Polyoxymethylene fibrides, process for their manufacture and their use.

[Detailed Description of the Invention]

It is understood as the roving which has the cellulose-like structure, i.e., limited, however unequal length, made [ the lengthwise direction ] to carry out for Arrangement to Fibriad, irregular density, the cracked surface, and the high degree of branching. Especially this is suitable for manufacture of paper above all according to the structure. Manufacture of such Fibriad is written in the German patent specification No. 1290040. the bit which manufactures a point Plexus filament according to this, then cuts this to staple length, and makes a staple fiber bit suspended into a fluid, and is in suspension -- the very thing -- a publicly known method -- Shred . here -- plexus -- a filament -- a term -- length -- Along -- it joins mutually together at an irregular interval, dissociates mutually, and makes for Arrangement have carried out in the direction of a vertical axis preferably It is related with the thread-like output which consists of crystalline plastics which has the three-dimensional meshes-of-a-net structure which does not have in practice the tunnel Mr. slot and cave which consist of many Fibriad like a film Young sliver thinner than 2 micro in thickness which carried out molecular orientation. This plexus filament and its manufacture are written in the Belgium patent specification No. 568524. In this case, in order to manufacture a plexus filament, it presses out to A room which is under low pressure through an orifice in the temperature which exists more than the boiling point of the solvent which measured the solution of the synthetic polymer under that spontaneous generation or high pressure by normal pressure. This manufacture of a plexus filament is also called flash silk thread spun or expansion silk thread spun again. manufacturing a plexus filament by this method also from polyoxymethylene -- and the next -- Fibriad -- Shred -- things are made. as the solvent for manufacturing a plexus filament -- in the Belgium patent specification No. 568524 -- a neutral solvent -- if it says in detail, a methylene chloride, ethylene chloride, acetonitrile, and methyl ethyl ketone will be used. A plexus filament arises chiefly, without Fibriad producing even 1% of the weight of weight object concentration among remarkable low polymer concentration, for example, methyl ethyl ketone, as the examination is shown. Since a plexus filament is not suitable for manufacture of paper, the filament must be processed into Fibriad by the second step with the above-mentioned German patent specification No. 1290040, and, as for the method, cost increases by it. Thus, the paper which obtained polyoxymethylene Fibriad carried out owner Perilla frutescens (L.) Britton var. crispa (Thunb.) Decne. of comparatively slight especially specific surface area and the low degree of Beating, and was manufactured has comparatively low intensity. Fibrous output is obtained like the case where polyoxymethylene is settled by the discharge to the super cooling or the precipitant of the solution to solution (refer to German patent application publication of examined applications No. 1241116). However, the paper which has the character with which it is made satisfied cannot be manufactured after this. It is because these textiles will be remarkably polluted very short and thickly by the structure like a two-dimensional film if it becomes what. It is also publicly known that textiles are finally obtained from JP,46-41110,B by churning of polyoxymethylene solution. However, this method takes time too much, and since it is that low yield again, it is not suitable for the industrial method. There is a subject of the present invention in providing polyoxymethylene Fibriad which does not have the fault and the especially above-mentioned fault of state of the art, or it does not have at least substantially, and its process. So, or [ that the object of the present invention consists of a gay polymer of annular oligomer of formaldehyde or formaldehyde ], Or it consists of a copolymer of annular oligomer of formaldehyde or formaldehyde, In that case, another oxyalkylene unit which has at least two carbon atoms other than a Oxy methylene unit is included, At that time, the copolymer carried out flash evaporation of the overheating solution of a polymer which has the first alcoholic end group under existence of the mixture which consists of 55~90 % of the weight of lower alcohol and 10~45 % of the weight of water as a solvent, and was formed, Conversion specific viscosity (measuring by the concentration of 0.5g/100 ml in 140degree[ in the Butyro lactone containing 2 % of the weight of diphenylamine ] C) 0.4 thru/or 2.0 dl/g^-1Preferably they are 0.6 thru/or 1.20 dlxg.^-1Specific surface areas (measuring using argon by the BET method) 50 thru/or 200m²/g, preferably 70 thru/or 110m²/g and Beating degree (it measures by Schopper-Riegler method) 30-80 *SR -- it is polyoxymethylene Fibriad which has 40 thru/or 70 *SR preferably. furthermore -- in the method of the present invention carrying out flash evaporation of the overheating solution of the above-mentioned polymer to a low-pressure area through a nozzle, and manufacturing the above-mentioned polyoxymethylene Fibriad It is related with the above-mentioned process using as a solvent the mixture which consists of 50 to 95 % of the weight of lower alcohol and 5 to 50 % of the weight of water which have one to four C-atoms. Polyoxymethylene publicly known as a material for manufacturing Fibriad by the present invention is suitable. Annular oligomer of formaldehyde or formaldehyde, for example, the gay weight object of trio Xan, was understood as this output, and that hydroxy end group is chemically stable to decomposition in etherification or etherification by the publicly known method. furthermore -- polyoxymethylene -- a concept -- the present invention -- again -- annular oligomer of formaldehyde or formaldehyde -- including the copolymer of trio Xan preferably In that case, the copolymer carries out owner Perilla frutescens (L.) Britton var. crispa (Thunb.) Decne. of at least 2 preferably 2 thru/or 8, and the oxyalkylene unit that has 2 thru/or 4 contiguity carbon atoms especially in [ other than a Oxy methylene unit ] the main valence chain, and has the first alcoholic end group. the Comonomer content in a copolymer -- advantageous -- 0.1 thru/or 20 -- desirable [ especially ], it is 0.7 to 5 % of the weight 0.5 thru/or 10% of the weight. annular oligomer of formaldehyde or formaldehyde -- as the compound which fits copolymerization with trio Xan preferably above all -- cyclic ether -- different cyclic acetal from the cyclic ether and/or trio Xan which have 3, 4, or five ring members preferably -- Formal which has 5 thru/or 11 preferably 5, 6, or seven ring members preferably, and/or line Polyase tar -- desirable -- Polyhol -- marc is used. As Comonomer about trio Xan, it is a formula especially.<img file="JPH0157166B2_D0001.tif" />((A) in formula R)¹And R²Same in Is or a different intermediary cage and the fatty series Alkyl residue machine which has a hydrogen atom, 1-6 preferably 1, 2 and 3, or four carbon atoms, respectively, or a phenyl Remaining machine is meant, and (a) x is 1, 2, or 3, y is zero, or (b) x is zero, Whether y is 1, 2, or 3, and z is 2, or (c) x is zero, and y is 1, and z is 3, 4, 5, or 6 or (B) R¹The alkoxy methyl Remaining machine or phenoxymethyl Remaining machine which has Is 2-6 preferably 2, 3, or four carbon atoms is meant, 1 and y of x are zero in that case, or y and z are 1, and it is R.²The compound which has a meaning of Is the same as is suitable. The EPO Xide, for example, ethylene oxide, propylene oxide, styrene oxide, cyclo Hexene oxide, Oxa cyclo butane, and phenyl glycidyl ether are used above all as cyclic ether. As cyclic acetal, the carbon chain can be interrupted by the oxygen atom at intervals of two carbon atoms above all, The fatty series which has 2 thru/or 8 preferably 2, 3, or four carbon atoms, or alicyclic [ alpha ] annular Formal of omega-Diol, for example, the Glico Ruhr, -- marc (1, 3-oxo run), Pro pansy all Formal (1, 3-dioxane), butanediol Formal (1, 3-Dioxevan), And diglycol Formal (1, 3, 6-trio Kisokan), 4-Chlor methyl 1, 3-dioxo run, and hexandiol Formal (1, 3-dioxo nan) are suitable. Unsaturated Formal (1 and 3-dioxa cyclohepten [5] is used.), for example, Butenediol formal Homo- of cyclic acetal or the copolymer and the fatty series or alicyclic [ alpha ] and omega-Diol which were defined above as line Polyase tar, aliphatic aldehyde, or Thiol aldehyde -- the line condensation product which consists of aldehyde preferably is suitable. The gay polymer (1, 3-dioxo run), for example, poly, Polly (1, 3-dioxane), and Polly (1, 3-dioxepane) of line Formal of fatty series alpha which has 2-8, preferably two to four carbon atoms especially, and omega-Diol are used. (The compound, for example, Alkyl glycidyl Formal, about trio Xan to which that it is additional has many polymerization machines in a molecule by a case as many polymers in a molecule in addition by a case as a monomer) polyglycol diglycidyl ether, Al Kandi all diglycidyl ether, or bis(Alekan triol)-Triol -- if marc says in detail, it will be used to the total amount of monomers in 0.05 thru/or 5, preferably 0.1 thru/or 2% of the weight of quantity. such -- as for the monomer, it is described in the German patent application publication of examined applications No. 2101817 that it is additional. Generally the values (RSV-value) of the conversion specific viscosity of Fibriad obtained from the polyoxymethylene and this which are used by the present invention are 0.4 thru/or 2.0 dl-g.^-1It is (measuring at the concentration of 0.5g/100 ml in 140degree[ in the Butyro lactone containing 2 % of the weight of diphenylamine ] C). The micro crystallite melting point of polyoxymethylene is the range of 140-180"C preferably 150degreeC thru/or 170 degreeC, and the density is 1.38 thru/or 1.45g and ml.^-1Preferably they are 1.40 thru/or 1.43g and ml.^-1It is measurement) by (DIN No. 53479. If the polymer which has a RSV-value lower than the above-mentioned value is used, Fibriad will arise indeed again. Nevertheless, this becomes comparatively short and is mixed with a remarkable quantity of a non-fiber part. So, since the length, the thin length ratio, and the degree of branching of textiles of Fibriad can be adjusted with the RSV-value of a polymer, the desirable range is influenced by the use field of Fibriad. In the case of a RSV-value higher than the above-mentioned value, the danger of generation of a plexus filament or a two-dimensional film-like structure mainly increases. By the preferably publicly known method used by the present invention, under existence of a positive ion active catalyst, a duality or 3 yuan oxymethylene copolymer polymerizes, and it manufactures 0 thru/or 100 degrees of monomers by C, preferably 50 thru/or 90 degreeC (refer to U.S. Pat. No. 3027352). in this case -- as a catalyst -- for example, the complex compound of Lewis acid, for example, 3 fluoridation boron, 5 fluoridation antimony, and Lewis acid -- preferably an etherification thing, for example, a Borrifrifur orgeat Ciruete rate, and a 3 fluoridation boron-G tertiary butyl Ete rate are used. Proton acid, for example, perchloric acid, and a Shio Mr. compound, for example, triphenylmethyl Hexafluor phosphate, triethyl oxo Nium tetrafluoride borate, or Acetyl perchlorate is suitable. A polymerization can be performed by mass, suspension, or solution polymerization. In order to remove an unstable ingredient, a copolymer is advantageously given to the partial decomposition by heat or hydrolysis by the time the first alcoholic end group is obtained (refer to U.S. Pat. No. 3103499 No. 3219623). The gay polymer of the formaldehyde or trio Xan by the present invention used is similarly manufactured by the contact polymerization of a monomer by a publicly known method (for example, refer to U.S. Pat. No. 2768994 and No. 2989505). Fibriad by the present invention cooks -- Listen -- it has the irregular length which is about 0.1 thru/or 5 mm, preferably 0.2 thru/or 2 mm. A form and the size of a cross section are irregular similarly, and appearance diameters are mainly about 1 thru/or 200 micrometers, preferably 2 thru/or 50 micrometers. As for Fibriad by the present invention, since it has branched remarkably, this is specific surface areas (using argon by the BET method) 50 thru/or 200m high again.²/g, preferably 70 thru/or 110m²It has /g and dries a sample by freeze-drying beforehand in that case. The degree of Beating is also high according to it, and it is 30 thru/or 80*R preferably 40 thru/or 70 *SR. The degree of Beating is by leaflet V / 7/61 of "Der Verein der Zellstoffand Papier-Chemiker and Ingenieure" (old edition July 1, 1961 [ 107 or ] issue). It is measured as Schopper-Riegler-value. polyoxymethylene Fibriad by the present invention carries out owner Perilla frutescens (L.) Britton var. crispa (Thunb.) Decne. of the hydrophilic surface nature, and so - cooks it -- Listen -- it may distribute without a wetting agent easily in - water again. The filter manufactured from now on has adsorbent [ which has been improved ]. When special, it can be advantageous to also make canal surface nature produce by addition of a canal agent suitable again. Based on the branched form, Fibriad by the present invention can be processed into paper very satisfactorily so that an account may carry in the German patent specification No. 1290040 by the publicly known method. The intensity (Tearing intensity, initial wet strength, surface intensity, Z-Tearing intensity, chip box-proof intensity) of this pure polyoxymethylene paper is superior to them of the corresponding paper by state of the art in this case. For example, the Tearing intensity of the paper sheet manufactured in Fibriad by the present invention or a Rapid-Ko *then sheet forming device is 2 thru/or 25Ns/mm.²Preferably it is 4 thru/or 20Ns/mm.²And [ especially ] it is 7 thru/or 17Ns/mm.²(Sheet weight of 160g/m)²measuring with the Instron sample testing machine in sample 15 mm in width, and pace-of-expansion a part for /and 100 mm of length measurement of 10 mm -- it is . Measurement is carried out with 23degreeC and 50% of relative humidity. Even if it mixes with a cellulose fiber, another textile materials, for example, cellulose, and a synthetic fiber, the outstanding paper can be manufactured, and by a usual state method, this can be made smooth, can be applied, and can be laminated and printed. The intensity of this mixed paper is also more remarkably [ than the paper which consists of publicly known polyoxymethylene Fibriad and which may be compared ] high. POM Fibriad by the present invention can be used for wallpaper, a filter, a label, graph paper, another special paper, etc. The paper which can process polyoxymethylene Fibriad also with a board manufacture machine, and is obtained in that case has the tolerance outstanding to water. It can be used in a nonwoven fabric and polyoxymethylene Fibriad by the present invention is a flash set cutback (Kaltbitumen) as a paste agent, It can be used for dye, plaster, adhesives, sealing material, and a paint (let unsaturated polyester, EPO Xide resin, Reared blue paste, and PVC-plastisol be bases). In the case of the process by the present invention of Fibriad, publicly known flash evaporation to the low-pressure area of the polymer solution which is indicated, for example in the Belgium patent specification No. 568524 and which is Like(ed) and overheated and is under pressurization is carried out. for this reason -- being alike -- point One -- preferably homogeneous polymer solution is manufactured, and dryness, solvent humid powder, or granulation can be left according to a process in that case, a polymer is mixed with a solvent, and it heats for example, in pressurization type autoclave by blowing in of the bottom of churning, for example, steam jacket heating, or steam. When polyoxymethylene is obtained as the solution or suspension in the alcohol / water-mixture of composition by the present invention in the case of stabilization - which follows it in the case of a polymerization, and a post-processing method, this liquid can also be directly used for the method according to the direct present invention again. Present invention - As already indicated, the mixture which consists of 50 to 95 % of the weight of lower alcohol and 5 to 50 % of the weight of water which have one to four C-atoms, respectively is used to - and all the solvents. For this reason, as lower alcohol, the mixture of methanol, ethanol, isopropanol, n-propanol, n-butanol, i-butanol, t-butanol, or these alcohol is used. When using more higher alcohol, for example, n-Hexanol, than four pieces, Fibriad is obtained indeed again, but a required temperature for manufacturing solution in that case is comparatively high. Methanol and isopropanol are used especially. alcohol and the quantity ratio of water -- manufacture of Fibriad -- an intermediary -- it is remarkably important. For example, if lower alcohol less than 50 % of the weight and more water than 50 % of the weight are used, a plexus filament will generate easily. the boundary between Fibriad and a plexus filament is natural -- not carrying out clearly -- and -- in addition -- to some extent -- selection of the temperature of until solution, and concentration -- selection of a molecular weight -- and it can be affected with the high level of the pressure in the size and expansion region of a nozzle. Along with the fall of the pressure in increase and the expansion region of the rise of temperature, the fall of polymer concentration, the fall of a molecular weight, and the ratio of the length/diameter of a nozzle, boundary [ this ] shifts to a side with much water somewhat. cooking a necessary solution temperature, if more lower alcohol than 95% and water less than 5% are used -- Listen -- it is uneconomically high. The mixture which consists of 45 to 10 % of the weight of water and 55 to 90 % of the weight of lower alcohol is preferred. The concentration of the polymer in a solvent mixture is per [ 10 thru/or 300g ] solution 1, preferably 50 thru/or 200g usually. Concentration lower than it is usually uneconomical. It is because this needs high solvent circulation if it becomes what. Concentration higher than it often includes the danger of generation of a plexus filament. in this case, acceptable concentration is higher as the maximum of polymer concentration has a to some extent low molecular weight depending on a until molecular weight. The concentration of the solution of polyoxymethylene is dependent on the molecular weight of a polymer, the kind of Comonomer, quantity, and solvent composition. As the minimum of temperature - Although it accepts as - and a necessary dissolution temperature as long as homogeneous solution is used, the maximum of temperature is mainly restricted by only economical consideration. Dissolution temperature is known by many examples, in other cases, can be easily changed by a person skilled in the art from publicly known data, or can be measured on an experiment target. There must be a minimum of temperature in the appearance to which evaporation sufficient on the selected pressure conditions in an expansion region for Fibriad formation is performed at any cases. this -- normal pressure -- the boiling point -- about 30degreeC -- the situation is usually so if the coagulating point of a polymer is reached highly and simultaneous. the desirable alcohol in the desirable mixture ratio -- an intermediary -- desirable temperature ranges are 150 thru/or 180degreeC. Although solution is under the peculiar steam pressure of a solvent mixture at the temperature of this usually, inactive gas pressure or a pump can raise this Pressure remarkably. Generally pressure is 15 thru/or 60 bars, preferably 15 thru/or 30 bars. (The auxiliary agent No. 1146649, for example, British patent specification, in which solution consists of polymerizations in addition besides a polymer) Like indicated to the German patent application publication before examination No. 1595705, No. 1595668, the German patent application publication of examined applications No. 1199504, and No. 1175882, Until the decomposition output or the first alcoholic end group of the catalyst for cationic polymerization is obtained The base reactivity compound for removing an unstable ingredient, for example, the low-grade third aliphatic amine or, for example, triethyl, triethanol amine, or the second alkali phosphate (U.S. Pat. No. 3174948), for example, phosphoric acid hydrogen disodium No. 3219623, the No. [ 3666714 ] reference and the reaction product, for example, methylal, acquired, trio Xan, Tetro oxane, formic acid, and methyl formate can be contained. Polymer solution can contain the publicly known additive agent of the most kinds. If it is considered as such a thing, it is an ordinary nucleating additive, for example, a branch, or reticulated-ized polyoxymethylene, Talc or nitriding boron can be used, and this can promote a crystal, and it can affect the form of Fibriad using this (refer to the German patent specification No. 2101817 and the German patent application publication before examination No. 1940132). The publicly known stabilizer (for example, Like indicated in the German patent application publication before examination No. 2043498) to heat, oxygen, and/or light is mentioned here. Especially for the purpose, alkaline-earth-elements Shio of a screw phenolic compound and carboxylic acid and a guanidine compound are suitable. The Alkyl residue machine which mainly contains one to four carbon atoms as a screw phenolic compound It is in a core, the ester, for example, omega, of single substitution or the monobasic 4-hydroxy phenylalkanoic acid (this contains 7-13 preferably 7, 8, or nine carbon atoms) replaced two times. -(3-tertiary butyl 4-hydroxyphenyl)- Pentanoic acid beta -(3-methyl 5-tertiary butyl 4-hydroxyphenyl)- Propionic acid (3,5-Di tertiary butyl 4-hydroxyphenyl)-acetic acid, beta -(3,5-tertiary butyl 4-hydroxyphenyl)- Propionic acid or (3,5-Diiso propyl 4-hydroxyphenyl)-acetic acid, and ethylene glycol, Ester with all [ a pro pansy / all / a pro pansy / (1, 2) and ] (1, 3), butanediol (1, 4), hexandiol (1, 6), 1 and 1, 1-Trimethi roll ethane, or pen Thierry Tritt is used. Especially as alkaline-earth-elements Shio of carboxylic acid, it has 2-20, preferably three to nine carbon atoms, a fatty series -- preferably the calcium or magnesium salt of alkaline-earth-elements Shio of hydroxy group content 1 and 2 or 3 base carboxylic acid, for example, stearic acid, recinoleic acid, lactic acid, Malden acid, malic acid, or citric acid is used. As a guanidine compound, it is a formula.<img file="JPH0157166B2_D0002.tif" />(The compound, for example, cyano guanidine, of (inside R of a formula means the Alkyl residue machine which has a hydrogen atom, a cyano group, or 1 thru/or 6 carbon atoms)) N-cyano N-cyano N'-methylguanidine, N-cyano N'-ethyl guanidine, N-cyano N'-isopropyl guanidine, N-cyano N'-tertiary butyl guanidine or N, and N'-dicyano guanidine is used. A guanidine compound is used by the case to full weight in 0.01-1, preferably 0.02 to 0.5% of the weight of quantity. solution -- Shrine -- another additive agent, for example, a publicly known spray for preventing static electricity, a flame-proofing agent, lubricant, or lubricant can be contained. Fibriad with which it was filled up is obtained by making a mineral matter bulking agent uniformly suspended in polymer solution, and then carrying out like a statement by the present invention. In this case, suitable paints are a titanium dioxide, calcium carbonate, talc, Wollastonite, a white-clouds stone, a silica dioxide, etc. The colored polyoxymethylene Fibriad can dissolve or distribute dye in polymer solution. Addition of a fluorescent brightener is also interested for some use. In order to improve the dispersibility of polyoxymethylene Fibriad, in solution, it is a surface-active agent, for example, Oxy ethylation alcohol, The polymer, for example, polyvinyl alcohol, or carboxymethyl cellulose which has carboxylic acid or amine, Alekan sulfonate, or a hydroxyl machine can also be added. In that case, polymer solution is pressed through the nozzle of 1 or a large number. although the design (a size, shape, and length) of the nozzle affects the size of generation Fibriad indeed, and is shown and some concentration limits of a solvent mixture can be changed -- however, the present invention -- an intermediary -- it is not important. It is indicated for suitable nozzle No. 568524, for example, the Belgium patent specification. The easy nozzle which has a diameter, for example, 0.5 to 5 mm, and 0.1 thru/or 1000 cm in length here, the circular nozzle which has an annular gap which may be compared, and a 2 material nozzle are mentioned, and fluids, for example, overheating water, such as inactive gas, for example, nitrogen, and vapor, can be used as a promotion medium in that case. The solvent of all or a part lets polymer solution pass via a nozzle to the low-pressure area which evaporates with nature. In this case, it is also possible to give the pressure release controlled by carrying out the electrical connection of the pipe which has derivation before from a nozzle for solution, and has a bigger diameter than A room or a nozzle derivation mouth for this. The remainder of existence To lower alcohol is removable with vapor by a case. A low-pressure area is an airtight container usually, and a pump removes solvent steam after this. This can be again returned to a process after condensation. The pressure in a low-pressure area is 0.02 bar thru/or 2.0 bars, preferably 0.1 thru/or 1 bar. Fibriad removes most solvents which have not evaporated succeedingly by centrifugal separation, publicly known mechanical method, for example, suction filtration, etc., In being required, it washes with water, then, use is supplied with a Moist form, a region is loosened in the density of 10 thru/or 200g/, preferably 30 thru/or 100g/, and it dries in a succeedingly hot gas stream. The remarkable strong point of the method according to the present invention is immediately acquired in the case of atomization of Fibriad, and is that two step-by-step procedures which consist of manufacture of a long plexus filament and subsequent mechanical fine pulverization infinitely complicated by this and which require energy are avoided. Since a plexus filament has a high pace of expansion, only Together can carry out energy expenditure with this high mechanical fine pulverization. The strong point by this method and the strong point on the material of polyoxymethylene Fibriad by the present invention could not be expected, and are a thing surprising so. The following example explains the present invention in detail. Example 1 In the pressurization machine provided with capacity 70 and the style stirrer for multi stage story-5 impeller types, it consists of 98 % of the weight of trio Xan, and 2 % of the weight of ethylene oxide, and dissolves 2 kg of copolymers which have RSV-value 0.82 dl/g, and 20 ml of triethyl amine in the mixture which consists of methanol 13 and water 7. 30 bars of total Pressure are used using nitrogen. the single hole which has 1 mm in diameter, and about 0.5 mm in length for the after-opening solution of a bottom valve -- it passes in the gas chamber of sealing Receiver which has seating capacity 200 through a nozzle and is filled up with water 40 and where a vacuum pump guarantees the pressure of 0.8 bar. the eradication by after-end vapor of atomization -- and methanol is driven out for bottom 30 minutes of maintenance with a pressure of 0.8 bar. Generation Fibriad suspension is taken out via a bottom valve, and it centrifuges to about 20% of solid content. In order to measure the specific surface area of obtained Fibriad, a sample is freeze-dried, and it is BET. - It measures using argon by law. Specific surface area is 73 m.²/g and the degree of Beating are 50 *SR(s). A textiles classification is used in the textiles classification by Brecht Holl as indirect measurement of fiber length distribution, 2 g of textiles are washed [ in this device ] the sieve of various sizes one by one using the water pressure of 0.5 bar, and a beat To suction film (it has the largest possible distance) with a stream pump for 10 minutes. Percentage shows the residue and passing material on the sieve which has mesh 1.2 mm in width, 0.4 mm, and 0.12 mm. The part for following drawing is measured in the above-mentioned textiles classification: Residue 1.2 mm : 0% Residue 0.4 mm : 17% residue 0.12 mm : 54% Passing material 0.12 mm : 29%, using this Fibriad, it is a Rapid-Ko *then sheet forming device, and is a 160g/m paper sheet.²It manufactures. The Tearing intensity which carried out To ask measurement at this sheet is 14.3Ns/mm.²It comes out. Controlled study 1 The same copolymer is dissolved in methyl ethyl ketone 20 under the same temperature - and a pressure condition, and it atomizes in the same container by the same nozzle, and keeps the pressure of 0.8 bar being the same as that of that time so that an account may carry in Example 1. Consisting the output obtained of a continuous plexus filament chiefly, this is not suitable for manufacture of paper in this form. So, disk type refining machines fine-grind a sample by 6 passage. Thus, measurement of To ask shows the following value to manufactured Fibriad. Specific surface area : 39 m²/g The degree of Beating : 27 *SR Textiles classification: 1.2 mm of residues : 3% 0.4 mm of residues : 4% 0.12 mm of residues : 26% Tearing intensity of a passing material 67% sheet : (160g/(m))²) :0.37N/mm²Even if it reduces polymer concentration to 0.01 kg/, a plexus filament unsuitable to manufacture of paper is obtained. Controlled study 2 It carries out as in Example 1. However, solvent composition is methanol 15 and water 5. The plexus filament which is not suitable for manufacture of paper in this form is obtained chiefly. Example 2 It carries out as in Example 1. However, the RSV-values of the used polymer are 1.0 dl/g, and solvent composition is methanol 15 and water 5. :specific surface area whose measured value of To ask is as follows at Fibriad obtained : 98 m²/g The degree of Beating : 61 *SR Textiles classification: 1.2 mm of residues : 0% 0.4 mm of residues : 5% 0.12 mm of residues : 55% 0.12 mm of passing materials : Tearing intensity of 40% paper : 13.2Ns/mm²Example 3 Although carried out as in Example 1, isopropanol is used instead of methanol. :specific surface area whose measured value of To ask is as follows at Fibriad obtained : 108 m²/g The degree of Beating : 68 *SR Textiles classification: 1.2 mm of residues : 6% 0.4 mm of residues : 4% 0.12 mm of residues : 24% 0.12 mm of passing materials : Tearing intensity of 66% paper : 11.7Ns/mm²