TW592657B - Wiper having excellent lint-free property - Google Patents

Abstract

Provided is a wiper excellent in lint-free property and having strong affinity to water, that is, water absorbing, hydrophilic and water swelling properties and the like. A lint-free wiper is made from polyvinyl alcohol type filament non-woven fabric. Said polyvinyl alcohol (A) has a viscosity average polymerization degree of 200 to 700, a saponification ratio of 90 to 99.99 mol% and a melting point of 160 to 230 DEG C, and contains 0.00001 to 3 parts by mass of (B) alkaline metal ions, based on 100 parts by mass of the (A).

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592657 A7 B7 V. Description of the Invention (f) Technical Field The present invention relates to a wipe which is formed of a thermoplastic polyvinyl alcohol-based long-fiber non-woven fabric with excellent non-pilling properties. The wipes used in the clean room in the prior art are used to wipe liquids, etc., and are used when cleaning the walls or beds in the clean room. Therefore, in addition to water absorption, oil absorption, and softness (for wiping objects such as walls or beds), In addition to good compatibility or compliance), high non-fuzzing properties are also required (rarely, there are few cases of dust or raw materials missing). In order to reduce the generation of fluff, it is necessary to prevent the products from generating dust or falling off a small amount of fibers, and in particular, it is necessary to prevent the fibers around the cut surface from being cut from the sheet when the cloth is cut. Therefore, it is extremely important that the fibers constituting the non-woven fabric are long-fiber systems. The method is preferably a melt spinning of a thermoplastic polymer, and the obtained long fibers are directly formed into a non-woven fabric, that is, an embossing method. At present, most of clean room wipes use non-woven fabrics mainly composed of cellulose fibers. However, cellulose fibers are highly water-absorptive fibers, have no thermoplasticity, and cannot be applied to the above-mentioned embossing method. In addition, in the case of a thermoplastic polymer, fibers can be prevented from being detached by thermal fusion, but cellulose fibers cannot be used. In addition, when a polyester fiber or the like is used as the thermoplastic fiber, it has to be subjected to a hydrophilic processing treatment because of its low water absorption. In this case, there may be problems such as an increase in eluted matter when wiping with an organic solvent or the like to improve water absorption. The invention shows that the object of the present invention is to provide an excellent non-fuzzing property, and have a paper size suitable for the Chinese National Standard (CNS) A4 (210 X 297 mm) 丨 丨 ---------- ----- ^ --------- (Please read the phonetic on the back? Matters before filling out this page) 592657 Printed by the Consumers' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7____ V. Description of Invention (V) Water-based, hydrophilic, water-swellable wipes with strong affinity for water. The present invention is made of a polyvinyl alcohol nonwoven fabric having a strong affinity for water, such as water absorption, hydrophilicity, and water swelling, by using a manufacturing technique of an embossed nonwoven fabric by a melt spinning method, and can provide an excellent hydrophilicity And a cloth with excellent non-fuzziness. In other words, the present invention provides a non-fluffing wiper formed from a thermoplastic polyvinyl alcohol-based long-fiber nonwoven fabric having an average viscosity of 200 to 700 and a melting point of 160 ° C to 230 ° C. Embodiments of the invention Of course, the polyvinyl alcohol in the polyvinyl alcohol nonwoven fabric of the present invention is a homopolymer of polyvinyl alcohol, for example, a modified polyvinyl alcohol containing a copolymer, terminal modification, and introduction of a functional group by post-reaction. The polyvinyl alcohol (hereinafter referred to as PVA) used in the present invention has an average viscosity polymerization degree (hereinafter referred to as polymerization degree) of 200 to 700, preferably 230 to 600, and more preferably 250 to 500. When the degree of polymerization is less than 200, sufficient drawability cannot be obtained during spinning, and fiberization cannot be achieved. If the polymerization degree is more than 700, the melt viscosity is too high, and the polymer cannot be stably ejected from the spinning nozzle. The degree of polymerization (P) of PVA is measured based on JIS-K6726. In other words, the intrinsic viscosity [々] (d 1 / g) measured in water at 30 ° C after completely re-saponifying and refining PVA was obtained by the following formula. P = ([7?] X 1 03 / 8.29) (1/0 62) If the degree of polymerization is within the above range, the purpose of the invention can be achieved. The degree of saponification of PVA used in the present invention is 90 ~ 99.99 mol%. (Please read the precautions on the back before filling in this page) # Order --------- line

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 592657 A7

V. Description of the Invention (3) The employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed 93 ~ 99.98 mole% for the better, 94 ~ 99.97 mole% for the better, and 95 ~ 99.96 for the best. Mole%. When the degree of saponification is less than 90 mol%, the thermal stability of PVA is not good, and satisfactory melt spinning cannot be performed due to thermal decomposition or gelation. In addition, if the degree of saponification is more than 99.99 mol%, large PVA cannot be produced stably. At this time, it cannot be stably fibrillated and a long-fiber nonwoven fabric cannot be formed. In addition, the obtained nonwoven fabric had a reduced water absorption property, and it was not possible to obtain satisfactory performance when used as a wiper. The melting point (Tm) of the PVA used in the present invention is 160 to 230X :, preferably 170 to 227 ° C, and more preferably 180 to 220 ° C. When the melting point is less than 160 ° C, the crystallinity of PVA decreases, the strength of the nonwoven fabric constituent fibers decreases, and the confidence strength of the nonwoven fabric decreases. Depending on the situation, there is a need for yarn pullability during melt spinning, and severe thermal decomposition occurs, making it impossible to obtain nonwoven fabrics. In addition, most of the obtained non-woven fabrics have fluff particles or fluff, and it is impossible to obtain satisfactory performance as a rag. In addition, if the melting point is higher than 230 ° C, the melt spinning temperature must be increased to ensure proper melt viscosity. Since the spinning temperature is close to the decomposition temperature of PVA, the spinning cannot be melted stably, and the nonwoven fabric cannot be manufactured stably. The melting point of PVA means that when DSC is used, the temperature is raised to 250 ° C at a temperature increase rate of 10 ° C / min in nitrogen gas, and then cooled to room temperature, and then heated to 250 ° C at a temperature increase rate of 10 ° C / min. The temperature of the peak point of the endothermic peak of the melting point of PVA. PVA is obtained by saponifying a vinyl ester unit of a vinyl ester polymer. The vinyl compound monomers used to form vinyl ester units include, for example, vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl decanoate, and the Chinese standard paper (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page) Spring order --------- line

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V. Description of the Invention (Pregnancy) The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed vinyl laurate, vinyl stearate, vinyl benzoate, vinyl trimethylacetate, and vinyl vinyl acetate, etc. For the production of PVA, vinyl acetate is preferred. The polymer constituting the PVA-based long fibers of the present invention may be a homopolymer of PVA or a PVA introduced with a copolymerization unit. In terms of melt spinning properties and fiber properties, a denatured PVA with a copolymerization unit introduced may be used. Better. The types of copolymerized monomers are, for example, α-olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-hexene, acrylic acid and its salts, methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate. Acrylic esters such as propyl esters, acrylamide, N-methacrylamide, N-ethyl acrylamide derivatives, acrylamide derivatives, methacrylamide, N-methacrylamide, N -Methacrylamide derivatives such as ethyl methacrylamide, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether Type, glycol vinyl ether, 1,3-propanediol vinyl ether, 1,4-butanediol vinyl ether and other hydroxyl-containing vinyl ethers, allyl acetate, propyl allyl ether, butylene Allyl ethers such as propyl ether and hexyl allyl ether, monomers having an alkylene oxide group, vinyl silyl groups such as vinyl trimethoxysilane, isopropenyl acetate, 3-butene-1-fluorenyl , 4-butene-1-fluorenyl, 5-hexene-1-fluorenyl, 7-octyl-1-fluorenyl, 9-decene-1-fluorenyl, 3-methyl-3-butene- 1-fluorenyl group-containing α- Hydrocarbons, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinylamine, fumaric acid, maleic acid, itaconic acid, horse Monocarboxylic acid-containing monomers such as maleic anhydride, phthalic anhydride, trimellitic anhydride, or itaconic anhydride, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-propenylamine-2-methylpropane The size of this paper is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page) See I ------ Order ------- --line

592657

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, i, invention description (t) and other monomers with sulfonic acid groups; vinyloxyethyltrimethylammonium chloride, vinyloxybutyltrimethylammonium chloride, vinyloxyethyl Dimethylamine, vinyloxymethyldiethylamine, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, methallyltrimethylammonium chloride, dimethyl A monomer having a cationic group such as allylamine and allylethylamine. The content of these monomers is usually 25 mol% or less. Among these monomers, α-olefins such as ethylene, propylene, 1-butene, isobutylene, and 1-hexene, acrylic acid and its salts, methyl vinyl ether, ethyl vinyl ether, Containing vinyl ethers such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, ethylene glycol ethylene ether, 1,3-propylene glycol vinyl ether, 1,4-butanediol vinyl ether, etc. Hydroxyl vinyl ethers, allyl acetate, propyl allyl ether, butyl allyl ether, hexyl allyl ether, allyl ethers, N-vinylacetamide, N-vinylpyrrolidone, etc. N-vinylamines, monomers having an alkylene oxide, 3-butene-1-fluorenyl, 4-butene-1-fluorenyl, 5-hexene-1-fluorenyl, 7-octyl Hydroxy-containing α-olefins such as methyl-1-fluorenyl, 9-decene-1-fluorenyl, and 3-methyl-3-butene-1-fluorenyl are preferred. In particular, those having strong affinity for water, such as copolymerization, melt-spinnability, fiber water absorption, and water swelling, include α such as ethylene, propylene, 1-butene, isobutylene, and 1-hexene. -Olefins, acrylic acid and its salts, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and other vinyl ethers, N-vinylacetamide And N-vinylpyrrolidone are preferred. Units of α-olefins, vinyl ethers, and N-vinylamines having a carbon number of 4 or less are preferably 0.1 to 20 mol% in PVA, and more preferably 1 to 15 mol%. -7- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) 0 Order --------- line

592657 A7 ___ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (Stone) In addition, when α-olefin is ethylene, it is especially useful to use an ethylene unit of 3 to 20 mol% and more for the fiber properties. The better is 5 ~ 18 mol% of modified P V Α. The PVA used in the present invention includes conventional methods such as a block polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among them, a block polymerization method or a solution polymerization method for polymerization in a solvent such as a solvent or an alcohol is generally used. In the solution polymerization, examples of the alcohol used in the solvent include lower alcohols such as methanol, ethanol, and propanol. The initiator used in the copolymerization is, for example, α, α′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl-valeronitrile), benzamyl peroxide, n- -Conventional initiators such as azo-based initiators such as propyl peroxide carbonate or peroxide-based initiators. The polymerization temperature is not particularly limited, but it is preferably 0 ° C to 200 ° C. The content ratio of the (B) alkali metal ions constituting the PVA of the non-woven cloth according to the present invention is 0.00001 to 0.05 parts by mass, more preferably 0.00005 to 0.04 parts by mass, and more preferably 100005 parts by weight (A) PVA in terms of sodium ions. The best is 0.00005 to 0.04 parts by mass, the most preferred is 0.0001 to 0.03 parts by mass, and the best is 0.0002 to 0.02 parts by mass. If the content of the alkali metal ion is less than 0.00001 parts by mass, it cannot be manufactured industrially. In addition, if the content of alkali metal ions is more than 0.05 parts by mass, a nonwoven fabric that is sufficiently decomposed and gelled during melt spinning cannot be obtained. In addition, since the elution of metal ions becomes high, it cannot be used as a clean room cloth. Examples of the "alkali metal ion" include potassium ion and sodium ion. In the present invention, the method of containing a specific amount of (B) alkali metal ions in the PVA is not particularly limited, for example, adding alkali metal ion-8 after polymerizing PVA (Please read the precautions on the back before filling this page) Order --------- Line

This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 592657 A7 ---- B7___ V. Description of the invention (;;) (Please read the precautions on the back before filling this page) In the method of saponifying a vinyl ester polymer in a solvent, an alkali metal ion containing an alkali metal ion is used as a saponification catalyst, an alkali metal ion is compounded in the PVA, and the saponified PVA is washed with a washing solution. The latter method is preferred to control the content of alkali metal ions contained in PVA. The content of the alkali metal ion can be determined by an atomic absorption method. As the saponification catalyst, an alkali metal substance is used, for example, potassium hydroxide or sodium hydroxide. The molar ratio of the alkaline substance used in the saponification catalyst is preferably 0.004 to 0.5 for vinyl acetate units, and more preferably 0.005 to 0.05. The saponification catalyst may be added together at the initial stage of the saponification reaction, or may be added during the saponification reaction. Examples of the solvent for the saponification reaction include methanol, methyl acetate, dimethylamorphine, and dimethylformamide. Among these solvents, methanol is preferable, methanol having a water content of 0.001 to 1% by mass is preferable, and methanol having a water content of 0.003 to 0.9% by mass is more preferable / controlling a water content of 0.005 to 0.8 mass. % Methanol is the best. Examples of the washing liquid include methanol, acetone, methyl acetate, ethyl acetate, hexane, water, and the like. Among these, methanol, methyl acetate, and water alone or a mixture thereof are more preferable. The amount of the cleaning solution is set to satisfy the content ratio of (B) alkali metal ions. Generally, it is preferably 300 to 10,000 parts by mass, more preferably 500 to 5,000 parts by mass, relative to 100 parts by mass of PVA. The washing temperature is preferably 5 to 8 ° C, and more preferably 20 to 70 ° C. The washing time is preferably 20 minutes to 1 hour, and more preferably 1 to 50 hours. Printed in (A) PVA used in the present invention by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, (C) The pKa at 25 ° C is 5.0 or less. The proportion of the acid with an acid group is α as shown in the following formula: 0.01 It is preferably from 1 to 1, more preferably from 0.03 to 0.8, and more preferably from 0.05 to 0.6. The content ratio of the (C) acid in the formula of α shown in the following formulas in the present invention refers to those in which 値 obtained by a neutralization titration method is converted into acetic acid. When the dissociation constant of pKa is Ka, it is defined by pKa = -logKa. When using (C) acid with an acid group having a pKa greater than 5.0 and the content ratio of (C) acid as shown below, α is in the range of 0.01 to 1-9-National Standard (CNS) A4 Specification (210 X 297 mm) 592657 Printed by A7 B7__ in the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. When the invention description ($) is outside, the PVA decomposes, gels, and breaks in the production of spunbond non-woven fabrics. In addition, (C) An acid having an acid group having a pKa of 25 ° C or lower of 5.0 is, for example, acetic acid, phosphoric acid, and sodium phosphate. Content of (C) acid in polyvinyl alcohol (mass%) / Content of (B) alkali metal ion in polyvinyl alcohol (mass%) In the present invention, a specific amount (C) of 25 ° C is contained in PVA The acid method having an acid group having a pKa of 5.0 or less is not particularly limited. After saponifying the polymer of the vinyl ester in a solvent, an acid having an acid group having a pKa of 5.0 or less is used, and the acid is blended with PVA, and The method of washing the PVA obtained by saponification with a washing liquid to control the acid content contained in the PVA, by treating the dried PVA with a solvent containing an acid to contain a specific amount of acid, and preparing the PVA by The method of adding a specific amount of acid to the pellets and the like. The acid content can be determined by neutralizing and titrating the methanol-extracted portion of PVA with an aqueous sodium hydroxide solution. In addition, as long as the purpose and effect of the present invention are not impaired, stabilizers, colorants, ultraviolet absorbers, and light stabilizers such as copper compounds can be added during the polymerization reaction or in subsequent processes as needed. , Prevent oxidants, antistatic agents, flame retardants, plasticizers, lubricants, crystallization rate retarders. In particular, the addition of organic stabilizers such as hindered phenol as thermal stabilizers, copper halide compounds such as copper iodide, and alkali metal halides such as potassium iodide can improve the melt retention stability during fiberization, and are therefore desirable. In addition, if necessary, fine particles having an average particle diameter of 0.01 to 5 μm can be added during the polymerization reaction or subsequent processes. There are no special restrictions on the type of particles, such as silica, alumina, and oxygen -10- (Please read the precautions on the back before filling this page) # Order ----- Line

This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7

Fifth invention description (f) Inert fine particles such as titanium oxide, calcium carbonate, barium sulfate, etc. These can be used alone or in combination of two or more kinds. In particular, inorganic particles having an average particle diameter of 0.02 to 1 μΐΏ are preferred, and spinnability and stretchability can be improved. (Please read the precautions on the back before filling out this page.) Next, the manufacturing method of the long-fiber non-woven fabric made of PVA non-pilling wipes according to the present invention will be described. The non-woven fabric constituting the long fibers of the present invention can be efficiently produced by a method of directly spun-bonded non-woven fabric, that is, spunbond non-woven fabric. In other words, the melt extruder is used to melt and knead the PVA, so that the melted polymer flow is introduced into the spinning head, the flow rate is measured, and the spinning nozzle is discharged. After the discharged yarn is cooled by the cooling device, the air-jet nozzle The suction device draws a sliver with a target fineness of 1000 to 6000 m / min. After being refined by high-speed air traction, the fiber is opened and stacked on a mobile collecting surface to form a non-woven corrugation, which makes the pulling The obtained corrugated part is melted and rolled to obtain a PVA-based long-fiber nonwoven fabric. When manufacturing the non-woven fabric of the present invention, the spinning mold temperature must be melt-spun within the range of (Tm + 10 ° C) ~ (Tm + 8 (TC) for the melting point Tm of the polymer. If the spinning mold temperature is less than At (Tm + 1 0 ° C), the melt viscosity of the polymer is too high, the yarn is drawn by high-speed air flow, and the fineness is not good. If it is higher than (Tm + 80 ° C), it cannot be caused by thermal decomposition of PVA. Stably spinning. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Furthermore, the melting point Tm of the PVA of the present invention is the peak temperature of the main absorption peak as observed by a differential scanning calorimeter (DSC: for example, Mettle Le · TA3000). The present invention In the use of the air jet and nozzle suction device to refine the sliver traction, the take-up speed of 1000 ~ 6000m / min sliver, and high speed -11-This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) 592657 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 i. Description of the invention (f) Airflow traction refinement is extremely important. The yarn extraction conditions by the suction device can be seen from the spinning nozzle holes Melt viscosity, spit The exit speed, spinning nozzle temperature, cooling conditions, etc. are appropriately selected. If it is less than 1 000 m / min, the slivers are melted between the slivers due to slow cooling and solidification, and the slivers cannot be oriented and crystallized. The composite nonwoven fabric is coarse and has low mechanical strength, so it is not desirable. In addition, if it is more than 6000m / min, it cannot follow the slivers and fineness of the sliver, resulting in a sliver cutting situation and a stable nonwoven fabric cannot be produced. In the present invention, the obtained PVA-based corrugation can be partially maintained by hot-pressing and melting. Specifically, the corrugated metal roll (embossed roll) and the smoothing roller are heated to pass the corrugation, so that Partially hot-melt to bond the long fibers to stabilize the non-woven fabric. The temperature of the heat-rolled heat roller, the pressure of heat-pressed, the processing speed, and the shape of the embossed roller can be appropriately selected according to the purpose. The non-woven PVA-based long fibers of the present invention can be active to water, and it can be known from the melting point reduction in the presence of water that the heating roller will be lowered when hot-pressed and melted after adding water. Temperature. The obtained spunbond nonwoven fabric has high dissolution to water and is not suitable for use as a rag. The nonwoven fabric can be adjusted by heat treatment. This is to promote crystallization of the resin that forms fibers by heat treatment. In the manufacturing process of non-woven fabrics, heat treatment may also be performed after winding. In addition, the heat treatment method may be a method of directly exposing the nonwoven fabric in a water bath, or may be performed by hot air, a hot plate, a hot roller, etc. PVA series long-fiber non-woven fabrics are manufactured at a temperature of 1 -12 at 20 ° C. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm). --- line (please read the precautions on the back before filling this page) 592657

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy cm or more. If the suction length is less than 2 cm, the water absorption of the nonwoven fabric is low, and a sufficient wiper function cannot be obtained. The suction length of the non-woven fabric is measured based on T IS-101 8-70 "Test Method for Raw Materials of Knitwear" (water absorption method B (Pelles method) KRT No. 4 11-2). The load at the lower end of the 2.5 cm X 17 cm non-woven fabric was measured, and the suction height was maintained for 1 minute in a water-soluble ink (ink / water = 1/5) until the lower end of the test piece sank by 1 cm. The non-fluffing wiper of the present invention can impart water absorption or strength required for the purpose by selecting PVA and setting conditions when manufacturing the nonwoven fabric. The focus of the wiper formed from the PVA-based long-fiber nonwoven fabric of the present invention is to use the melt-spinning method as described above to manufacture a PVA-based long-fiber nonwoven fabric having reasonable hydrophilicity or non-piling property, and use the same. Therefore, the present invention is not particularly specific to the fineness or cross-sectional shape of the long fibers constituting the non-woven fabric, or to the mechanical properties of the non-woven fabric, such as the mechanical properties of the non-woven fabric, tensile strength, tensile strength, morphological properties such as thickness, volume, or softness. Limitations are usually appropriately selected within a settable range. Examples The present invention will be described in more detail by examples and the like in the following, but the present invention is not limited by these examples. In addition, in the examples, each physical property was determined as follows. In addition, in the examples, the content and% are not particularly limited, and are related to quality. [Analytical method of PVA] -13- This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -------- Order --------- Line (please first (Read the notes on the back and fill out this page)

592657 A7 B7 V. Description of the Invention (l >) When the analysis method of PVA is not specifically described, it is based on JIS-K6726. (Please read the precautions on the back before filling in this page.) The modified mass is determined by measuring with a modified polyethylene ester or modified PVA using a 500MHz proton NMRdEOL GX-500. The content of the alkali metal ion is determined by an atomic absorption method. [Melting point] The melting point of PVA is DSC (Meton La, TA3000), which is heated to 250 ° C at a temperature of 10 ° C / min in nitrogen, and then cooled to room temperature, and then heated at a temperature of 10 ° C. When the temperature rises to 250 ° C / min, it is expressed by the peak point temperature of the endothermic peak indicating the melting point of PVA. [Formability] The state of the melt-spun yarn, that is, the state of the obtained non-woven fabric was visually observed and felt by hand, and evaluated based on the following criteria. ◎: Excellent, 〇: Good, △: Slightly poor, X: Not good [mesh (weight per unit area) and thickness] Measured based on JIS L1 906 "General Long Fiber Nonwoven Test Method". [Strong] Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs TIS L1 906 "General Long Fiber Nonwoven Test Method" [Suck-up length] Measured on the basis of J I S L1 0 1 8-70 "Test Method for Raw Materials of Knitwear" (water absorption method B (Pelles) method KRT No. 41 1-2). Measure the load at the lower end of 2.5cm × 17cm non-woven fabric, and in water-soluble ink -14- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592657 A7 B7 5 In the description of the invention (θ) (ink / water = 1/5), the upper end of the test piece sinks 1 cm, and the suction height is maintained for 1 minute. [Water retention rate] The non-woven fabric, which is finely weighed 20cm X 20cm after being completely dried, is immersed in 500cc pure water at 20 ° C for 5 minutes, and the non-woven fabric is kept in the water state for about 30 seconds. The total weight at the time of fall 'is to obtain the water retention of the non-woven fabric. [Wipe Residual Capacity] 1 g of distilled water was added to a timepiece (diameter 9 cm), and the residual water content of a 5 cm × 5 cm nonwoven fabric was measured after 5 seconds. [Hair particles fall off] Using a circular urethane sheet with a diameter of 7cm, draw a circle 10 times on the surface of a non-woven cloth of 15cmXl5cm with a load of 200 grams (forward direction + reverse direction once), and visually observe The amount of fiber was evaluated in five stages. Judgment: Poor 1 to 5 [Fuzziness in water of non-woven fabric] 20cm × 20cm non-woven fabric was immersed in a flask filled with 500cc of 20 ° C pure water, and the flask was shaken sideways up and down 100 times, and the water was visually observed The amount of residual water is evaluated in five stages. Judgment: Poor 1-5 Best Example 1 [Production of Ethylene Modified PVA] Equipped with a stirrer, nitrogen inlet, ethylene inlet and -15 at 100 liters-This paper size applies Chinese National Standard (CNS) A4 specifications ( 210 X 297 mm) -------- Order --------- line (Please read the note on the back? Matters before filling this page)

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V. Description of the invention (2 (29.0 kg of vinyl acetate and 31.0 kg of methanol are added to the pressurized reaction tank of the initiator addition port, and the temperature is increased to 60 ° C, and then nitrogen is replaced in the system by bubbling nitrogen for 30 minutes.) Ethylene was introduced at a reaction tank pressure of 5.9 kg / cm2 (5.8 X 105 Pa). As a starter, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) ( AMV) was dissolved in methanol and adjusted to a solution with a concentration of 2.8 g / L, and replaced with nitrogen by a nitrogen gas bubble treatment. After the internal temperature of the polymerization tank was adjusted to 60 ° C, 170 ml of the above-mentioned initiator was injected. The polymerization of the solution was started. During the polymerization, the pressure of the reaction vessel for introducing ethylene was 5.9 kg / cm 2 (5.8 × 10 5 Pa), the polymerization temperature was maintained at 60 ° C., and AMV was continuously added at 610 ml / hour using a starter solution to perform polymerization. After 10 hours, the polymerization rate was cooled to 70%, and the polymerization was stopped. The reaction tank was opened, and after deethylene was removed, nitrogen gas was bubbled to completely deethylene. Then, unreacted vinyl acetate monopolymer was removed under reduced pressure. To form a methanol solution of polyvinyl acetate. To this polyvinyl acetate solution was added methanol to a methanol solution of polyvinyl acetate adjusted to a concentration of 50% (polyvinyl acetate in solution 100 g), and 46.5 g (for vinyl acetate in polyvinyl acetate) In terms of units, the molar ratio (MR) is 0.10) alkali solution (10% methanol solution of NaOH) for saponification treatment. The saponified person in the system is pulverized by a pulverizer about 2 minutes after the addition of the alkali, and the temperature is 60 ° C. After standing for 1 hour for saponification, 1000 g of 0.5% acetic acid 0.5% water / methanol = 20/80 mixed solution was added to neutralize the remaining alkali. After confirming the completion of neutralization with a phenolphthalein indicator, the white solid obtained was filtered. Add 2000 g of water / methanol = 20/80 mixed solution to PVA, and wash it at room temperature for 3 hours. Repeat -16- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ------------- # ·! (Please read the notes on the back before filling in this page) Order --------- line

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 592657 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description ((r) After the above washing operation 3 times, add another 1,000 grams of methanol and leave it at room temperature After washing for 3 hours, the PVA obtained by centrifugal deliquoring was left in a dryer at 70 ° C. for 2 days to obtain dry PVA (PVA-1). The degree of saponification of the obtained ethylene-modified PVA was 98.4 mol%. After the modified PVA was ashed, the sodium content measured by an atomic absorption spectrophotometer was 0.0005 parts by mass with respect to 100 parts by mass of the modified PVA using those dissolved in an acid. In addition, unreacted vinyl acetate was removed after polymerization. After adding the methanol solution of the obtained polyvinyl acetate to n-hexane, and taking the precipitated vinyl acetate, the polyvinyl acetate was dissolved in acetone, and the n-hexane was added again for three times for precipitation and reprecipitation. And dried under reduced pressure at 80 ° C for 3 days to obtain a purified polyvinyl acetate. The polyvinyl acetate was dissolved in d6-DMSO, and 500 MHz proton NMR (JEOL GX-500) was used at 8 (TC When measuring, ethylene content It is 10 mol%. After the methanol solution of the above polyvinyl acetate is alkalized with an alkali mol ratio of 0.5, the pulverized one is left at 60 ° C for 5 hours and then saponified, and then the methanol sogreat is made. Three days after the method was implemented, and then dried under reduced pressure at 80 ° C for three days, a refined ethylene modified PVA was obtained. The average degree of polymerization of the PVA was measured based on JIS K67 26 in the conventional method as 330. In addition, The 5% aqueous solution of the refined and modified PVA was adjusted to make a cast film having a thickness of 10 micrometers. The film was dried under reduced pressure at 80 ° C for 1 day, and then DSC (Mayton La, TA3000) was used in the above method. When measuring the melting point of PVA, it is 206 ° C (refer to Table 1). -17- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -------- Order ---- ----- line (please read the notes on the back before filling this page) 592657 A7 _B7 V. Description of Invention (A) Table 1 Printed Polymerization Degree Saponification Degree (Molar%) by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Tm (° C) Type of modification (Mole%) Sodium ion (parts by mass) a 1} PVA-1 330 98.4 206 Ethylene 10 0.000 5 0.04 PVA- 2 560 98.2 192 Ethylene 18 0.003 0.1 PVA- 3 230 98.9 207 Ethylene 11 0.0008 0.09 PVA-4 330 99.7 216 Ethylene 10 0.002 0.07 PVA- 5 290 94.1 188 Ethylene 5 0.0004 0.2 PVA-6 350 98.3 222 Μ y \\\ — 0.003 0.1 PVA-7 450 98.7 208 Propylene 3 0.001 0.08 PVA- 8 320 98.1 179 Ethyl vinyl ether 6 0.003 0.2 PVA-9 280 98.2 195 N-vinylacetamide 3 0.002 0.1 PVA- 1 0 330 98.4 206 ethylene 10 0.03 0.08 PVA- 1 1 330 98.4 206 ethylene 10 0.00005 0.4 PVA- 1 2 330 98.4 206 ethylene 10 0.0009 0.9 PVA- 1 3 290 88.0 178 ethylene 5 0.0001 0.2 PVA- 1 4 450 98.7 208 propylene 3 0.07 0.09 PVA- 1 5 380 98.3 176 Ethylene 28 0.01 1.2 PVA- 1 6 230 98.9 207 Ethylene 11 0.006 0.007 PVA- 1 7 1050 97.8 206 Ethylene 7 0.0006 0.1 PVA- 1 8 150 98.6 207 Ethylene 10 0.005 0.2 PVA- 1 9 350 99.8 234-0.001 0.07 PVA-20 410 99.0 153 Ethyl vinyl ether 10 0.002 0.1 1) a = Content of acetic acid in PVA / Content of sodium ions in PVA -18- ------------- i — (Please read the notes on the back before filling this page) Order --------- line

This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 592657 A7 B7 i. Description of the invention (fp: The PVA obtained above is melt-kneaded at 225 ° C and melt-polymerized The flow is introduced into the spinning head, which is ejected from a spinning mold with a hole diameter of 0.25 mm and a 24-hole diameter, so that the spinning sliver is cooled under a cooling air of 20 ° C and is introduced into a circular absorption jet device, which is substantially 3,500 meters per minute. The traction is refined at the pulling speed, and the single-fiber group of open fibers is accumulated on the mobile capture belt device to form a long fiber corrugation. The corrugation is heated to 180 ° under a line pressure of 20 kg / cm. The embossed pattern between the embossing roll and the flat roll of C is embossed and thermally melted. In addition, the corrugations are passed through a 200 ° C hot air dryer for heat treatment. The passage time in the dryer is 2 minutes. A good long-fiber non-woven fabric made of long fibers with a single fiber fineness of 4.4 dtex and a net weight of 34 g / m2 was prepared. The manufacturing conditions and formability of the non-woven fabric are shown in Table 2. Direction), water retention rate, suction length, wiping residue, hair particle shedding, and water fluff results are shown in Table 3. (Please read the note on the back? Matters before filling out this page) Staff Consumption of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Cooperatives-19- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 592657 A7B7 V. Description of invention () Table 2 PVA plasticizer non-woven fabric printed by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Manufacturing conditions Moldability (parts by mass) Spinning temperature Pull speed Embossing temperature heat treatment Warm-spun non-woven fabric state degree (m / min) Degree (° c) Degree (° c) State Example 1 PVA- 1 • 225 3500 180 200 ◎ Example 2 PVA-2 220 3000 170 Μ j \\\ ◎ Example 3 PVA-3-225 3500 180 200 ◎ Example 4 PVA-4-2235 3500 190 200 ◎ Example 5 PVA -5-210 3000 170 180 ◎ Example 6 PVA-6 Diglycerol 3 240 2500 200 200 〇 Example 7 PVA-7-230 3500 190 200 ◎ Example 8 PVA-8-200 3500 160 180 ◎ Example 9 PVA-9-215 3500 170 180 ◎ Example 10 PVA-10-225 350 0 180 200 ◎ Example 11 PVA-11-225 3500 180 200 200 ◎ Example 12 PVA-12-225 3500 180 200 ◎ Example 13 PVA-13 — 200 2500 160 180 〇 ~ △ 〇 ~ △ Only slightly decomposed odor Example 14 PVA-14-230 2000 190 200 〇 ~ △ △ Only a slight yarn breakage Example 15 PVA-15-195 2000 150 Μ J \ \ N 〇 ~ △ △ There is a slight yarn breakage Example 16 PVA -16 — 225 2500 180 200 〇 ~ △ 〇 ~ △ Only slightly decomposed odor Comparative Example 1 PVA-17 280 1000 X-Spinning cannot be stabilized due to thermal decomposition Comparative Example 2 PVA-18-220 — — — X — Most Yarn breakage occurred Comparative Example 3 PVA-19 Diglycerol 3 255 X-Spinning could not be stabilized due to increased viscosity Comparative Example 4 PVA-20 — 175 2500 120 140 XX Fierce adhesion between fibers-20 — Applicable to this paper size China National Standard (CNS) A4 Specification (210 X 297 mm) (Please read the notes on the back before filling out this page) 592657 A7B7 V. Description of the invention (1) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 P Estimated results: strong thickness (horizontal direction) Length water retention rate Wipe remaining hair particles (g / m2) (mm) (N / 2.5cm) (cm) (%) (g) Judgment of shedding property Example 1 34 0.25 32 5.6 1005 0.13 5.0 5.0 Example 2 35 0.28 38 4.2 691 0.23 5.0 5.0 Example 3 35 0.25 30 5.8 1029 0.11 5.0 4.5 Example 4 32 0.20 31 4.9 955 0.16 5.0 5.0 Example 5 37 0.31 28 7.5 1071 0.08 4.5 4.5 Example 6 35 0.26 27 6.1 1038 0.10 4.5 4.5 Example 7 28 0.17 30 5.7 993 0.14 5.0 5.0 Example 8 34 0.23 32 5.4 971 0.15 5.0 5.0 Example 9 32 0.27 33 5.9 1035 0.11 5.0 5.0 Example 10 35 0.29 34 5.4 976 0.15 5.0 5.0 Example 11 36 0.29 34 5.5 989 0.14 5.0 5.0 Example 12 35 0.26 32 5.2 962 0.15 5.0 5.0 Example 13 37 0.29 29 5.6 1065 0.09 4.5 4.5 Example 14 34 0.20 23 5.2 961 0.13 4.5 4.5 Example 15 28 0.18 25 2.9 382 0.29 4.5 4.0 Example 16 37 0.29 28 5.5 987 0.15 4.5 4.5 Comparative Example 4 34 0.28 29 5.1 987 0.14 4.5 4.5 -21-This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ----- --------------- Order --------- line (please read the back first Notes on filling out this page) 592657 A7

V. Description of the invention (β) Examples 2 to 16 PVA long fibers were produced under the same conditions as in Example 1 except that the PVA described in Table 1 was used instead of the PVA used in Example 1, and the manufacturing conditions shown in Table 2 were used. After the formed non-woven corrugations, a long-fiber non-woven fabric is produced by a set embossing treatment temperature and a heat treatment temperature. Table 3 shows the results of the evaluation of the target, thickness, strength (horizontal direction), water retention rate, suction length, wiping residue, hair shedding, and fluff in the obtained nonwoven fabric. Comparative Examples 1 to 4 The PVA described in Table 1 was used in place of the PVA used in Example 1, and the manufacturing conditions shown in Table 2 were used. The same conditions as in Example 1 were used to prepare a non-woven corrugation made of long PVA fibers. A long-fiber non-woven fabric is produced at a set embossing treatment temperature and heat treatment temperature. When the PVA shown in Comparative Example 1 was used, since the melt viscosity was too high, it could not be stably ejected from the spinning hole, so that the nonwoven fabric ripples could not be formed. When the spinning temperature is increased to 280 ° C, the melt viscosity decreases, decomposition and gelation occur, and the condition becomes worse. In the case of using the PVA of Comparative Example 2, the melt viscosity was too low, water droplet-like discharge was mixed, and stable fibers could not be formed, and non-woven ripples could not be formed. In Comparative Example 3, since the spinning head temperature of 240 ° C was close to the melting point of the polymer, the melt viscosity was too high. Therefore, when the temperature of the spinning head is increased to 255 ° C, the melt viscosity is too low, decomposition and gelation occur, and the situation becomes worse. In Comparative Example 4, due to the decrease in the crystallinity of PVA, the adjacent spun single yarn -22- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _____________ * ^ 1 _ — (Please read first Note on the back then fill out this page) Order --------- line

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 592657 A7 _ ______ B7 5. The invention description (w) is glued together. It cannot be formed into a non-woven corrugation under the open fiber, but can only form a rough sheet. Effect of the Invention 1 According to the present invention, a polyvinyl alcohol-based non-woven fabric having strong affinity for water, such as water absorption, hydrophilicity, and water swelling, can be produced by a melt spinning method and an embossed non-woven fabric manufacturing technology. It can be obtained, and it can provide the rag which is excellent in hydrophilicity, and is excellent in non-pilling property. -------- Order --------- ^ ^ __ ww (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-23- Applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

6. Patent Application No. 90 1 062 1 6 "Paper with Excellent Non-Fuzzing Property" (crossed out on February 13, 1993) 6. Application for Patent: 1 · A non-fuzzing cleaning material, which It is characterized by a thermoplastic polyvinyl alcohol-based long-fiber nonwoven fabric having an average viscosity of 200 to 700 and a melting point of 160 ° C to 230 ° C. 2. The non-fuzzy wipes as described in item 1 of the scope of patent application, in which the length of water absorption in 2 minutes is more than 2 cm. 3 · The non-fluffy wipes according to item 1 or ^ of the scope of application for a patent, wherein the polyvinyl alcohol contains 0.00 to 0.00 parts by mass of (A) polyvinyl alcohol (B) ) Alkali metal ions. 4. The non-fluffy wipes as claimed in any one of claims 1 to 3, wherein (A) the polyvinyl alcohol contains α with respect to (A) polyvinyl alcohol, which can satisfy O. Ol ^ aSl (C) Polyvinyl alcohol having an acid group at a pKa of 25 ° C or lower of 5.0 or less, where α = the content of α (mass%) of the acid in the polyvinyl alcohol in polyvinyl alcohol / in the polyvinyl alcohol (B) The content rate (mass%) of an alkali metal ion. 5. The non-fluffy wipes according to any one of claims 1 to 4, wherein the degree of saponification of (A) polyvinyl alcohol is 90 to 99.99 mole%. 6. The non-fluffy wipes according to any one of the claims 1 to I, wherein (A) the polyvinyl alcohol is at least one selected from a carbon number of 4 containing a total of 0.1-20 mol% The following α-olefin units, vinyl ether units, and N-ethyl alcohol amines. 592657 t. Application for patent scope 7. For the non-fluffy wipes of item 6 of the patent application scope, (A) Polyvinyl alcohol is modified polyvinyl alcohol containing 3 to 20 mole% of ethylene units