with 3 ZC~ 3t;
times the paper weight of a cleaning agent comprising a surfactant (polyethylene dodecyl ether (p=10)), ethylene glycol and water (1/19/80). The impresnated paper was evaluated in ~he same manner as in ~xample 1, ar.d the results obtain2d a-e shown in Table 11 below.
CO~IPARATIVE EXAMPLE 10 The web as described in Example 13 was sprayed with 10%
the web weight of a wat2r-soiuble sodium carboxymethyl ceilulose and dried to obtain water-disintegrable paper.
The water-disintegrable paper was impregnated with a cleaning agent in the same manner as in Example ~3. Properties of the impregnated paper are shown in Table 11.
Compaxative Example 13 Exam~le 10 Wet Tensile Strength tg/25 mm):
Dusting o x Water Disintegrability o o The crepe paper as described in Example 11 was coated with 3% the paper weight of a water-soluble methacxylic acid-lauryl methacrylate copolymer (7/3 by mol) potassium-calcium mixed salt (K:Ca=1/1 by mole) with a gravure coater and dried to obtain water-disintegrable paper.
2~ 2~, 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 a..d water (1/19/80), and the impregnated pape- was evaluated in the same manner as in Example 1. The resul's 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 cbtain water-soluble binder-containing paper.
The water-soluble binder-containing paper was impregnated with a cle~ning agent in the same manner as in Example 14. Properties o~ the impregnated paper are shown in Table 12 below.
Comparative Example 14 Exam~le 11 Wet Tensile Strength (g/25 mm):
Dusting o x Water Disintegrability o o A water-disintegrable paper shee~ having a basis weight of 25 g/m2 was produced from a bleached kraft pulp of conifer '~00'~2~6 beaten to a CSF (Canadian Standard Freeness) of 680 cc using an ordinary paper machine.
The water-disintegrable paper sheet was sprayed with 3%
~he paper weisht (corresponding to 0.75 g/m2) of a scdium carboxyr,ethyl 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.
Separately, the water-disintegrable paper sheet was sprayed with 3% the paper weighl (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 CMC-containing sheet and the polyacrylate-containing sheet were impregnated with 1.7 times the sheet weight of a cleaning agent comprising calcium chloride, polyoxyethylene dodocylether (p=8), ethanol and water (l/l/20/78) to obtain a water-disinteyrable cleaning sheet.
Wet tensile strength, dusting and fuzzing on use, and water disintegrability of the resulting cleaning sheet were evaluated in accordance with the following test methods. The results obtained are shown in Table 13 below.
1. Wet Tensile Strenqth:
The same as in Example 1.
20(~ ~Z9~i 2. _Dustinq and Fuæzinq:
The same as in Example 1.
3. Water Disinteqràbility.
In 1 R-volume beaker was put 500 m~ of tap water and a Teflon coated stirrer bar, and agitated by means of a magnetic stirrer at 300 rpm.
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/m~) of carrageenan having a mean molecular weight of 300,000 (produced by Tokyo Kasei R.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.
Z~ 9~
Wet Tensile Dusting Water Strenath (q~2~mm! and Disinte-MD _ CD Fuzzin~qrability Exa.T~le 15 (sec.) CMC-containing430 270 o 14 Sheet ~olyacrylic aci.d- 620 390 o 45 containing Sheet Comparative Example 12 Carrageenan- i8 46 ~ 17 containing Sheet While t~le invention has been described in detail and with reference to specific embodiments thereof, it will be apoarent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
WATER-DISINTEGRABLE CL~ANING S~EET
FIELD OF THE ~i2NTION
Th s inven_ion relates to a water-disintegrable _leaning sheet, and more particularly to a water-dislntegrable cleaning sheet comprising a specific water disintes-able paDer having incorporated or impregnated thereinto an a~ueous cleaning agent containing an organic solvent, which is suitable for cleaning or sterilization o. floors or walls Oî rooms or toilet rooms, furniture, toilet seats, toilQt basins, etc. or useful as toilet paper, and can be thrown into flushing water.
B~CXGROUND OE THE_INVENTION
Water-disintegrable papers or cleaning goods made of a chemicai-&or.taining wa.er-disintegrable paper which can be ~hrown into water have been used as toilet paper or for cleaning a toilet room or toilet equipment. Conventio~a water-disintegrable paper usually contains a dry s~rength agent such as polyvinyl alcohol, carboxymethyl cellulose, and cationic starch, for enhancing dry paper strength without impairing water d:isintegrability.
However, 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 w th a cleaning asent for cleaning or sterilization of floors, walls, furniture, and toilet equipment or for use as ~0~296 toilet paper, the cleaning agent to be combined with has been limiteà to liquid substances or chemicals having no or very low wa~er content.
In using z cleaning agenL cS high water content, it has beer necessary that the cleaning agent should be foamed and sp~ayQd on a water-disintegrable pa?er i.~ediately befo-e use and be used without delay in order to suppress water absorption iII ~0 paper and to pr2vent strength reduction.
Polyacrylamiàe or the like dry strength agent endows paper with strength enough lo withstand use even with a small amount of water being impregnated in the paper sheet, but tends to impair water di~inteyrability of the sheet.
Hence, 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.
It has been proposed to spray a binder solution containing polyvinyl alcohol and borax on a paper sheet followed by drying by heat whereby polyvinyl alcohol and borax are reacted to provide water-disintegrable paper having temporary water resistance, which is useful as absorbent materials such as napkin or diaper, as disclosed in JP-A-47 9486 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"3. Further, JP-A-61-296159 discloses a water-disintegrable paper in which an 200 ~296 aqueous solution containing salts such as potassium salt, calciu~ salt nd barium sa't, is impregnated into a fiorous sheet contain ng carrageenan as a bin~er, which is used for a wetting tissue p~per. F~rthermore, JP-A-55-lQ3393 ~isclGses a method for preparing a paper having high strength in a dry state while lcw in we~ ctate~ wh ch comp~lsec tre~ting 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. These water-disintegrabl~ papers, however, does not withstand the mechanical force in cleaning work when impregnated with water.
S~Y OF THE INVENTION
An object of the present invention is to provide a wate--disinteg able cleaning sheet containing a claaning agent, which has strength enough for cleaning use under a mechanical forca while retaining satisfactory water disintegrability.
As a _esult of extensive invastigations, 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.
ZOO~X96 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 carboxyi group; at least one polyvalent metallic ion selected from the group consisting of io~s of al~zlina eart~ me'als, manganese, zirc, cobalt and nickel; and an a~ueous cleaning agent containing an organic solvent.
DETAILED DESC~IPTION OF THE INVENTION
Water-dispercible fibers which constitute a water-disintegrable cleaning sheet of the present invention are not particularly restricted as long as they ars fibrous materials substantially dispersible in water. Examples of suit~ble ~ater-dispersible fibers are wood pulp fibe,s, non-wood vegetable fibers, and synthecic fibers such as rayon fibers and polyester fibers.
Water-soluble binders having a carbo~yl group which can be used in the present invention include polysaccharide derivatives, synthetic high polymers, and naturally-occurring substances.
Examples of suitable polysaccharide derivatives include carboxymethyl cellulose, carboxyethyl cellulose, and carboxymethylated starch, with carboxymethyl cellulose being preferred.
Examples of suitable synthetic high polymers include homopolymers of an unsaturated carboxylic acid, copolymers of Z1)0~96 two or more unsatura,ed carboxylic acids, and copolymers of an unsaturated carboxylic acid and other copolymeriæable monomer.
Specific examples of suitable Insaturated carboxylis acids are acrylic acid, methacrylic ac~d, itaconic acid, crotonic acid, maleic anhydride, maleic acid, ~nd fumaric acid. Monomers copolymerizable with the unsa~urated carboxylic acid include esters of these ur.saturated carbox-fllc acids, vinyl aceta~e, olefins (e.g., etilylene~, acrylamide, and vinyl ether.
Preferred of these high polymers are those contain~ng an acryl c 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.
Examples of suitable naturally-occurring water solub'e binders are alginic acid, xan~han g-~., arabic gum, tragacanth aum, and pectin.
Among these water-soluble binders, carboxy~ethyl cellulose is particl1larly 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 cleanin~ sheet of the present in-~ention (hereinafter refexred to as an 'essential metallic ion-) is at 29~
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.
Of ~he metal'ic ions as desc_ibed abo-ve, calcium, strontium, barium, zinc, cobalt, and nickei ions are preferred -rom the standpoi~t of ,ufficient st ength fcr clearing ~-ork of the cleaning sheet of the present invention.
Monovalent metallic ions other than Ihose described above satisfy water disintegrability but cannot arford strength withstanding cleaning work. Divalent metallic ions other than those described above, e.g., Cu2', Fe2+ or Sn2+, and trivalent metailic ions other than those described above, e.g., Fe~ or A~3+, afford strength enough for cleaning work but do not sa~isfy water disintegrability.
The essential metallic ion is preferably used in an amount of al least 1/4 mol, more preferably at least 1/2 mol, per mol of carboxyl group of the water-soluble binder.
The essential metallic i~n is incorporate~ into the water-disintegrable cleaning sheet of the present invention in the forms:
(A) an intermolecular mixed salt of the water-soluble binder formed between the carboxyl group thereof and (a) an alkali metal and (b) at least one selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt and nickel; and/or ;~0~296 (B) at least one of water-soluble salts such as hydroxides, chlorides, sulfates, nitrates, carbonates, formates and acetales, of at least one selected from the group consist~ng of an alkaline earth metal, mangznes~, zinc, cobal and nickel.
In the inter~olecu7~r rrlixe-~ sal~ zs ment-oned abov2 as form (A), a molar ratio of (a)~(b) is in the range of from l/0.01 to 1/10, preferably from l/0.05 to 1~3.
When the metal ion is incorporated into the cleaning sheet of the present invention in the form (B) above, an alkali metal salt of the binder which formed a salt between the carboxyl group and an alkali metal such as sodium and po~assium, is preferably used as a water-soluble binder.
The above forms (A) and (B) of th~ essential metallic ion are used each aione, or combination thereof to incorporate the essential metallic ion into the cieaning sheet of the present inv2ntion.
The wzter-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. For example, 2C0~29~
when the essential metallic ion is incorporated in the water-disintegrable paper in the form (B) above, the water-disintegrable pape- can be obtained by spraying or coating an aqueou~ solution of the waEer-soluble salt of at least one selected from the group consistins of alkaline earth metals, man~anese, zinc, ccbal~ and nickei, to a dry web conlzini..g carboxyl-containing water-soluble binder, and then drying. The paper containing carboxyl-cont2ining water-~oluble binder is obtained by adding a carboxyl-con~aining water-soluble binder into an aqueous dispersion of water-dispersible fibers and then sub~ecting 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 ODtaine~ by spraying or coating a carboxyl-cont2ining water-soluble b nder and an aqueous solution containing water-soluble salt of at least one selected from the g-oup consisting of an alkaline earth metal, manganes , zinc, cobalt and nickel, and then drying.
When the essential metallic ion is incorporated in the water-disintegrable paper iIl the form (A) above, namely a form of an intermolecular mixed salt of the water-soluble binder, 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 2(~0 ~296 salt binder to a web composed of water-dispersible fibers and then drying.
Further, when the essential metallic ion is incorporated in the water-disintegrable paper in combination of forms (~ and (~) above, the above-ment-oned incorporating prGcesscs are optionally comb1ned to obtain _he paper.
Processes for producir.g the water-disintegrable cleaning sheet of the present invention aIe not particularly restric'ed, and it can be produced, for ex2mple, by incorporating or impregrating an aqueous cleaning agent into the water-disintegrab~e paper as described above, or adding an aqueous cleaning agent into the water-disintegrable pzper 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. In such production, 1he 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.
_ 9 _ Z(~O~Z96 The aqueous cleaning agent which is incorporated in the cleanir.g sheet essentially contains an organic solvent fo-obtainlng nigh strength withstanding cleaning ~-ork. Suitable organ-c solvents are watel-compatible (cr water-soluble) solvents typically including mor.ohydric lower alcohols such as e'hanol, meth_nol, and propar.ol; g]ycols such 2S 2thylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, buthylene glycol and hexylene glycol; mono- or dlethers of the aforementioned glycols and lower alcohols such as methanol, ethanol and butanol; esters of the aforementioned glycols and lower fatty acids; and poiyhydric alcohols such as glycerine and sorbitol. In using 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, prererably 1 to 2.5 times the weight of water-disintegrable paper.
The content of the organic solvent in th~ aqu20us 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. For sterilization of toilet equipment, etc., cleaning agents rich in organic solvent, e.g., ethanol and isopropyl alcohol, are employed.
For removal of hydrophilic dirt from living rooms, kitchens or toilet rooms, aqueous cleaning agents rich in water are 2(~ 29~
employed. In this case, the water content ranges from 30 to 9S~ by weight, preferably from 40 to 92% by weigh~, more preferably from O0 to 90~ by wei~ht, ard the organic solv~nt conter.t ransQs from 5 to 70% ~y ~eight, preferably fro~ 8 to 60% by weight, more preferably from 1~ to 40~ by weight.
Ir desired, the aqueous cle3r.ing ~gents may furtner contain surfactants, sterilizers, deodorizers, perf~es, and t he like ~ s the s-~rfactants which may be contained in the cleaning agent of the present invention, 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 ato~s or lower alkyl gr.up, sulfcbetaines or hydroxysulfobetaines having alkyl group containing 8 to 22 carbon aioms, and carbobetaines having alkyl group cont~ir.ing 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 alkenyl) succinates containing 6 to 22 carbon atoms, and paraffinsulfonates containing 8 to 22 carbon atoms, as anionic surfactants; polyoxyalkylenes (mainly, polyoxyethylene, 2~0~'36 polyoxypropylene, or a mixture of these), glycol ethers, polyoxyalkylene alkyl phenyl ethers, alkyl glycosides, and sucrose fa~ty acid esters, as nonionic sur actants; quatQrnary a.~monium salts having an aiky-l srcup con.air.ing ~ to 11 carbon atoms, 2S cationic surfactants. These surfactants a--e added into the cleanirg zgents to 're ircGr~C~atQ ir. o wa~er-disintegrable cleaning sheet in an amount of generally from C.i to 5~ by weight.
A cleaning sheet prepared by simply impregnatina water-disintegrable paper containing a carboxyl~containing water-soluble binder with an aqueous solution having dissolved therein the above-dsscribed metallic ion, or by simply incorporating the web composed of water-dispersible fibers with an intermolecular mi~ed 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 forma~ion 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. Further, when spent water-disintegrable paper is discarded into toilet flushing wa~er, etc., the metallic ion and organic solvent in the sheet are diluted with a large quantity of water to make the insolubilized binder water-soluble, thereby maintaining water disintegrability.
~ 3~j As described above, the water-disintegrable cleaning sheet of the present invention, e-~en when using a cleaning agent of high water content, exhibits strength withstanding cleaning work and satisfactory watcr disintegrability in good balance and proàuces great effects as cle~nin~ sheet.
The p~esent invention is now illustrated in greater detail by way of the following Examples, but it should be understood th~t the present invention is not construed as being limited thereto. All the percents, parts, and ratios are given on a wei~ht basLs unless otherwise indicated.
A toilet paper-like water-disint~grable paper sheet having a basis weight of 25 g/m2 was produced from a bleached ~raft pulp of coni,er beaten to a CS~ (Canadian Stand~rd Freeness) of fi80 cc using an ordinary paper machine.
The water-disintegrable paper sheet was sprayed with 3% (corresponding to 0.75 g/m2) of a sodium car~oxymethyl cellulose CMC 2200" (produced by Daisel ~agaku R.R.) in the form of a 1% aqueous solution and dried to obtain a CMC-containing sheet.
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-disinte~rable cleaning sheet.
Z~ Z96 Wet tensile strength, dusting and fuzzing on use, and water disintegrability of the resulting cleaning sheet were evaluated in a~cordance with the following test methods. The results ~btained are shown in Table 1 below.
l. We~ Ter.sile ~trenqth:
A s~rip 25 mm w~de and 100 mm long was cut 01t of the cleaning sheet, and breaXing strength of the strip in the machine direction (~D) 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.
2. Dustinq and Fuzzinq:
The cleaning sheet W2S used for wiping black tiles inclusive of the joints for 5 minutas. Dusti~g on the tiles and fuzzing of the sheet were observed and evaluated according to the following rating system.
o: ~either substantial dusting nor fuzzing was observed.
~: Sligh.t dusting was observed, but fuzzing was not observed.
x: Dusting and fuzzing were observed.
3. Water Disinteqrabilitv:
In l ~-volume beaker was put 500 m~ of water and agitated with a stirrer at 300 rpm.
The cleaning sheet was cut to pieces of 50 mm x 50 mm and put into the water under stirring. After 90 seconds, the ;~0~ 9~;
disintegrated and dispersed state of the sheet was observed and evaluated according to the following rating system, taking co~ercially available toilet paper as a standard having satisf2ctory dispersioility.
o: Satisfacto-y dispersion ~: Sligntly poor disrersion x: Door dispersion COMPARATI~/E ~:XAMPLE 1 A cleaning sheet was produced in the same manner as in Example l, except for using an impregnating solution containing no calcium chloride. The resulting cleaning sheet was ~valuated in the same manner as in Example 1, and -ths results obtained ar~ sho~n in Table l below.
XOO~X9~
Ethanol/hacer (w/w) Example 1 50/50 20/80 10/90 0/100 -Wet Tersile MD CDMD CD MD CD MD CD
StrengthlQ20 620 ~80 '10 370 22~ ~0 28 (g/25mm)`
Dusting and o c o x Fuz7ing Water- o o o o Disintegrability Comparative Example l Wet lensile MD CD MD CD MD CD MD CD
Strength 350 200 90 50 35 20 30 17 (gt25mm) Dusting and Q x x x Fuzzing Watsr- o o o o Disintegrability Each of calcium chloride, bari~m 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.
Each of the resulting water-disintegrable cleaning sheets was evaluat0d in the same manner as in Example 1, and the results obtained are shown in Table 2 below.
ZCi~ 36 COMPA~ATIVE EXAMPLE 2 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 potâssium cnloride, copper sulfGte, ferrous chloride, ferric chloride, stannouC chloride, or aluminum sulf2te.
Each of the resulting sheets was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 2 below.
Z0~ .Z9~, MetallicWet Tensile Dusting Water Ion inStrenqth (g/25mm! and Disinte-SolutionMD CD Fuzzinq Grabili~y Example 2_ Ca2+ 480 310 o o Sr7+ 492 322 o o Ba2 524 340 o o ~n2+ 273 163 o o Zn~+ 472 302 o o Co2+ 396 194 o o Ni2+ 440 276 o o Comparative Example 2 K 42 19 x o Cu2+ 540 348 o x Fe2+ 442 283 o x Sn2+ 480 320 o x Fe3+ 686 390 o x A~3 760 41i o x EXAMPLE_3 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 i.n 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 200~ZI'3~i ratio of 1/4, 1/2, or 1/1 to the carboxylate lon of CMC.
Each of the resulting cleaning sheets was evaluated in the same manner as ir. Example 1, and the rssults obtained are shown in Table 3 below.
~ Tensile Dustlng Ca2+/COO~ strength ~q/~5mm! ar.d Water Molar RatioMD CD Euzzinq Disintearability 1/1 560310 o o 1/2 490290 o o 1/4 345190 o o A web of split and deposited fibers of a conifer fluff pu]p (basis weight: 30 g/m2) was sprayed with ]5% of a sodium salt of an acrylic acid-2-etnylhexyl acrylate copolymer (~3 by mol~, followed by d-ying to obtain a water-soluble bir.der-containing water-disintegrable sheet.
The resl~lting sheet was impregnated with 1.5 t mes the sheet weight of an aqueous clear.ing agent comprising zinc sulfate, polyoxyethylene dodecyl ether (p=8), propylene glycol and water at a ratio of 1/1/15/83 to obtain a water-disintegrable cleaning sheet.
The resulting cleaning sheet was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4 below.
0~9~i COMPARATIVE ~XAMPL~ 3 Thewater-solublebinder-cor.taining-~G er-c sin~egr2ble shee~ as prepared in Example ~ was im2regnated with an a~ueous c1ean7ng ager.t comprising polyox~ethylene dcdecyl ether (p=8~, propylene glycol, and water at a ratio of 1/15/84 in the same manner as in Exampie 4.
The resulting cleaning sheet was evaluated in the same manner as in Example 1, and the results obtained are shown in Table 4 below.
T~BLE 4 Net Tensile Example Streng~h (q/2577.7~) Dusting and ~ater No. MD CD Fuzzinq Disintea-ability Example 12O0 280 o o Comparative 15 13 x o ~xample 3 EX~PLE 5 Crepe paper having a basis weight of 25 g/m2 (crepe ratio: 20%) 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 l 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 ~he sheet 20~) ~29~
weight of a cleaning agent comprising a surfactant (Softanol 70), ethanol, and water (1/20/79). The resul~ing cleanir.g sheet was evaluated in the same manne. as in Example 1, znd the results obtained ale shown in Table 5 below.
The C~C-containing crepe paper as described in Exa.~ple 5 was impregnated with 1.5 times the paper weight of the same clear,ing agent as used in Example 5. The resulting cleaning sheet was evaluated in the same manner as in Example 1, and ~he results obtained are shown in Table 5 below.
Compar~tive Example 5 Example 4 Wet Tensile Strength (g/25 mm):
Dusting o x Water Disintegrability o o 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.
~ ~ O~t~ ~
The CMC-containing paper was uniformly sprayed with 1 part of a 2% aqueous solution of zinc sulfate per part of the paper and dried to obt~in water-disintegrable paper.
The resulting water-disintegr2ble pa~er was iJmpregnated wi~h 2.0 times the paper weight of a cleaning agent comprising a surfactznt (polyoxyethylene dodecyl ether (p=12)), propylene glycol, and water (2/15/83), and the properties of the impregnated paper were evalua~ed in the same manner as in Example 1. The results obtained are shown in Table 6 below.
COMPARATIVE EXAMP_E 5 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 ev~luated in the same manner as in Example 1, and the -esu~ts obtained are shol~ ln Table 6 below.
E~MPLE 7 The crepe paper as descri'oed in Exampie 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.
The water disintegrable paper was impregnated with 2.0 times the paper weight of 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 are shown in Table 6 below.
~00 ~29~i Comparative Example 6 Example 7 Example 5 Wet Tensile Strength (g/25mm):
Dustir.g o o x Water Disintegrability o o o A web of spiit 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 payer.
The water-disinte~rable paper was impregnated with 3 times the paper weight of a clean.ng ~oent com~risins polyethylene dodecyl ether (p=10), ethylene glycol and water (1il9/80), and the properlies of the impregnated paper were evaluated in the same manner as in Example 1. The results ob'ained are shown in Table 7 below.
COMPARATIVE EX~MPLE_6 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.
200~296 TA~LE 7 Comparative Example 8 Example 6 ~et Tensile ~trength ~g/25 mm):
Dusting o x Water Disintegrability o o ~ he 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 spr2yed with l part Oc a 2 calcium chlori~e aqueous solution per par~ of the pape- and dried to o~tain water-dis~ntegrable paper.
The water-disintegr2ble paper was impregnated with 1.5 times the pape- weight of a cleaning agent comprising a surfactant (dodecyldimethylamine oxide), polyethylene glycol 400 and water (1/20/79). Prcperties of the impregnated paper were evaluated in the s~me manner as in Example 1, and the results obtained are shown in Table 8 below.
The water-soluble binder-containing paper as obtained in Example 9 was impregnated witn a cleaning agent in the same Z0~9~i manner as in Example 9. Properties of the impregnated paper are shown in Table 8 below.
Con,parative Example 9 Exam~le 7 Wet Tensile S-treng~h (g/25 mm):
Dusting o x ~ater ~isintegrability o o 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 carboxymethyl cellulcse scdium-calcium mixed salt (Na:Ca=l~l by mol; produced by Daisel K.K.) using a cylindrical net-Yankee machine.
The water-disintegrable paper was ~mpregnated 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/mZ (crepe ratio: 15~) was produced from a raw material comprising 100 parts of NBKP and 10 parts of a water-soluble - 2~ -~OO ~Z9~
sodium carboxymethyl cellulose (produced by Daisel X.K.) using a cylindrical net-Yankee machine.
The water-disintegrable paper was impregnated with a cleaning asen ir. the s2me m~nner 2S in Exampl2 10. ~-oper_ies of the impregnated paper are shown in Table 9.
T~PLE 9 Comparative Example 10 Example 8 Wet Tensile Strength (g/25 mm):
MD 300 ~5 Dusting o x Water Disintegrability o o Toilet paper-like crepe pap~r having a basis weight of 20 g/m2 (crepe ratio: 10%) was produced from a raw material comprising /0 parts of NBRP and 30 parts of LDKP using a cylindrical net-Yankee machine.
The crepe paper was coated with 3% the paper weight of a water-soluble carboxymethyl cellulose sodium-zinc mixed salt (Na:Zn=10/1 by mol; produced by Daisel K.K.) and dried to obtain water-disintegrable paper.
The water-disintegrable paper was impregnated with 2.0 times the paper weight of a cleaning agent comprising a surfartant (polyoxyethylene dodecyl ether (p=12)), propylene glycol and water (2/15/83). The impregnated paper was 9~i evaluated in the same manner as in Example 1, and the results obtained are shown in Table 10 below.
The crepe paper 2S described in E~ample 11 was coated witn 3% the paper weighi of a wa~er-soluble sodium corbo.Yymethyl cellulose with 2 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.
ZC~O,~X9G
EXA~PLE 12 The crepe paper as described in Example 11 was coated with 3% the paper weight of a water-soluble carboxymethyl cellulose sodium-calcium mixed salt (Na:Ca-10/1 by mol;
produced by Daisel X.~<.) and dried to obtaill water-disintegrable paper.
The water-disintegrable paper was impresnated wi~h 2.0 times the paper weight of a cleaning agent comprising surfactant, propylene glycol and water. The impregnated paper was evaluated in the same manner as in ~xample 1, and the results obtained are shown in Table 10 below.
Comparative Example 11 Exam?le l2 Example 9 Wet Tensile Strength (g/25 mm):
Dust ng o o x Water Disintegrability o o o A web of split and deposited fibers of conifer fluff pulp having a basis weight of 40 g/m2 was sprayed with 10% the web weight of a water-soluble carboxymethyl cellulose sodium-calcium mixed salt (Na:Ca=l/1 by mole) and dried to obtain water-disintegrable paper.
The water-disintegrable paper was impregnated with 3 ZC~ 3t;
times the paper weight of a cleaning agent comprising a surfactant (polyethylene dodecyl ether (p=10)), ethylene glycol and water (1/19/80). The impresnated paper was evaluated in ~he same manner as in ~xample 1, ar.d the results obtain2d a-e shown in Table 11 below.
CO~IPARATIVE EXAMPLE 10 The web as described in Example 13 was sprayed with 10%
the web weight of a wat2r-soiuble sodium carboxymethyl ceilulose and dried to obtain water-disintegrable paper.
The water-disintegrable paper was impregnated with a cleaning agent in the same manner as in Example ~3. Properties of the impregnated paper are shown in Table 11.
Compaxative Example 13 Exam~le 10 Wet Tensile Strength tg/25 mm):
Dusting o x Water Disintegrability o o The crepe paper as described in Example 11 was coated with 3% the paper weight of a water-soluble methacxylic acid-lauryl methacrylate copolymer (7/3 by mol) potassium-calcium mixed salt (K:Ca=1/1 by mole) with a gravure coater and dried to obtain water-disintegrable paper.
2~ 2~, 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 a..d water (1/19/80), and the impregnated pape- was evaluated in the same manner as in Example 1. The resul's 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 cbtain water-soluble binder-containing paper.
The water-soluble binder-containing paper was impregnated with a cle~ning agent in the same manner as in Example 14. Properties o~ the impregnated paper are shown in Table 12 below.
Comparative Example 14 Exam~le 11 Wet Tensile Strength (g/25 mm):
Dusting o x Water Disintegrability o o A water-disintegrable paper shee~ having a basis weight of 25 g/m2 was produced from a bleached kraft pulp of conifer '~00'~2~6 beaten to a CSF (Canadian Standard Freeness) of 680 cc using an ordinary paper machine.
The water-disintegrable paper sheet was sprayed with 3%
~he paper weisht (corresponding to 0.75 g/m2) of a scdium carboxyr,ethyl 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.
Separately, the water-disintegrable paper sheet was sprayed with 3% the paper weighl (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 CMC-containing sheet and the polyacrylate-containing sheet were impregnated with 1.7 times the sheet weight of a cleaning agent comprising calcium chloride, polyoxyethylene dodocylether (p=8), ethanol and water (l/l/20/78) to obtain a water-disinteyrable cleaning sheet.
Wet tensile strength, dusting and fuzzing on use, and water disintegrability of the resulting cleaning sheet were evaluated in accordance with the following test methods. The results obtained are shown in Table 13 below.
1. Wet Tensile Strenqth:
The same as in Example 1.
20(~ ~Z9~i 2. _Dustinq and Fuæzinq:
The same as in Example 1.
3. Water Disinteqràbility.
In 1 R-volume beaker was put 500 m~ of tap water and a Teflon coated stirrer bar, and agitated by means of a magnetic stirrer at 300 rpm.
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/m~) of carrageenan having a mean molecular weight of 300,000 (produced by Tokyo Kasei R.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.
Z~ 9~
Wet Tensile Dusting Water Strenath (q~2~mm! and Disinte-MD _ CD Fuzzin~qrability Exa.T~le 15 (sec.) CMC-containing430 270 o 14 Sheet ~olyacrylic aci.d- 620 390 o 45 containing Sheet Comparative Example 12 Carrageenan- i8 46 ~ 17 containing Sheet While t~le invention has been described in detail and with reference to specific embodiments thereof, it will be apoarent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (12)
1. A water-disintegrable cleaning sheet comprising a web of water-dispersible fibers having incorporated thereinto a water-disparsible binder having a carboxyl group; at least one metallic ion selected from the group consisting of ions of alkaline earth metals, manganese, zinc, cobalt, and nickel;
and an aqueous cleaning agent containing an organic solvent.
and an aqueous cleaning agent containing an organic solvent.
2. The water-disintegrable cleaning sheet as claimed in Claim 1, wherein said water-soluble binder is an alkali metal salt formed between the carboxyl group thereof and an alkali metal.
3. The water-disintegrable cleaning sheet as claimed in Claim 1, wherein said at least one metallic ion selected from the group consisting of ions of alkaline earth metals, manganese, zinc, cobalt, and nickel, is incorporated thereinto in the forms of:
(A) an intermolecular mixed salt of said water-soluble binder formed between the carboxyl group thereof and (a) an alkali metal and (b) at least one selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt and nickel; and/or (B) a water-soluble salt.
(A) an intermolecular mixed salt of said water-soluble binder formed between the carboxyl group thereof and (a) an alkali metal and (b) at least one selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt and nickel; and/or (B) a water-soluble salt.
4. The water-disintegrable cleaning sheet as claimed in Claim 3, wherein a molar ratio of (a) an alkali metal and (b) at least one polyvalent metal selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt, and nickel, of said intermolecular mixed salt (A) is in the ranges from 1/0.01 to 1/10.
5. The water-disintegrable cleaning sheet as claimed in Claim 3, wherein said water-soluble salt is at least one selected from the group consisting of a hydroxide, a chloride, a sulfate, a nitrate, a carbonate, a formate and an acetate, of at lease one selected from the group consisting of alkaline earth metals, manganese, zinc, cobalt, and nickel.
6. The water-disintegrable cleaning sheet as claimed in Claim 1, wherein said water-soluble binder is present in a amount of from 0.1 to 30% by weight based on the dry weight of the web.
7. The water-disintegrable cleaning sheet as claimed in Claim 1, wherein an amount of said at least one metallic ion selected from the group consisting of ions of alkaline earth metals, manganese, zinc, cobalt, and nickel, is at least 1/4 mol per mol of the carboxyl group of said water-soluble binder.
8. The water-disintegrable cleaning sheet as claimed in Claim 1, wherein said water-soluble binder is a carboxymethyl cellulose.
9. The water-disintegrable cleaning sheet as claimed in Claim 1, wherein said water-soluble binder is a polymer of an unsaturated carboxylic acid, a copolymer of two or more of an unsaturated carboxylic acid, or a copolymer of an unsaturated carboxylic acid and other copolymerizable monomer.
10. The water-disintegrable cleaning sheet as claimed in Claim 9, wherein said unsaturated carboxylic acid is acrylic acid or methacrylic acid.
11. The water-disintegrable cleaning sheet as claimed in Claim 1, wherein said organic solvent contained in said aqueous cleaning agent is a water compatible solvent.
12. The water-disinteyrable cleaning sheet as claimed in Claim 1, wherein said aqueous cleaning agent is containing said organic solvent in an amount ranges from 5 to 95% by weight, and water in an amount ranges from 95 to 5% by weight.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63303159A JPH0724636B2 (en) | 1988-11-30 | 1988-11-30 | Water-degradable cleaning articles |
| JP303160/88 | 1988-11-30 | ||
| JP63303160A JP2549159B2 (en) | 1988-11-30 | 1988-11-30 | Hydrolyzed paper |
| JP303159/88 | 1988-11-30 | ||
| JP47534/89 | 1989-02-28 | ||
| JP1047534A JP2584508B2 (en) | 1989-02-28 | 1989-02-28 | Water disintegration paper for cleaning supplies |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2004296A1 true CA2004296A1 (en) | 1990-05-31 |
Family
ID=27293008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2004296 Abandoned CA2004296A1 (en) | 1988-11-30 | 1989-11-30 | Water-disintegrable cleaning sheet |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0372388B1 (en) |
| CA (1) | CA2004296A1 (en) |
| DE (1) | DE68913161T2 (en) |
| ES (1) | ES2051344T3 (en) |
| HK (1) | HK121294A (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5264269A (en) * | 1989-09-21 | 1993-11-23 | Kao Corporation | Water-disintegratable cleaning article in laminated sheet form |
| WO1992013032A1 (en) * | 1991-01-25 | 1992-08-06 | Battelle Memorial Institute | Base dispersible polymer composition and dispersible articles |
| EP0801172B1 (en) * | 1995-10-13 | 2003-01-02 | Uni-Charm Corporation | Biodegradable and hydrolyzable sheet |
| JP3566044B2 (en) * | 1997-09-24 | 2004-09-15 | ユニ・チャーム株式会社 | Water-disintegrable fiber sheet and wiping sheet on which it is stacked |
| US6127593A (en) * | 1997-11-25 | 2000-10-03 | The Procter & Gamble Company | Flushable fibrous structures |
| JP3553348B2 (en) * | 1997-12-26 | 2004-08-11 | ユニ・チャーム株式会社 | Water-decomposable fiber sheet using alkyl cellulose |
| 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 |
| 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 |
| US6423804B1 (en) | 1998-12-31 | 2002-07-23 | Kimberly-Clark Worldwide, Inc. | Ion-sensitive hard water dispersible polymers and applications therefor |
| JP3703661B2 (en) * | 1999-10-05 | 2005-10-05 | ユニ・チャーム株式会社 | Water-decomposable fiber sheet containing gel compound |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| EP1167510A1 (en) * | 2000-06-23 | 2002-01-02 | The Procter & Gamble Company | Flushable hard surface cleaning wet wipe |
| 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 |
| US20060037724A1 (en) * | 2004-08-20 | 2006-02-23 | Kao Corporation | Bulky water-disintegratable cleaning article and process of producing water-disintergratable paper |
| US8197830B2 (en) | 2005-01-18 | 2012-06-12 | Gojo Industries, Inc. | Dissolvable pads for solution delivery to a surface |
| FR2940331B1 (en) | 2008-12-18 | 2010-12-17 | Georgia Pacific France | METHOD FOR MANUFACTURING SINGLE PAPER SHEET, USE OF SHEET FOR MANUFACTURING ROLLER SUPPORTING CHUCK, DELIBERABLE PAPER SHEET, AND CHUCK MADE OF AT LEAST ONE OF SAID SHEETS |
| FR2940330B1 (en) * | 2008-12-18 | 2017-06-23 | Georgia-Pacific France | PAPER SHEET DELITEABLE IN WATER, CHUCK FOR PAPER ROLL CONSISTING OF SUCH SHEET |
| FR2948696A1 (en) | 2009-08-03 | 2011-02-04 | Georgia Pacific France | METHOD FOR MANUFACTURING A DELIBERABLE PAPER SHEET, DELICIOUS PAPER SHEET, CHUCK MADE OF AT LEAST ONE SUCH SHEET |
| EP2785914B1 (en) | 2011-11-30 | 2016-03-16 | Dow Global Technologies LLC | Water-disintegratable non-woven fibrous sheet |
| GB2513124B (en) * | 2013-04-15 | 2018-12-12 | Welland Medical Ltd | Flushable wipe |
| ES2560354B1 (en) * | 2015-11-18 | 2016-11-22 | Juan SALVADOR VALERO | Hydrodispersible hygienic microfiber |
| ES2613889B1 (en) * | 2015-11-25 | 2018-03-12 | Juan SALVADOR VALERO | Hydrodispersible hygienic microfiber, perfected |
| JP6211160B1 (en) * | 2016-09-30 | 2017-10-11 | 大王製紙株式会社 | Water disintegratable sheet |
| TR201816478T4 (en) | 2016-11-30 | 2018-11-21 | Chem&P Gmbh & Co Kg | Fiber-containing, moisture-resistant substrate with adjustable moisture and wet strength, and a method for the production thereof. |
| DE102017115930A1 (en) * | 2017-07-14 | 2019-01-17 | Chem&P Gmbh & Co. Kg | Moisture-resistant, water-decomposable fiber composite material |
| EP3575466B1 (en) * | 2018-05-29 | 2022-05-11 | Intervisa Beteiligung und Verwaltung GmbH | Water disintegratable fibre composite material |
| JP7443360B2 (en) | 2018-10-26 | 2024-03-05 | モノソル リミテッド ライアビリティ カンパニー | Multilayer water dispersible article |
| EP4048724A1 (en) | 2019-10-25 | 2022-08-31 | Monosol, LLC | Multilayer water-dispersible articles |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2903218A1 (en) | 1979-01-27 | 1980-08-07 | Basf Ag | METHOD FOR PRODUCING PAPER WITH HIGH DRY RESISTANCE AND LOW WET STRENGTH |
| NZ206331A (en) * | 1982-11-26 | 1986-05-09 | Unilever Plc | Liquid-permeable,flexible,sheet-like articles |
| JPH076122B2 (en) | 1985-06-19 | 1995-01-30 | ア−ス製薬株式会社 | Water-degradable non-woven fabric |
-
1989
- 1989-11-30 CA CA 2004296 patent/CA2004296A1/en not_active Abandoned
- 1989-11-30 ES ES89122081T patent/ES2051344T3/en not_active Expired - Lifetime
- 1989-11-30 DE DE1989613161 patent/DE68913161T2/en not_active Expired - Fee Related
- 1989-11-30 EP EP19890122081 patent/EP0372388B1/en not_active Expired - Lifetime
-
1994
- 1994-11-03 HK HK121294A patent/HK121294A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| HK121294A (en) | 1994-11-11 |
| EP0372388A2 (en) | 1990-06-13 |
| EP0372388A3 (en) | 1991-12-18 |
| DE68913161T2 (en) | 1994-07-07 |
| EP0372388B1 (en) | 1994-02-16 |
| DE68913161D1 (en) | 1994-03-24 |
| ES2051344T3 (en) | 1994-06-16 |
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