CN1364064A - Wiper with excellent lint-free property - Google Patents
Wiper with excellent lint-free property Download PDFInfo
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- CN1364064A CN1364064A CN01800550A CN01800550A CN1364064A CN 1364064 A CN1364064 A CN 1364064A CN 01800550 A CN01800550 A CN 01800550A CN 01800550 A CN01800550 A CN 01800550A CN 1364064 A CN1364064 A CN 1364064A
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- Prior art keywords
- pva
- rag
- polyvinyl alcohol
- adhesive
- acid
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H13/00—Other non-woven fabrics
-
- 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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Artificial Filaments (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
Abstract
A lint-free wiper which comprises a nonwoven fabric made of long fibers of polyvinyl alcohol having a viscosity-average degree of polymerization of 200 to 700 and a melting point of 160 to 230 DEG C. It has excellent lint-free properties. It further has a high affinity for water and has properties such as water-absorbing properties, hydrophilicity, and the property of swelling in water.
Description
Invention field
The present invention relates to a kind of nonlinting rag, this rag is made by thermoplastic polypropylene alcohol radical long fibre nonwoven fabric.
Background of invention
Be used for things such as wiping liquid in the toilet or sweep the wall of toilet or the rag needs that use during the floor highly phozy; promptly seldom produce the thin dust or the fine hair of rag material; and have good water imbibition, good oil absorption and good pliability, promptly be easy to the profile that loosely covered or followed object such as wall, floor to be cleaned.
In order to reduce fluffing to greatest extent, rag must be able to not produce dust and fall small fiber from rag.Specifically be, should prevent that micro fiber from splitting away off from cut surface or its periphery, described cut surface is to form in the process of making rag by the cutting sheet material.For reaching this purpose, importantly, preferably utilize so-called spun-bond process to produce non-woven fibre by long fibre, in described spun-bond process, thermoplastic polymer is carried out melt-spun, make synthetic long fibre directly form adhesive-bonded fabric.
At present, utilized the adhesive-bonded fabric of mainly making to make the rag that uses in many clean rooms already by cellulose fibre.Although cellulose fibre is the suitable raw material with high water absorptivity, these fibers are not thermoplastic, therefore are not suitable for it is used the melt-spun method.By being separated, the fiber hot melt can prevent to split away off from adhesive-bonded fabric by the fiber that thermoplastic polymer makes together.Yet this technology is not suitable for cellulose fibre.
Already with polyester fiber etc. as thermoplastic fibre.Yet because fiber water absorption rates such as polyester fiber are low, it is hydrophilic therefore must these fibers to be become by processing.Even improved water absorption rate, but brought another problem: when things such as wiping organic solvent, can increase the amount of wash-out from rag by these rags that made by the fiber of hydrophilic treated by processing.
DISCLOSURE OF INVENTION
An object of the present invention is to provide a kind of nonlinting rag, it can show the high wettability to water, and this wetability is represented with water absorption rate, hydrophily and swellability.
According to the present invention, produce the production technology of using in the spunbond non-woven fibre process by utilizing the melt-spun method, produce nonlinting rag by adhesive-bonded fabric based on polyvinyl alcohol, described adhesive-bonded fabric shows the height wetability to water, this wetability is represented that by water absorption rate, hydrophily and swellability described rag shows fabulous hydrophily.
More precisely, phozy rag of the present invention is to be made by the long fibre nonwoven fabric based on polyvinyl alcohol, and described long stapled viscometric degree of polymerization is 200 to 700, and fusing point is 160 to 230 ℃.
Implement best mode of the present invention
According to the present invention, as utilizing the raw-material polyvinyl alcohol of making adhesive-bonded fabric based on the long fibre of polyvinyl alcohol to comprise: except that alcotex, the modified polyvinylalcohol of introducing by the postreaction after copolymerisation, the terminal-modified or polymerisation with another functional group.
The viscometric degree of polymerization of the polyvinyl alcohol that is suitable for using in the present invention (after this only being called " PVA " frequently) is 200 to 700, is preferably 230 to 600, more is preferably 250 to 500.When viscometric degree of polymerization was lower than 200, polyvinyl alcohol can not show enough spinnabilitys, thereby polymer can not be made fiber.When sticking homopolymer was higher than 700, it is too high that melt viscosity becomes, so that can not be stably from the spinneret extruded polymer.
Can measure the degree of polymerization (P) of PVA according to JIS-K6726.Say exactly, in 30 ℃ water with the complete resaponifying of PVA and purifying (dl/g) with intrinsic viscosity [η].Calculate the degree of polymerization (P) of PVA by the inherent viscosity of being surveyed [η] according to following formula:
P＝([η]×10
3/8.29)
(1/0.62)
When the degree of polymerization is positioned at above scope, just can reach effect of the present invention fully.
Preferably, the saponification degree of PVA used in the present invention is 90 to 99.99mol%, more is preferably 93 to 99.98mol%, more preferably 94 to 99.97%, and most preferably be 95 to 99.96%.When saponification degree is lower than 90%mol%, the poor heat stability of PVA, this causes PVA that thermal decomposition or gelatification take place, and is difficult to thus PVA is melt-spun into fiber effectively.In addition, when the saponification degree of PVA is higher than 99.99mol%, be difficult to produce with stationary mode.Therefore, as a result of also be difficult to stably form PVA, also just can not obtain gratifying long fibre nonwoven fabric.Furtherly, because water absorption rate reduces, the rag of being made by these PVA fibers can not show the needed gratifying character of rag.
The fusing point of PVA used in the present invention (Tm) is 160 to 230 ℃, is preferably 170 to 227 ℃, more is preferably 180 to 220 ℃.When fusing point was lower than 160 ℃, PVA showed low crystallizability, thus the PVA fiber and by its adhesive-bonded fabric of making in variation aspect the mechanical strength.Under the certain situation, PVA does not possess is enough to carry out the required spinnability of melt-spun, and causes serious thermal decomposition, thereby can not form adhesive-bonded fabric.In addition, the adhesive-bonded fabric that is made by these PVA can produce many fine hair or fine fleece, and it can not show gratifying character as rag.When fusing point was higher than 230 ℃, the melt-spun temperature of PVA must raise to guarantee suitable melt viscosity.Because the melt-spun temperature is in close proximity to the decomposition temperature of PVA, therefore be difficult to stably PVA be carried out melt-spun and stably produces adhesive-bonded fabric.
The fusing point of PVA is meant the peak temperature of PVA endothermic curve, this endothermic curve utilizes Differential Scanning Calorimeter (DSC) to record in the following manner: the programming rate with 10 ℃/min in the atmosphere of nitrogen is heated to 250 ℃ with sample, with its cool to room temperature, the programming rate with 10 ℃/min is heated 250 ℃ once more.
Make PVA by saponification corresponding to the vinyl acetate unit of vinyl acetate polymer.The vinyl monomer that forms the vinyl acetate unit can comprise: vinyl formate, vinylacetate, propionate, valeric acid vinyl acetate, capric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, new vinyl acetate acid and vinyl versatate ester.In these vinyl monomers, vinylacetate is preferred.
As mentioned above, PVA base long fibre polymer constructed in accordance both can be the PVA homopolymers, also can be the modified PVA of having introduced copolymerization units.Wherein, consider melt-spun and fibre property, the modified PVA with copolymerization units is preferred.The example of copolymerisable monomer comprises: a-alkene, for example ethene, propylene, 1-butylene, isobutene and 1-alkene; Acrylic acid and acrylates thereof; Acrylate, for example methyl acrylate, ethyl acrylate, acrylic acid n-propyl diester and acrylic acid i-propyl diester; Methacrylic acid and methacrylate thereof; Methacrylate, for example methyl methacrylate, EMA, methacrylic acid n-propyl ester and methacrylic acid i-propyl ester; Acrylamide; The derivative of acrylamide is such as N methacrylamide and N-ethyl acrylamide; Methacrylamide; The derivative of Methacrylamide, for example N-methyl acrylamide and N-ethyl-methyl acrylamide; Vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether and n-butyl vinyl ether; The vinyl ethers of hydroxyl, ethylene glycol ethene ether, 1 for example, ammediol vinethene and 1,4-butanediol vinethene; Allyl ether, for example acetate allyl ether, propyl group allyl ether, butyl allyl ether and basic allyl ether; The monomer that contains oxyalkylene; Vinyl silylation compound is such as vinyltrimethoxy silane; Isopropenyl acetate; The a-alkene of hydroxyl, 3-butene-1-alcohol for example, 4-amylene-1-ol, 5-be alkene-1-alcohol, 7-octen-1-ol, 9-decen-1-ol and 3-methyl-3-butene-1-alcohol; The N-vinylamine, N-ethylene carboxamide for example, N-ethene acetamide and N-vinylpyrrolidone; Monomer with carboxylic acid, it is that 4-benzenetricarboxylic anhydride and itaconic anhydride derive out by fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, 1,2; Have sulfonic monomer, it is born by ethionic acid, allyl sulphonic acid, metering system sulfonic acid and 2-acrylamide-2-methyl-propyl sulfnic acid derivatives; And the monomer with cation group, they are by ethyleneoxy ethyl-trimethyl salmiac, ethyleneoxy butyl trimethyl ammonium chloride, ethyleneoxy ethyl dimethyl amine, ethyleneoxy methyl diethylamide, N acrylamide ylmethyl trimethyl ammonium chloride, N acrylamide base ethyl-trimethyl salmiac, N acrylamide base dimethyl amine, pi-allyl trimethyl ammonium chloride, methylpropenyl trimethyl ammonium chloride, DMAA, pi-allyl ethylamine and their derivative.The content of comonomer is generally 25mol% and subtracts lower in the modified PVA.
In these monomers, in view of being easy to get property, preferably: a-alkene, for example ethene, propylene, 1-butylene, isobutene and 1-alkene; Vinethene, for example ethylene methacrylic ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether and n-butyl vinyl ether; The vinethene of hydroxyl, ethylene glycol ethene ether for example, 1, ammediol vinethene and 1,4-butanediol vinethene; Allyl ether, allyl acetate for example, propyl group allyl ether, butyl allyl ether and basic allyl ether; The N-ethernamine, N-ethylene carboxamide for example, N-ethene acetamide and N-vinylpyrrolidone; The monomer that contains oxyalkylene; And the a-alkene of hydroxyl, 3-butyl-1-alcohol for example, 4-amylene-1-ol, 7-octen-1-ol, 9-decen-1-ol and 3-methyl-3-butyl-1-alcohol.
In addition, consider copolymerized ability, melt-spun and, preferably have 4 or still less the a-alkene of carbon atom, for example ethene, propylene, 1-butylene and isobutene such as the fiber of water absorption rate and swellability high wettability to water; Vinethene, for example ethylene methacrylic ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether and n-butyl vinyl ether; N-ethernamine, for example N-ethylene carboxamide, N-ethene acetamide and N-vinylpyrrolidone.Preferably, by having 4 or the a-alkene of the carbon atom construction unit of deriving out still less, vinethene and N-ethernamine are preferred, and the amount with 0.1 to 20mol% is present among the PVA, more is preferably 1 to 15mol%.
Strengthened fiber properties owing to have the modified PVA of ethylene unit, therefore particularly preferably be, the amount of the contained ethylene unit of modified PVA is 3 to 20mol%, is preferably 5 to 18mol%.
Can utilize known method to make PVA used in the present invention, for example polymerisation in bulk of these methods, polymerisation in solution, suspension polymerisation and emulsion polymerisation.In these methods, use polymerisation in bulk and polymerisation in solution usually, polymerisation in bulk need not solvent, and polymerisation in solution need be such as the solvent of ethanol.The example of used ethanol is a lower alcohol in the polymerisation in solution, for example methyl alcohol, ethanol and propyl alcohol.The initator of copolyreaction can be known azo or peroxide initiator, a for example, a '-azodiisobutyronitrile, 2,2 '-azo two (2, the 4-methyl pentane nitrile), benzoperoxide and n-propyl group peroxidating carbonate.Not concrete limit polymerization temperature, suitable is 0 to 200 ℃.
According to the present invention, the PVA that makes the adhesive-bonded fabric rag preferably includes the alkali metal ion (B) of 0.00001 to 0.05 mass parts, more be preferably 0.00005 to 0.04 mass parts, 0.0001 to 0.03 mass parts more preferably, most preferably be 0.0002 to 0.02 mass parts, it is unit based on the mass parts 100 of PVA with the sodium ion.The PVA that alkali metal ion content measured is lower than 0.00001 mass parts is difficult to carry out suitability for industrialized production.When alkali metal ion content measured surpassed 0.05 mass parts, PVA tended to thermal decomposition or gelatification take place in the melt-spun process, thereby can not produce gratifying adhesive-bonded fabric.In addition, along with the amount increase of the metal ion that comes out from the adhesive-bonded fabric wash-out, thereby cause the adhesive-bonded fabric rag not use in the toilet.The example of alkali metal ion comprises potassium ion and sodium ion.
Specifically do not limit alkali metal ion (B) with specified amount and be incorporated into method among the PVA.For example, can be after polymerisation the compound of alkali metal containing ion be added among the PVA.What can select is, can be in existing as the solution of the alkaline matter that comprises alkali metal ion of saponification catalyst saponification vinethene polymer, so that alkali metal ion is incorporated among the PVA, then utilize the PVA of cleaning solution washing, so that the control alkali metal ion content measured as saponification resultant.The method of back is preferred.Can detect alkali metal ion content measured by atomic absorption method.
The alkaline matter example that is used in the saponification catalyst comprises potassium hydroxide and NaOH.Alkaline matter consumption preferably as the saponification catalyst is 0.004 to 0.5 mole of every molar ethylene ether unit, more preferably 0.005 to 0.05 mole.Incipient stage in saponification will add whole saponification catalyst immediately, or divides several parts to add the saponification catalyst in the saponification process.
The examples of solvents of saponification can comprise methyl alcohol, methyl acetate, dimethyl sulfoxide (DMSO) and dimethyl formamide.In these solvents, methyl alcohol preferably, more preferably water content is the methyl alcohol of 0.001 to 1 quality %, and further preferably water content is the methyl alcohol of 0.003 to 0.9 quality %, and most preferably water content is the methyl alcohol of 0.005 to 0.8 quality %.The example of cleaning solution comprises methyl alcohol, acetate, methyl acetate, ethyl acetate, hexane, water etc.In these washing agent, methyl alcohol preferably, methyl acetate, water and their mixture.
Specifically not limiting used amount of liquor, as long as the content (B) of alkali metal ion can satisfy above-mentioned scope among the PVA, but is 100 when be basic with the mass parts of PVA, and it is preferably 300 to 10000 mass parts, more is preferably 500 to 5000 mass parts.Wash temperature is preferably 5 to 80 ℃, more is preferably 20 to 70 ℃, and wash time is preferably 20 minutes to 100 hours, more is preferably 1 to 50 hour.
PVA used in the present invention (A) can comprise a kind of acid (C), and the pKa of the acid group that this is sour is 5.0 or littler in the time of 25 ℃, determines ratio a by following formula:
A=(acid among the PVA (C) content (quality %))/(content (quality %) of alkali metal ion among the PVA (B)),
The amount of acid makes ratio a be preferably 0.01 to 1, more is preferably 0.03 to 0.8, most preferably is 0.05 to 0.6.In following formula, can measure the content of acid (C) by acid-base titration, and represent with the acetate form.Define term pKa with following formula:
pKa＝-logKa
Wherein Ka is a dissociation constants of acids.
When the pKa of the acid group of acid (C) surpasses 5.0 or when sour (C) content can not make a value be 0.01 to 1, the production that PVA tends to be subjected to serious decomposition, gel and destroys spunbond adhesive-bonded fabric can not stably form fiber thus.The pKa of 25 ℃ of following acid groups be 5.0 or the example of lower acid (C) comprising: acetate, phosphoric acid and sodium dihydrogen phosphate.
Specifically do not limit acid (C) with specified amount and be incorporated into method among the PVA.For example, can the PVA that obtain by saponification vinethene polymer in solvent is mixed with acid (C), wash with cleaning solution so that acid (C) content is adjusted to top specified scope then.What can select is, can be in the granulation process of PVA implements acid among the PVA and introduces by handling dry PVA with the solvent that contains acid (C) or the acid (C) of specified amount being added to.
Can utilize methyl alcohol from PVA, to extract the content that sour (C) determined among the PVA in acid (C), methanol extract liquid be carried out acid-base titration with the aqueous solution of NaOH.
If desired, PVA can further comprise various additives, for example, can influence purpose of the present invention and effect unfriendly unless add these additives such as stabilizing agent, colouring agent, ultra-violet absorber, light stabilizer, antioxidant, antistatic additive, fire retardant, plasticiser, lubricant and the crystallization inhibitor of copper compound.Both can in polymerization process, also can in subsequent step, add additive to PVA.Particularly, for example adding, the heat stabilizer of organic stabilizer (for example hindered phenol), copper halide compound (for example cupric iodide) and alkali halide metallic compound (such as KI) is better than melt pressurize (melt-dwelling) stability that improves in the fiber forming process.
In addition, can or in subsequent step, be that 0.05 to 10 quality %, average grain diameter are the fine grained of 0.05 to 5 μ m in polymerisation if desired to the PVA addition.Specifically do not limit the fine grained that is added, for example they can comprise inertia fine graineds such as silicon, aluminium, titanium oxide, calcium carbonate, barium sulfate.These fine graineds can use separately, also can two or more be used in combination.In these fine graineds, can improve spinnability and tensile properties because average grain diameter is the fine inorganic particles of 0.02 to 1 μ m, so they are particularly preferred.
To describe below according to the present invention and produce technology as the adhesive-bonded fabric of making by the PVA long fibre of phozy rag.Utilize the method that adopts in the spunbond adhesive-bonded fabric process of production to produce the adhesive-bonded fabric of making by long fibre efficiently according to the present invention, in the method that is adopted, directly form adhesive-bonded fabric by melt spun fibre.
More precisely, in extruder, PVA carried out melt kneading after, the polymer of fusion is imported spinning head and with its extruding spinning head, measures its flow velocity simultaneously.The single thread (strand) that utilizes cooling device cooling to be extruded, utilize then have air nozzle aspirator by jet-stream wind single thread is attenuated with the corresponding speed of 1000 to 6000m/min hauling speed, thus the single thread reduced down in thickness is arrived desirable fineness.Then, break single thread and it is deposited on mobile the cohesion face to form non-woven fabric fiber network.Then, local extrusion fiber net and with fleece around to roller, to obtain the long fibre nonwoven fabric of PVA base.
In production process according to adhesive-bonded fabric of the present invention, the spinning head temperature of melt-spun PVA need be arrived surely in Tm+10 ℃ to Tm+80 ℃ the scope, wherein Tm represents the fusing point of polymer.When the spinning head temperature was lower than Tm+10 ℃, the melt viscosity of polymer was too high, will form the resistance to spinning and jet stretching.When the spinning head temperature was higher than Tm+80 ℃, PVA was subjected to thermal decomposition, can not stably spin to polymer thus.
The fusing point Tm of the PVA of indication represents that for example described calorimeter is the TA3000 that buys from Mettler company by the peak temperature of the main endothermic peak of differential scanning calorimeter (DSC) observation herein.
In the present invention, importantly utilize aspirator to spray the single thread of extruding is attenuated with the corresponding speed of 1000 to 6000m/min hauling speed by air with air nozzle.Select the traction condition of aspirator according to melt viscosity, rate of extrusion, spinning mouth temperature and the cooling condition etc. of the molten polymer that is pushed through the spinning mouth to single thread.If hauling speed is lower than 1000m/min, the cooling of the single thread of being extruded and curing will be very slow, so that adjacent single thread may fuse together.In addition, because directed the delay and crystallization, the adhesive-bonded fabric of producing can be very coarse, and its mechanical strength is also very poor.When pulling speed was higher than 6000m/min, because speed is too high, it had surpassed their spinnability and tensile properties, and therefore the single thread of extruding can rupture, so that had stoped the steady production of adhesive-bonded fabric.
In the present invention, local hot pressing PVA base non-woven fabric fiber network so that with fibre fusion together, makes fleece keep their shape thus.More precisely, make fleece by between the top thermometal roller and hot flat roll that the burr decorative pattern arranged.This is the hot pressing long fibre partly, and they are fused together, and can keep the shape of adhesive-bonded fabric thus.The heating roller temperature that can suitably select to adopt in the above-mentioned heat fused step according to needs, thermal pressure, processing speed, burr decorative pattern etc.
The long fibre based on PVA that constitutes adhesive-bonded fabric according to the present invention is hydrophilic, thereby can obviously reduce the fusing point of fiber when water exists.Based on this reason, before the heat fused step, can reduce heat roller temperature by add water to fleece.
If spunbond adhesive-bonded fabric is not suitable as rag owing to having highly-water-soluble, then can heat-treat to control water-soluble to adhesive-bonded fabric.This is because heat treatment can promote the crystallization of the resin of formation fiber.Both can in the production process of adhesive-bonded fabric, also can after to roller, heat-treat at fabric.
In addition, can utilize hot-air, heating plate or hot-rolling adhesive-bonded fabric to be heat-treated, fabric directly is exposed in the water, for example avoid being dipped in the water-bath fabric just passable as long as can avoid by any suitable method.
Preferably, when when down measuring 1 minute for 20 ℃, PVA base long fibre nonwoven fabric used in the present invention shows 2cm or longer suction length, 2.5cm or longer more preferably, and more preferably 3cm or longer most preferably is 3.5cm or longer.When suction length during less than 2cm, water absorption rate is very poor, is not suitable for use in rag with regard to this adhesive-bonded fabric of its function.
Measure the suction length of adhesive-bonded fabric according to JISL1018-70 " knitted fabric method of testing " (water absorption rate method of testing B (Byreck method), KRT, 411-2 number).Say exactly, asking the adhesive-bonded fabric sample of 2.5cm * 17cm that it is dipped into 1cm the ink (China ink/water=1/5) from the bottom from its bottom, and keeping 1 minute, measure because the water height that capillarity sucks.
Thus, the working condition by suitable selection PVA and adhesive-bonded fabric can provide the water absorption rate and the toughness of level of hope according to requiring for phozy rag of the present invention.
Key character according to rag of the present invention is: rag is textile by PVA base long fibre nonwoven, and described long fibre is by the melt-spun manufactured, and it shows rational hydrophily and phozy characteristic.Therefore, in the present invention, specifically do not limit following content: long stapled fineness and shape of cross section, the basic weight of adhesive-bonded fabric, mechanical property such as tensile elongation, tensile strength, tearing strength, such as the structure of thickness and fluffy degree, and, can suitably select them according to the scope that adopt usually this area such as other characteristic of flexibility.
Example
By describing the present invention in more detail with reference to following example.Yet these examples only are illustrative, do not plan to limit the present invention with them.In following example and comparative example, measure each characteristic and feature by the following method, unless specify separately, " umber " and " % " represents " mass fraction " and " quality % " respectively.
1, the analysis of PVA
Unless otherwise specified, by the methods analyst PVA that describes among the JISK6726.
Utilize 500MHZ's
1H NMR (JEOLGX-500) measures the modification degree of modified poly ethylene ester or modified PVA.
Utilize atomic absorption method to measure alkali metal ion content measured.
2. fusing point
The fusing point of representing PVA with the peak temperature of the endothermic curve of PVA, described endothermic curve is to utilize differential scanning calorimeter (TA3000 that buys from Mettler company) to record by following steps: the programming rate with 10 ℃/min the atmosphere of nitrogen is heated to 250 ℃ with sample, and cool to room temperature, the programming rate with 10 ℃/min is heated to 250 ℃ with sample again.
3. plasticity
Visual and by touch observing melt-spun state and resulting adhesive-bonded fabric, according to following grade they are estimated:
A: excellent; B: good; C is slightly poor; And D: poor.
4. basic weight and thickness
Measure the basic weight and the thickness of adhesive-bonded fabric according to JIS L 1906 " method of testing of the adhesive-bonded fabric of making by filament yarn ".
5. toughness
Measure the basic weight and the thickness of adhesive-bonded fabric according to JIS L 1906 " method of testing of the adhesive-bonded fabric of making by filament yarn ".
6. suction length
Measure the suction length of adhesive-bonded fabric according to JIS L 1018-70 " method of testing of knitted fabric " (water absorption rate method of testing B (Byreck method), KRT, 411-2 number).
That is, asking adhesive-bonded fabric sample to be immersed in 1cm the ink (China ink/water=1/5) from its bottom, and keeping 1 minute, measuring because the water height that capillarity absorbs from its bottom with 2.5cm * 17cm.
7. water-retaining property
Behind the finish-drying, the adhesive-bonded fabric after 20cm * 20cm accurately weighed was immersed in the 50cc pure water under 20 ℃ 5 minutes.Then, from water, take out adhesive-bonded fabric, and it was kept above the water surface 30 seconds.When water no longer when adhesive-bonded fabric drips, measure the gross weight of adhesive-bonded fabric, calculate water retention.
8. not wiping amount
1 gram distilled water is placed in the surface plate that diameter is 9cm.The adhesive-bonded fabric of 5cm * 5cm is immersed 5 seconds in the distilled water, and remove fabric from it, measure the water yield of staying in the surface plate.
9. fine fleece or fine hair comes off
With diameter is the circular urethane sheet of 7cm become the to enclose the land adhesive-bonded fabric 10 times (each friction clockwise once, then counterclockwise once) of friction 15cm * 15cm.The fibre weight that perusal is come off by fabric.The result is divided into 5 grades: 1 to 5, wherein 1 expression seriously comes off, and 5 expressions do not come off basically.
10. the phozy characteristic of adhesive-bonded fabric in the water
The adhesive-bonded fabric of 20cm * 20cm is dipped in the flask in the 500cc pure water under 20 ℃.Flask is couched and dandle 100 times.After this, the fine hair amount in the perusal water.The result is divided into 5 grades: 1 to 5, wherein 1 expression forms serious fine hair, and 5 expressions do not form fine hair basically.
The production of ethene modified PVA
29.0kg vinyl acetate and 31.0kg methyl alcohol are installed to 100 boost in the power reactor, described reactor is provided with agitator, nitrogen inlet, ethene inlet and initator inlet.After the content of reactor is heated to 60 ℃,, purged reaction system 30 minutes with nitrogen by making the nitrogen boiling.Ethene is imported to reactor, reach 5.9kg/cm up to internal pressure
2(5.8 * 10
5) till.
Prepare separately 2 of 2.8g/l, 2 '-azo two (4-methoxyl group-2,4-dimethylbutyl cyanogen) methanol solution (AMV) is as initator, and purges them with nitrogen boiling bubble.After the internal temperature of reactor is adjusted to 60 ℃, the 170ml initiator solution is injected in the reactor with initiated polymerization.In polymerization process, the internal pressure of reactor is remained on 5.9kg/cm by importing ethene
2(5.8 * 10
5Pa), and make internal temperature keep 60 ℃, inject initiator solution continuously with the speed of 610ml/hr simultaneously.
When the degree of polymerization reached 70% after 10 hours, cooling reactor was to stop polymerisation.Open reactor and discharge ethene, make the reactant mixture boiling so that thoroughly remove ethene with nitrogen.Then, under reduced pressure, remove unreacted vinyl acetate monomer to obtain the methanol solution of polyvinyl acetate.
The methanol solution of resulting polyvinyl acetate and the methyl alcohol of magnitude of recruitment are mixed, so that the content of polyvinyl acetate is adjusted into 50%.In the methanol solution (polyvinyl acetate that contains 100g) of the resulting polyvinyl acetate of 200g, add the methanol solution (mol ratio of NaOH and vinyl acetate unit (MR) is 0.10) of the NaOH of 46.5g10%, thereby make the polyvinyl acetate saponification.After 2 minutes gel reaction takes place at adding alkali lye.By grinding machine gel is rolled into powder, makes mixture under 60 ℃, leave standstill 1 hour to carry out saponification.To in the mixture of saponification, adding water/methyl alcohol (20/80) mixed solution that 1000g contains 0.5% acetate, with the remaining alkali that neutralizes.After utilizing phenolphthalein indicator to determine that neutralization is finished, reactant mixture is filtered, obtain the PVA of white solid, its water/methyl alcohol (20/80) mixed solution with 2000g is mixed, and make it at room temperature leave standstill 3 hours to wash PVA.After the repeated washing step 3 time, further that the methyl alcohol of PVA and 1000g is mixed, and make it at room temperature leave standstill 3 hours so that wash.Then, by centrifugal removal liquid phase, isolated PVA is placed 70 ℃ drier 2 days, thereby obtained dry PVA (PVA-1).The saponification degree of ethene modified PVA is 98.4%.
Grind modified PVA, and it is dissolved in the acid, utilize Atomic Absorption Spectrometer to measure sodium content.The result represents that sodium ion accounts for 0.0005 mass parts based on 100 mass parts of modified PVA.
In addition, will be added in the n-hexane by the methanol solution of from polymerization reaction mixture, removing the polyvinyl acetate that unreacted vinyl acetate obtains, so that polyvinyl acetate is precipitated.The polyvinyl acetate that precipitates is dissolved in the acetate, once more gained solution is added in the n-hexane with the precipitation polyvinyl acetate.To precipitate again and purification step repeats 3 times, then under the reduced pressure under 80 ℃ with polyvinyl acetate drying precipitate 3 days, obtained purified polyvinyl acetate thus.Purified polyvinyl acetate is dissolved among the d6-DMSO, uses 500MHz's down at 80 ℃
1HNMR (JEOL GX-500) analyzes.The result represents that ethylene contents is 10mol%.
The methanol solution of the polyvinyl acetate that is obtained above the saponification in mol ratio is alkali-vinyl acetate of 0.5 is rolled into powder with grinding machine with it, and it is left standstill carried out saponification in 5 hours under 60 ℃.Utilize the Soxhlet extractor to extract saponification mixture with methyl alcohol, then under 80 ℃ of following reduced pressure with dry 3 days of extract to obtain purified ethene modified PVA.The average degree of polymerization of the ethene modified PVA that records by the universal method according to JISK6726 is 330.
Purified ethene modified PVA is dissolved in the water the aqueous solution to prepare 5%, it is poured into the thick film of 10 μ m.Make film drying after 1 day under the reduced pressure under 80 ℃, utilizing DSC (TA3000 that buys by Mettler company) to measure the fusing point of PVA by said method.As its measurement result, the fusing point of PVA is 206 ℃.
Prepare the ethene modified PVA by the same manner: PVA-2 is to PVA-20.Its feature is shown among Fig. 1.
Table 1
Table 1 (continuing)
1)(acetic acid content) of α=PVA/(sodium ions content)
| Degree of polymerization saponification degree Tm (mol%) (℃) |
| ?PVA-1?????330????98.4????206 ?PVA-2?????560????98.2????192 ?PVA-3?????230????98.9????207 ?PVA-4?????330????99.7????216 ?PVA-5?????290????94.1????188 ?PVA-6?????350????98.3????222 ?PVA-7?????450????98.7????208 ?PVA-8?????320????98.1????179 ?PVA-9?????280????98.2????195 ?PVA-10????330????98.4????206 ?PVA-11????330????98.4????206 ?PVA-12????330????98.4????206 ?PVA-13????290????88.0????178 ?PVA-14????450????98.7????208 ?PVA-15????380????98.3????176 ?PVA-16????230????98.9????207 ?PVA-17????1050???97.8????206 ?PVA-18????150????98.6????207 ?PVA-19????350????99.8????234 ?PVA-20????410????99.0????153 |
| Modifier | Modification degree (mol%) | Sodium ion (mass fraction) | ????α 1) | |
| ??PVA-1 ??PVA-2 ??PVA-3 ??PVA-4 ??PVA-5 ??PVA-6 ??PVA-7 ??PVA-8 ??PVA-9 ??PVA-10 ??PVA-11 ??PVA-12 ??PVA-13 ??PVA-14 ??PVA-15 ??PVA-16 ??PVA-13 ??PVA-14 ??PVA-15 ??PVA-16 | Ethene ethene ethene ethene ethene-propylene ethyl vinyl ether N-ethernamine ethene ethene ethene ethylene, propylene ethene ethene ethene ethene-ethyl vinyl ether | ????10 ????18 ????11 ????10 ????5 ????- ????3 ????6 ????3 ????10 ????10 ????10 ????5 ????3 ????28 ????11 ????7 ????10 ????- ????10 | ????0.0005 ????0.003 ????0.0008 ????0.002 ????0.0004 ????0.003 ????0.001 ????0.003 ????0.002 ????0.03 ????0.00005 ????0.0009 ????0.0001 ????0.07 ????0.01 ????0.006 ????0.0006 ????0.005 ????0.001 ????0.002 | ????0.04 ????0.1 ????0.09 ????0.07 ????0.2 ????0.1 ????0.08 ????0.2 ????0.1 ????0.08 ????0.4 ????0.9 ????0.2 ????0.09 ????1.2 ????0.007 ????0.1 ????0.2 ????0.07 ????0.1 |
Example 1
Under 225 ℃ in melt extruder melt kneading PVA-1.The polymer of fusing is imported in the spinneret, and from the spinning head that possesses 24 spray orifices it is extruded, each injection diameter is 0.25mm.The single thread that is spun into is imported in the columniform jet aspirator, simultaneously with the cooling of 20 ℃ cooling air, this with the hauling speed of about 3500m/min with the single thread drawing-down.The broken composition of the single thread that will attenuate from fiber, and be collected in from level to level on mobile the conveyer belt forming long stapled fleece.Make fleece be 20kgf/cm, be heated between 180 ℃ the inhomogeneous relief printing roller and flat roll, so that partly make fiber generation hot melt at burr by linear pressure.Make fleece in 2 minutes by the hot air dryer under 200 ℃ so that fleece is done further heat treatment, having obtained by basic weight thus is 34g/m
2, monofilament fineness is the adhesive-bonded fabric that the long fibre of 4.4dtex is made.
Make the process conditions of adhesive-bonded fabric and the plasticity of PVA and be shown in Table 2, the evaluation result of the following each side of prepared adhesive-bonded fabric has been shown in table 3: basic weight, thickness, transverse toughness, water-retaining property, suction length, not wiping amount, cilium or fine hair come off and water in phozy characteristic.Example 2 to 16
PVA-2 in utilizing table 1 replaces PVA-1 and changes the working condition as shown in table 2 to PVA-16, makes the long stapled nonwoven web of PVA by the mode identical with example 1.Under the temperature shown in the table 2, resulting adhesive-bonded fabric is impressed and heat treatment, thereby obtained long stapled adhesive-bonded fabric.The evaluation result of prepared adhesive-bonded fabric in following each side has been shown in table 3: basic weight, thickness, transverse toughness, water-retaining property, suction length, the amount of not smearing, cilium or fine hair come off and water in phozy characteristic.Comparative example 1 to 4
PVA-17 in utilizing table 1 replaces PVA-1 and changes the working condition as shown in table 2 to PVA-20, makes the long stapled nonwoven web of PVA by the mode identical with example 1.Under the temperature shown in the table 2, resulting adhesive-bonded fabric is impressed and heat treatment, thereby obtained long stapled adhesive-bonded fabric.
In the comparative example 1 that utilizes PVA-17, the melt viscosity of PVA is too high, so that can not be stably with melt polymer extruding spinning mouth, thereby can not obtain nonwoven web.Although can obviously reduce melt viscosity when spinneret is heated to 280 ℃, yet thermal decomposition and gelatification can take place in this, bring more undesired result thus.
In the comparative example 2 that utilizes PVA-18, the melt viscosity of PVA is too low so that melt polymer can drippage the process of extruding from spinning head under, thereby stably producd fibers and nonwoven web.
In the comparative example 3 that utilizes PVA-19, the melt viscosity of PVA is too high under 240 ℃ spinning temperature, because this spinning temperature point is very approaching.Although can significantly reduce melt viscosity when spinneret is heated to 255 ℃, the thermal decomposition and the gelatification that take place can be brought more unwanted results.
In the comparative example 4 that utilizes PVA-20, adjacent is spun into silk because their crystallizations reduce and fusion each other.The silk that has fused can not be divided into the fiber of separation, has caused forming coarse nonwoven web.
Table 2
| ????PVA | Plasticiser (mass parts) | Working condition | |||
| The spinning temperature (℃) | Pulling speed (m/min) | Imprint temperature (℃) | Heat treatment temperature (℃) | ||
| 1 PVA-1,2 PVA-2,3 PVA-3,4 PVA-4,5 PVA-5,6 PVA-6,7 PVA-7,8 PVA-8,9 PVA-9,10 PVA-10,11 PVA-11,12 PVA-12,13 PVA-13,14 PVA-14,15 PVA-15,16 PVA-16 comparative examples, 1 PVA-1,2 PVA-2,3 PVA-3,4 PVA-4 | ????- ????- ????- ????- ????- ????DG*(3) ????- ????- ????- ????- ????- ????- ????- ????- ????- ????- ? ????- ????- ????DG*(3) ????- | ????225 ????220 ????225 ????235 ????210 ????240 ????230 ????200 ????215 ????225 ????225 ????225 ????200 ????230 ????195 ????225 ? ????280 ????220 ????255 ????175 | ????3500 ????3000 ????3500 ????3500 ????3000 ????2500 ????3500 ????3500 ????3500 ????3500 ????3500 ????3500 ????2500 ????2000 ????2000 ????2500 ? ????1000 ?????- ?????- ????2500 | ????180 ????170 ????180 ????190 ????170 ????200 ????190 ????160 ????170 ????180 ????180 ????180 ????160 ????190 ????150 ????180 ? ????- ????- ????- ????120 | ????200 ????- ????200 ????200 ????180 ????200 ????200 ????180 ????180 ????200 ????200 ????200 ????180 ????200 ????- ????200 ? ????- ????- ????- ????140 |
The DG=diglycerol
Table 2 (continuing)
| Plasticity | ||
| Spinning | Adhesive-bonded fabric | |
| 1 PVA-1,2 PVA-2,3 PVA-3,4 PVA-4,5 PVA-5,6 PVA-6,7 PVA-7,8 PVA-8,9 PVA-9,10 PVA-10,11 PVA-11,12 PVA-12,13 PVA-13,14 PVA-14,15 PVA-15,16 PVA-16 comparative examples, 1 PVA-1,2 PVA-2,3 PVA-3,4 PVA-4 | ????A ????A ????A ????A ????A ????B ????A ????A ????A ????A ????A ????A ????B-C ????B-C ????B-C ????B-C ? ????D ????D ????D ????D | A-B-A-A-B-B-A-A-A-A-A-A-B-C slightly has and decomposes smell C and slightly have fibrous fracture C slightly to have fibrous fracture B-C that decomposition smell-because thermal decomposition and the fiber that can not stably spin-again and again have disconnects-D that can not stably spin has the bonding of serious fiber and fiber because viscosity increases is arranged slightly |
Table 3
| Evaluation result | ||||||||
| Basic weight (g/m 2) | Thickness (mm) | Transverse toughness (N/2.5cm) | Suction length (cm) | Water-retaining property (%) | The amount of not smearing (g) | Fine hair disengaging amount | Phozy character in the water | |
| Example 123456789 10 11 12 13 14 15 16 comparative examples 4 | ????34 ????35 ????35 ????32 ????37 ????35 ????28 ????34 ????32 ????35 ????36 ????35 ????37 ????34 ????28 ????37 ????34 | ??0.25 ??0.28 ??0.25 ??0.20 ??0.31 ??0.26 ??0.17 ??0.23 ??0.27 ??0.29 ??0.29 ??0.26 ??0.29 ??0.20 ??0.18 ??0.29 ??0.28 | ????32 ????38 ????30 ????31 ????28 ????27 ????30 ????32 ????33 ????34 ????34 ????32 ????29 ????23 ????25 ????28 ????9 | ????5.6 ????4.2 ????5.8 ????4.9 ????7.5 ????6.1 ????5.7 ????5.4 ????5.9 ????5.4 ????5.5 ????5.2 ????5.6 ????5.2 ????2.9 ????5.5 ????5.1 | ??1005 ??691 ??1029 ??955 ??1071 ??1038 ??993 ??971 ??1035 ??976 ??989 ??962 ??1065 ??961 ??382 ??987 ??987 | ??0.13 ??0.23 ??0.11 ??0.16 ??0.08 ??0.10 ??0.14 ??0.15 ??0.11 ??0.15 ??0.14 ??0.15 ??0.09 ??0.13 ??0.29 ??0.15 ??0.14 | ????5.0 ????5.0 ????5.0 ????5.0 ????4.5 ????4.5 ????5.0 ????5.0 ????5.0 ????5.0 ????5.0 ????5.0 ????4.5 ????4.5 ????4.5 ????4.5 ????4.5 | ????5.0 ????5.0 ????4.5 ????5.0 ????4.5 ????4.5 ????5.0 ????5.0 ????5.0 ????5.0 ????5.0 ????5.0 ????4.5 ????4.5 ????4.0 ????4.5 ????4.5 |
Industrial applicibility
According to the present invention, PVA-based adhesive-bonded fabric shows the high wettability to water, these wetabilitys are water imbibition, hydrophily and swellability for example, this adhesive-bonded fabric is to make by the melt-spun method that adopts in the production process of spunbond adhesive-bonded fabric, has fine hydrophilic phozy rag thereby provide.
Claims (7)
1. nonlinting rag, it comprises the adhesive-bonded fabric of being made by thermoplastic polyvinyl alcohol base long fibre, and described long stapled viscometric degree of polymerization is 200 to 700, and fusing point is 160 to 230 ℃.
2. phozy rag according to claim 1, wherein, the suction length when rag is dipped in the water 1 minute under 20 ℃ is 2cm or higher.
3. phozy rag according to claim 1 and 2, wherein the polyvinyl alcohol amount of comprising is the alkali metal ion (B) of 0.00001 to 0.05 mass parts, this mass parts is based on the mass parts 100 of polyvinyl alcohol (A).
4. according to each described phozy rag in the claim 1 to 3, wherein, polyvinyl alcohol (A) comprises a kind of acid (C), acid (C) comprise when pKa when measuring down for 25 ℃ be 5.0 or lower acid group, it is 0.01 to 1 that the amount of acid makes the ratio a scope by the polyvinyl alcohol of following formula definition: a=(content (quality %) of sour (C) content (quality %)/alkali metal ion (B))
5. according to each described phozy rag in the claim 1 to 4, wherein the saponification degree of polyvinyl alcohol (A) is 90 to 99.99mol%.
6. according to each described phozy rag in the claim 1 to 5, wherein polyvinyl alcohol (A) is a modified polyvinylalcohol, it comprises a unit of selecting in the group of being made up of following material at least: have 4 or the a-olefin unit of carbon atom still less, vinethene unit and N-ethernamine unit, the total amount of these unit account for 0.1 to 20mol%.
7. phozy rag according to claim 6, wherein polyvinyl alcohol (A) is a modified polyvinylalcohol, it comprises that content is 3 to 20mol% ethylene unit.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP75810/2000 | 2000-03-17 | ||
| JP75810/00 | 2000-03-17 | ||
| JP2000075810 | 2000-03-17 | ||
| JP93629/00 | 2000-03-30 | ||
| JP93629/2000 | 2000-03-30 | ||
| JP2000093629A JP4368492B2 (en) | 2000-03-17 | 2000-03-30 | Wiper with excellent lint-free properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1364064A true CN1364064A (en) | 2002-08-14 |
| CN1175135C CN1175135C (en) | 2004-11-10 |
Family
ID=26587775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB018005500A Expired - Fee Related CN1175135C (en) | 2000-03-17 | 2001-03-13 | Wiper with excellent lint-free property |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4368492B2 (en) |
| KR (1) | KR100799012B1 (en) |
| CN (1) | CN1175135C (en) |
| TW (1) | TW592657B (en) |
| WO (1) | WO2001070089A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871391B (en) * | 2003-07-16 | 2010-11-10 | 弗莱斯纳有限责任公司 | Cloth for wet cleaning, method and device for the production of said cloth |
| CN101146472B (en) * | 2005-05-09 | 2012-07-11 | 约翰逊父子公司 | Method of cleaning using a device with a liquid reservoir and replaceable non-woven pad |
| CN101353847B (en) * | 2007-06-14 | 2013-04-24 | 卡尔弗罗伊登柏格两合公司 | Cleaning article and its use |
| CN103280250A (en) * | 2013-05-20 | 2013-09-04 | 世源科技(嘉兴)医疗电子有限公司 | Disposable protective garment for nuclear industry and processing method after disposable protective garment is used |
| CN105671794A (en) * | 2014-11-18 | 2016-06-15 | 深圳科宏健科技有限公司 | Wiping cloth and preparation method thereof |
| CN108024683A (en) * | 2015-10-02 | 2018-05-11 | 宝洁公司 | With the preferably cleaning pad with the performance of water |
| EP4321669A1 (en) * | 2022-08-13 | 2024-02-14 | Aquapak IP Limited | Polyvinyl alcohol fibres and spunbond fibrous products |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3280469B2 (en) * | 1993-06-08 | 2002-05-13 | 株式会社クラレ | Composite fiber with excellent light resistance |
| JPH09266873A (en) * | 1996-04-03 | 1997-10-14 | Kuraray Co Ltd | Thick wiping cloth |
-
2000
- 2000-03-30 JP JP2000093629A patent/JP4368492B2/en not_active Expired - Fee Related
-
2001
- 2001-03-13 CN CNB018005500A patent/CN1175135C/en not_active Expired - Fee Related
- 2001-03-13 WO PCT/JP2001/001961 patent/WO2001070089A1/en active Application Filing
- 2001-03-13 KR KR1020017014644A patent/KR100799012B1/en not_active IP Right Cessation
- 2001-03-16 TW TW090106216A patent/TW592657B/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871391B (en) * | 2003-07-16 | 2010-11-10 | 弗莱斯纳有限责任公司 | Cloth for wet cleaning, method and device for the production of said cloth |
| CN101146472B (en) * | 2005-05-09 | 2012-07-11 | 约翰逊父子公司 | Method of cleaning using a device with a liquid reservoir and replaceable non-woven pad |
| CN101353847B (en) * | 2007-06-14 | 2013-04-24 | 卡尔弗罗伊登柏格两合公司 | Cleaning article and its use |
| CN103280250A (en) * | 2013-05-20 | 2013-09-04 | 世源科技(嘉兴)医疗电子有限公司 | Disposable protective garment for nuclear industry and processing method after disposable protective garment is used |
| CN105671794A (en) * | 2014-11-18 | 2016-06-15 | 深圳科宏健科技有限公司 | Wiping cloth and preparation method thereof |
| CN108024683A (en) * | 2015-10-02 | 2018-05-11 | 宝洁公司 | With the preferably cleaning pad with the performance of water |
| EP4321669A1 (en) * | 2022-08-13 | 2024-02-14 | Aquapak IP Limited | Polyvinyl alcohol fibres and spunbond fibrous products |
| EP4321668A1 (en) * | 2022-08-13 | 2024-02-14 | Aquapak IP Limited | Polyvinyl alcohol fibres and spunbond fibrous products |
| WO2024037988A1 (en) * | 2022-08-13 | 2024-02-22 | Aquapak Ip Limited | Polyvinyl alcohol fibres and spunbond fibrous products |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1175135C (en) | 2004-11-10 |
| WO2001070089A1 (en) | 2001-09-27 |
| JP4368492B2 (en) | 2009-11-18 |
| KR100799012B1 (en) | 2008-01-28 |
| JP2001329458A (en) | 2001-11-27 |
| TW592657B (en) | 2004-06-21 |
| KR20020006717A (en) | 2002-01-24 |
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