Porous sheet material and production thereof

[Detailed Description of the Invention]

(Field of the Invention) The present invention relates to a porous sheet material and a manufacturing method for the same, and an object of the present invention is to excel in performances, such as surface slippage, water repellence (waterproof pressure), resistance to contamination, wash endurance, mechanical properties, and water-vapor-permeation nature, and to provide the good porous sheet material of A feeling. (PRIOR ART) Conventionally, many methods of manufacturing the porous sheet material and them which consist of polyurethane system resin as a natural leather substitute etc. are known, and if it divides roughly, they will be divided into wet process and a dry method. (Problem which the invention is going to solve) Law has merits and demerits, respectively and the dry method is both excellent from the field of productivity. The method of the statement is known by JP,48-4380,B, JP,48-8742,B, JP,51-41063,A, JP,54-66961,A, JP,54-68498,A, etc. as such a dry method. These publicly known problems of surface slippage and A feeling being inferior to a sake although it method C Is natural although the porous sheet material of the moisture permeability outstanding, respectively is provided if it depends, but these porous sheet materials are porous, and also being easy to become dirty exist. As a result of being a communicating hole for the purpose of moisture permeability, since permeation of the water from the outside is easy, when the detailed hole of these porous sheets is used in case of rainy weather etc., it has the problem that water permeates even an inside and an inside gets wet. As a method of solving such a problem, I am doing it widely the method of making what is called softening agents and Water repellent, such as a fluoridation carbon system compound and a compound of a fluoride system, include in a porous layer, The softening agent and Water repellent like the above are a compound of low-molecular quantity comparatively, since it carves to fJ-One polyurethane system resin and compatibility is inferior, Bleed out of them is temporally carried out on the surface of a porous layer, and the problem of the contamination nature that the surface is sticky or dust adheres easily produces them. By repeating wash, a softening agent and Water repellent were removed and the problem of the wash endurance that the performance of the surface slippage given by a softening agent and Water repellent, A feeling, ll11 water (waterproof pressure), and resistance to contamination is lost has arisen. Therefore, though it is porous, development of the porous sheet material excellent in surface slippage, good A feeling, waterproof pressure, resistance to contamination, and wash endurance is demanded. When using a specific polyurethane emulsion wholeheartedly as a result of research so that this artificer may meet the account request of 1 A, the fault of the conventional technology like Above was solved, and he did the knowledge of offer of the porous sheet material which can fully meet the request of the above-mentioned industry being possible, and completed the present invention. (A means to solve a problem) Namely, the present invention consists of two inventions and is the first invention, It is a porous sheet material, wherein an account [ of setting-to porous sheet material provided in fellows Murakami-porous layer which consists of polyurethane system resin" 2 ] porous layer has a silicone segment and a fluoridation carbon segment in a main chain and/or a side chain. In the manufacturing method of the porous sheet material which consists of impregnating and/or applying, and the second invention gelling and drying an oil Nakamizu type polyurethane emulsion to a substrate, The above-mentioned polyurethane emulsion is a manufacturing method of a porous sheet material making it come to emulsify water in an organic solvent solution of polyurethane system resin which has a silicone segment and a fluoridation carbon segment in a main chain and/or a side chain, and/or dispersion liquid. (OPERATION) Next, he is this artificer if the present invention is explained still in detail, The problem of the conventional technology like the above-mentioned carries out the knowledge of being solved by using the polyurethane system resin which has a silicone segment and a Fluoride depression matter segment for the polyurethane specific to formation, i.e., the main chain, and/or the side chain of a porous layer. Namely, the result by which the silicone compound and fluoride compound as a softening agent or Water repellent are included by the covalent bond in polyurethane in the present invention, Also after forming in a porous layer, an iffff Soft softener Water agent carries out Bleed out to the surface temporally, or it is not removed by wash, and the surface slippage outstanding almost eternally, high pliability, waterproof pressure, resistance to contamination, washing resistance, etc. can be held. (Desirable embodiment) The desirable embodiment of the present invention is mentioned, and the present invention is further commented and is Brief description(ed). About the polyurethane system resin which A f Carries out the silicone segment and fluoridation carbon segment by which use it in the present invention and the present invention is mainly characterized, Polyol, polyisocyanate, a chain extension agent, etc. are made to react, and it faces obtaining polyurethane system resin, It is obtained using the silicone compound and fluoride compound which consist reactive functional groups, such as an amino group, an epoxy group, a hydroxyl group, a carboxyl group, and a Thio record machine, as all of polyol, polyisocyanate, or 3n extension agents, or one copy. The polyurethane system resin which has a silicone segment using the silicone compound which carries out, and has a reactive functional group when compounding polyurethane system resin is compounded like the above, The polyurethane system resin which has a fluoridation carbon segment in a similar manner on the other hand may be compounded, and these may be mixed and used by a suitable ratio. As a desirable example of the silicone compound which has the above reactant organic functional groups, the compound like the following is mentioned, for example. (1) Amino denaturation silicone oil (m-1 l01n-2 thru/or 10, R-CH3, or OC1+3) (l-1 1O1n=2 thru/or 10, R-CI+3, or OCH) (m-0 thru/or 200) (n-2 thru/or 10) (Turning point-2 thru/or 3, R and a low-grade Alkyl machine, !-2 to 200, ra-2 to 200, n-2 to 200) (2) epoxy denaturation silicone oil (n= 1 thru/or 200, R-low-grade Alkyl machine) (n= 1 thru/or 200) (l-1 l01n-2 thru/or 10) (ni thru/or 200) (Turning point-2 thru/or a 3.R~low-grade Alkyl machine, 1-2 to 200, II+-2 to 200, n-2 to 200) (n-1 thru/or 10) (m-1 thru/or 1O1n-2 thru/or 1G) (3) Carry out denaturing alcohol silicone oil (n-! thru/or 200) (+ m-1 thru/or 10, rr2 to 10), and it is II3L11-13(shoulder-0 A Postcode50, n-Q, or 200)CH2. (+=1 101 m - 1 n thru/or 200, lows 11 thru/or 5) (4) Mel Caputo denaturation silicone oil (n-1 thru/or 200, R-low-grade Alkyl) (m-1 l01n=2 thru/or 10) (n-2 thru/or 10) (Turning points 2 thru/or 3, R and a low-grade Alkyl machine, 1-2 to 200, 11-2 to 200, n-2 A 'XJj, and 200) (5) carboxyl denaturation silicone oil (n-1 thru/or 200, R-low-grade Alkyl, 1$) II 1Gl13CII3 C*118 (:0011 (lows 1 thru/or 200) (m-1 l01n-2 thru/or 10)) (Turning point-2 thru/or a 3.R-low-grade Alkyl machine, ■and2 to 200, ta-2 to 200, lows 2 thru/or 200) It carries out and is 11.11113. bn= (Lows 1 thru/or 200, and R and a low-grade Alkyl machine) It is a reactant functional group (the compound like the next is mentioned as an example of the fluoridation carbon compounds to f carry out.) like the above again. (1) It(CF2CF2) nC1120H (n-1 thru/or 7) (2) (:F3 (CF2CF2)) CIl, CI+2011 (n-1 thru/or 10) (:l) CFt(CF2CF2)-COO!i (n-1 thru/or 1n) (4) CF3 (CF2CF2), CIIzCIIzSH (low l thru/or In) (5) II(CF2CF2) l (CIl2) - (Of:1Izc11□ (OH) C112) 041(1-1 10.o=1 thru/or 1O1 n-IP)13 (6) F (:F2 (:F)) I (reactivity like more than C112>-(OGII, CIl□(OH) CI) nOH (i-i l05-m-1 l01n-1 thru/or 3) (a silicone compound and fluoridation carbon compounds which have an one-set functional group)), In the present invention, it is illustration of a desirable compound, and the present invention is not limited to these illustration, and a compound of above-mentioned illustration and other compounds are marketed now, and may be obtained from a market to 8 Spinning. It is absent and can also use I in the present invention. Like polyisocyanate furthermore mentioned below with the silicone compound and/or fluoridation carbon compounds like the account of L, The intermediate produced by making few To bury of the isocyanate group of the reactant machine of a silicone series compound and/or fluoridation carbon compounds, or a polyisocyanate machine react so that one side may remain, For example, make rich the reactant machine of a silicone compound and/or fluoridation carbon compounds, it is made to react to the thing which made the polyisocyanate of many organic functions react to the silicone compound of two organic functions, and/or fluoridation carbon compounds by isocyanate group Rich, or a contrary, it is obtained, and Intermediate can be used similarly. The reactant machine of a silicone compound and/or fluoridation carbon compounds is a hydroxyl group, When it is an amino group, a carboxyl group, a Eboshi machine, etc., polyester polyol, polyamide polyamine, polyether polyol, etc. which are produced by making react to below-mentioned polyol, chain extension agent or polyvalent carboxylic acid, or Many value amine can be used similarly. As polyol, conventionally, each publicly known polyol for polyurethane can be used, and is example O'clock, An end group is a hydroxyl group as a desirable thing, and a molecular weight is poly ethylene adipate of 300 thru/or 4,000, Polyethylene propylene Ajibe polyethylene Butylene adipate, polydiethylene horse mackerel Beat, poly butylene horse mackerel Pate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, poly butylene sebacate, They are Xamethylene adipate and carbonate polyol to polytetramethylene ether glycol, Polly epsilon-Capro lactone Diol, and Pori, The thing containing the polyoxyethylene chain of hl suitable in the above-mentioned polyols, such as polypropylene glycol, is mentioned. Although any publicly known thing can be conventionally used as organic polyisocyanate, they are 4.4'-diphenylmethane diisocyanate (MD I), water addition MDI, isophorone diisocyanate, and 1.3-xylylene diisocyanate, for example as a desirable thing. 1.4-xylylene diisocyanate, 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, 1.5-naphthalene diisocyanate, Naturally the urethane pre polymer etc. which there are [ polymer ] m-Off 22 range isocyanate, P-Off 22 range isocyanate, etc., or make these organic polyisocyanates, and the polyols and polyamine of low-molecular quantity react so that it may become end isocyanate, and are obtained can be used. Although any publicly known thing can be conventionally used as a chain extension agent, For example, as a desirable thing, they are ethylene glycol and propylene glycol, Diethylene glycol, 1.4-butanediol, 1.6-hexandiol, ethylene diamine, 1.2-propylene diamine, trimethylene diamine, tetramethylen Diamine, hexamethylenediamine, decamethylene Diamine, There are Iso lounge amine, m-Misery range amine, hydrazine, water, etc. The blend thing of the polyurethane system resin which has content polyurethane system resin or a silicone segment for the silicone segment and fluoridation carbon segment which are obtained from the material like Above together, and the polyurethane system resin which has a fluoridation carbon segment, Although all can be used in the present invention, as for a desirable thing, the sum total of a silicone segment and a fluoridation carbon segment occupies about 0.2 thru/or 50 % of the weight in resin. It becomes insufficient [ less than about 0.2 % of the weight ] desired end attaining the total quantity of a silicone segment and a fluoridation carbon segment of the present invention, and problems, such as an adhesive fall to a substrate, arise in quantity exceeding about 50 % of the weight, and it is not desirable. The weight ratio of the silicone segment in resin and a fluoridation carbon segment has the preferred range of former:latter =95 thru/or 5:5 thru/or 95, Since Be swayed and 5, i.e., a silicone segment, become insufficient [ the pliability and surface slippage of few There and A feeling ] about this range and a fluoridation carbon segment becomes insufficient [ few There, waterproof pressure or wash endurance ], it is not desirable. The molecular weight of a desirable thing is a thing of 20,000 thru/or 500,000, and the most desirable thing is a thing of molecular weights 2 thru/or 250,000. The silicone segment and fluoridation carbon segment content polyurethane system resin like the above can be conventionally obtained easily with a publicly known manufacturing method. although the thing which may be prepared with a non-solvent and which was carried out and was prepared in the A 1-opportunity solvent may be sufficient as these polyurethane system resin -- a process ---like Since it can use for manufacture of a polyurethane emulsion the 4 present state by [ which have the organic solvent which should prepare a polyurethane emulsion, i.e., water and a certain amount of mutual solubility, ] carrying out the product made from one in a +l * machine In the melt agent, it is advantageous. Things desirable as such an organic solvent are methyl ethyl ketone and methyl n-propyl ketone, Methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, they are propyl formate, acetic acid methyl, ethyl acetate, butyl acetate, etc. -- moreover Acetone, cyclohexane, a tetrahydro franc, dioxane, methanol, Ethanol, an iso Prop flare record, butanol, toluene, xylene, Dimethylform amide, dimethyl sulfoxide, par Chlor ethylene, trichloroethylene, methyl cellosolve, butyl cello Sorb, a cellosolve acetate, etc. can be used. The thing which does not have a limit in mutual solubility with water in these organic solvents, or the thing which is not dissolved at all considers it as a mixture with other organic solvents, and gives and uses a limit for mutual solubility with water. with, the A 1-opportunity solvent to - boil is natural -- it can be used also as a mixed organic solvent. Although a polyurethane system resin solution is obtained by preparing polyurethane system resin in such an organic solvent, It is convenient that the solid content considers it as the range of the amount % of about 5 A 160i1i by addition or removal of the - or other solvents, What account polyurethane system resin of A dissolved enough into the organic solvent in the present invention may be used, and the dispersion liquid in the state where it deposited partially or extensively may be sufficient (only henceforth solution). For preparing a polyurethane emulsion from the above-mentioned polyurethane solution, It is obtained by adding the water below saturation-1i, for example, the water of 1500 weight sections of about 50 A per 100 weight sections of solid content in solution, in this, adding a suitable quantity of an oil Nakamizu type emulsifier in the above-mentioned polyurethane solution if needed, and agitating this powerfully in it. although each publicly known oil Nakamizu type emulsifier can be conventionally used as an emulsifier -- especially a suitable thing -- the inside of a molecule -- A -- this! It is a polyurethane system interface slippage agent which has a polyoxyethylene chain of 4. As for an emulsifier, it is preferred to use it at a rate of about j per solid content tooxTcli section of polyurethane system resin solution and ten-fold Noon l one copy. Thus, an obtained polyurethane emulsion is a milky creamy fluid. A stable state is held even if it neglects it for several months then. Such a polyurethane emulsion can add a publicly known additive agent arbitrarily if needed like various kinds of additive agents, for example, colorant, a crosslinking agent, stabilizer, a bulking agent, etc. -As a substrate used for manufacturing a porous sheet from the polyurethane emulsion like F accounts, what kind of substrate may be sufficient as textiles 1 knitted fabric of each d, a nonwoven fabric, mold-releasing paper, a plastic film, a metal plate, a glass board, etc., for example. The application method of the above-mentioned polyurethane emulsion for the substrate, For example, a coating method, immersion nature, these methods of put together, etc. are not, but the publicly known method of I may be used and it can change the being impregnated and/or the amount of applications in the wide range like /(combination liquid) The according to the object 2.000 g of about 5 Nobu. Each gelling and dryness of a substrate which impregnated with and/or applied a polyurethane emulsion of an account of A may be the same as that of conventional technology. For example, a polyurethane porosity sheet material which has the characteristic which was excellent in temperature about about 40 thru/or 200 degreeC by dryness for several hours for several minutes is obtained. (EFFECT OF THE INVENTION) with, the hole in which the porous sheet material obtained using the polyurethane emulsion of the present invention like J2 is very minute -- having structure and having the water-vapor-permeation nature which was excellent while excelling in each paste nature -- as materials, such as various kinds of synthetic leather It is useful in filters, such as garments, shoes, waterproof cloth, a tent, wallpaper, a flooring material, a filter medium, and an air-conditioner, etc. It is especially polyurethane system resin in the polyurethane emulsion of the present invention, As a result of Contains f Carrying out the silicone segment and the fluoridation carbon segment into main Ri n of the molecule, and/or a side chain, even if it forms a porous layer from the emulsion, The surface slippage, A feeling, the waterproof pressure nature, resistance to contamination, and wash endurance which the silicone segment and fluoridation carbon segment in a porous layer did not carry out Bleed out to the surface of the porous layer temporally, therefore were semipermanently excellent can be held. Next, a reference example, an example, and a comparative example are given, and the present invention is explained concretely. It is a weight standard that it is with the sentence central part or %, as long as there is no notice especially. Reference example 1 (example of manufacture of an intermediate) While carrying out Adding body coronate to 3 mol of tolylene diisocyanate (TDI) with 1 mol of Trimethi roll propane, and 50degreeC may be sufficient and the product made from Japanese polyurethane, N00%12.5, and 175 copies of 75% solid content are agitated, 880 copies of end aminopropyl poly dimethylsiloxane (a molecule, ff12,200) which consists the following structure in this is dropped gradually, and is made to react. (n is a value from which a molecular weight is set to 2,200) Behind reaction way Y, when ethyl acetate was evaporated, 976 copies of transparent fluid-like intermediates were obtained. According to the infrared absorption spectrum of this intermediate, the absorption by the isolation isocyanate group of 2270/c m remains, and showed 1090-/cn+ the absorption belt by a 5i-0-C basis. When the free isocyanate group in this intermediate was quantified, the actual measurement was 0.78% to a theoretical value being 0.83%. Therefore, a main structure of the above-mentioned intermediate is presumed to be a following formula. Reference example 2 (example of manufacture of an intermediate) - Added 24 copies of phenyl isocyanate, and 60degreeC may be sufficient, agitate to 196 copies of end hydroxypropyl poly dimethylsiloxane (molecule ff1980) which has the following structure, it was made to react to it, and 213 copies of transparent liquefied reaction products were acquired. While 60degreeC may be sufficient and 52 copies of accretionary prisms (Jura Nate 24A-100, voice transformation make, NC0%23.5) of (n being a value from which a molecular weight is set to 980) next hexamethylene di-isocyanate, and water are agitated, 220 copies of above-mentioned reaction products are dropped gradually, and were made to react into this, and 263 copies of water-white liquefied intermediates were obtained. According to the infrared absorption spectrum of this intermediate, the absorption by the isolation isocyanate group of 2270-/cm remains, and showed the absorption belt by a 5i-0-G basis to 1090-/cm. When the free isocyanate group in this intermediate was constant 1a Carried out, the actual measurement was 1.37% to a theoretical value being 1.54%. Therefore, a main structure of the intermediate of the account of 1. A is presumed to be a following formula. Reference example 3 (example of manufacture of an intermediate) To 230 copies of end aminopropyl poly dimethylsiloxane (molecular weight 1,150) which has the following structure, 80degreeC could be sufficient, agitate 15 copies of n-butylaldehyde and made it to add and react, and it was made to react for 3 hours, removing out of a system under decompression of the generated water, and 238 copies of transparent liquefied reaction products were acquired. (n being a value from which a molecular weight is set to 1,150), next 1 mol of Trimethi roll propane, and A and 1 Addition object DIION with 3 mol of xylylene diisocyanate (Takenone) Agitating well the product made from the Narita medicine, NC0%11.5, and 186 copies of 75% solid content at room temperature, 490 copies of above-mentioned reaction products were gradually dropped into this, and it was made to react by 60 degreeC. After the end of a reaction, when ethyl acetate was evaporated, 610 copies of transparent fluid-like intermediates were obtained. According to the infrared absorption spectrum of this intermediate, the absorption by a 22707-cm isolation isocyanate group remains, and showed 1090-/e+a the absorption belt by a 5i-0-C basis. When the free isocyanate group in this intermediate was carried out constant h1, the actual measurement was 1.25% to a theoretical value being 1 or 34%. Therefore, a main structure of the intermediate of -11 account is presumed to be a following formula. Reference example 4 (example of manufacture of an intermediate) 60degreeC being sufficient and stirring 35 copies of 2 and 6 1 A 2 lungi isocyanate, and 110 copies of ethyl acetate, 316 copies of end Mercap 1 Heprovirbori dimethylsiloxane (molecular weight 1.580) which has the following structure is dropped gradually, and is made to react into this. After the end of 0ISi(CL) z03+si3 (C113) (+, m, and n are values from which molecular weight is set to 1,580) reaction, when ethyl acetate was evaporated, 340 copies of transparent fluid-like intermediates were obtained. According to the infrared absorption spectrum of this intermediate, the absorption by the isolation isocyanate group of 2270-/cm remains, and showed the absorption belt by a 5i-0-C basis to 1090-/cm. When the free isocyanate group in this intermediate was quantified, the actual measurement was 2.12% to a theoretical value being 2.39%. Therefore, a main structure of the above-mentioned intermediate is presumed to be a following formula. (1, m, and n are values from which molecule Bt, is set to 1,580) Reference example 5 (example of manufacture of an intermediate) 60degreeC being sufficient and agitating 52 copies of hexamethylene di-isocyanate, and 160 copies of ethyl acetate, 450 copies of end hydroxypropyl poly dimethylsiloxane (molecule fi2,250) which has the following structure is dropped gradually, and is made to react into this. (n is a value from which a molecular weight is set to 1,580) After the end of a reaction, when ethyl acetate was evaporated, 488 copies of transparent fluid-like intermediates were obtained. The absorption [ according to the infrared absorption spectrum of this intermediate ] by the isolation isocyanate group of 2270-/cm remains, and is 5i-0 to 11 Thu l O907cm. - (: the absorption belt by a basis was shown.) When the free isocyanate group in this intermediate was quantified, the actual measurement was 1 or 52% to a theoretical value being 1.67%. Therefore, the t cask structure of the above-mentioned intermediate is presumed to be a following formula. Reference example 6 (example of manufacture of an intermediate) Adding body Jura Nate 24A-100 of hexamethylene di-isocyanate and water, and voice -- transformation -- while 60degreeC may be sufficient and make and 800%23.5 52 copy are agitated 53 copies of fluorination alcohol which has the following structure is dropped gradually, and was made to react into this, and 103 copies of water-white liquefied intermediates were obtained. II (CF2CF2) i, Oll According to the infrared absorption spectrum of this intermediate, the absorption by the isolation isocyanate group of 22707 c m remains, and showed the absorption belt by a -cF2-basis to 1190-/cm. When the free isocyanate group in this intermediate is quantified, to a theoretical value being 2.65%, an actual measurement is 2.51% and is That's it.. Therefore, a main structure of the above-mentioned intermediate is presumed to be a following formula. Reference example 7 (example of manufacture of an intermediate) While 50degreeC may be sufficient and 1 mol of Trimethi roll propane and 120 copies of accretionary prisms (carrying out coronate Japanese polyurethane fellows, NC0%12.5, 75% of solid content) with 3 mol of tolylene diisocyanate (TDI) are agitated, Fluorine and 114 copies of 11-ized Arco 1 Le which have the following structure are dropped gradually, and are made to react into this. 198 copies of transparent fluid-like intermediates were obtained after the end of Ch (f;Fz[:Fz) 30+1 reaction. According to the infrared absorption spectrum of this intermediate, the absorption by the isolation isocyanate group of 2270/am showed the absorption belt by -CF and - basis to Remaining and 1190-/cm. When the free isocyanate group in this intermediate was quantified, the actual measurement was 2.68% to a theoretical value being 2.83%. Therefore, a main structure of the above-mentioned intermediate is presumed to be a following formula. Reference example 8 (example of manufacture of an intermediate) While agitating well 1 mol of Trimethi roll propane, and 186 copies of accretionary prisms (Takenate D11ON, the product made from the Narita medicine, NC0%11.5, 75% of solid content) with 3 mol of xylylene diisocyanate at room temperature, 172 copies of fluorination Thio records which have the following structure were dropped gradually, and were made to react into this. CF3 (320 copies of transparent fluid-like intermediates were obtained after *Cl12CIIzSH Reaction end r.) (:F2CF2) According to the infrared absorption spectrum of this intermediate, the absorption by the isolation isocyanate group of 22707 c m remains, and showed the absorption belt by -CF and - basis to 1190-/cm. When the free isocyanate group in this intermediate was quantified, the actual measurement was 2.51% to a theoretical value being 2.69%. Therefore, a main structure of the above-mentioned intermediate is presumed to be a following formula. (X = 5GH2CH2 (C:F2CF2) 3CF3) Reference example 9 (denaturation - side 3m of resin) 1,000 copies of poly ethylene adipate (average molecule Placement 1,000, hydroxyl value 112), They are 144 copies of 1.4-butanediol, 1,144 copies of methyl ethyl ketone, and 650 copies of diphenylmethane diisocyanate after an 8-hour reaction at 70 degreeC, Methyl ethyl ketone of 3,042 more copies was added, and it equalized, and it cooled to normal temperature, agitating, and obtained the polyurethane dispersion liquid of the milk white of 30% of solid content. Five copies of intermediates of reference example 1 and five copies of intermediates of reference example 6 were added to 100 copies of these polyurethane dispersion liquid, and the denaturation resin liquid (1) of the milk white which was made to react by 70 degreeC for 4 hours, and an intermediate and polyurethane resin combined was obtained. As for the isocyanate group, the denaturation resin obtained above was not accepted with an infrared absorption spectrum. This is presumed to be that in which the intermediate carried out graft combination at resin. Reference example io (denaturation and - side chain of resin) 1,000 copies of 1.4-butane Eden Asibe and - A (\-division-into-equal-parts Child amount 1,000, hydroxyl value 112), They are 125 copies of 1.4-butanediol, 1.144 copies of methyl ethyl ketone, and 650 copies of diphenylmethane diisocyanate after an 8-hour reaction at 70 degreeC, Methyl ethyl ketone of 3,042 more copies was added, and it equalized, and it cooled to normal temperature, agitating, and obtained the polyurethane dispersion liquid of the milk white of 30% of solid content. Five copies of intermediates of reference example 2 and five copies of intermediates of reference example 7 were added to 100 copies of these Boliv 1 Notan dispersion liquid, and the denaturation resin liquid (2) of the milk white which was made to react by 70 degreeC for 4 hours, and an intermediate and polyurethane resin combined was obtained. Denaturation Il which was alike and was acquired in the account! As for 4 fat, the isocyanate group was not accepted with an infrared absorption spectrum. This is presumed to be that in which the intermediate carried out graft combination at resin. Reference example 11(denaturation of resin .. - side chain)1.6 - 1,000 copies of affected methylene horse mackerel Beat (average part A-bomb 2.000, Hydrocolloid value 56), They are 125 copies of 1.4-butanediol, 1,200 copies of methyl ethyl ketone, and 1,472 copies of diphenyl methane Diisocyanate- after an 8-hour reaction at 70 degreeC, Methyl ethyl ketone of 2,526 more copies was added, and it equalized, and it cooled to normal temperature, agitating, and obtained the polyurethane dispersion liquid of the milk white of 30% of solid content. Five copies of intermediates of reference example 3 and five copies of intermediates of reference example 8 were added to 100 copies of these polyurethane dispersion liquid, and the denaturation resin liquid (3) of the milk white which was made to react by 70 degreeC for 4 hours, and an intermediate and polyurethane resin combined was obtained. As for the isocyanate group, the denaturation resin obtained in" 2 account was not accepted with an infrared absorption spectrum. This is presumed to be that in which the intermediate carried out graft combination at resin. Reference example 12 (denaturation and - side chain of resin) Polytetramethylene glycol (average molecule Placement 1.000, hydroxyl value 112) l They are 000 copies, 93 copies of ethylene glycol, 21.500 copies of methyl Ethyl keto, and 625 copies of diphenylmethane diisocyanate after an 8-hour reaction at 70 degreeC, Methyl ethyl ketone of 2,500 more copies was added, and it equalized, and it cooled to normal temperature, agitating, and obtained the polyurethane dispersion liquid of the milk white of 30% of solid content. Five copies of intermediates of reference example 4 and five copies of intermediates of reference example 7 were added to 1O0 copy of these polyurethane dispersion liquid, and the denaturation resin liquid (4) of the milk white which was made to react by 70 degreeC for 4 hours, and an intermediate and polyurethane resin combined was obtained. As for the isocyanate group, the denaturation resin obtained above was not accepted with an infrared absorption spectrum. Stiffness is presumed to be that in which the intermediate carried out graft combination at resin. 1,000 copies of reference example 13 (denaturation of resin ... side chain) polycarbonate polyols (- A division-into-equal-parts About clams 2.000 and hydroxyl value 56), They are 93 copies of ethylene glycol, 1.200 copies of methyl ethyl ketone, and diphenyl methane Diisocyanate-509 copy after an 8-hour reaction at 70 degreeC, Methyl ethyl ketone of 2.522 copies was added and it equalized, and it cooled to normal temperature, agitating, and obtained the polyurethane dispersion liquid of the milk white of 30% of solid content. Five copies of intermediates of reference example 5 and five copies of intermediates of reference example 8 were added to 100 copies of these polyurethane dispersion liquid, and the denaturation resin liquid (5) of the milk white which was made to react by 70 degreeC for 4 hours, and an intermediate and polyurethane resin combined was obtained. As for the isocyanate group, the denaturation resin obtained in" 2 account was not accepted with an infrared absorption spectrum. This is presumed to be that in which the intermediate carried out graft combination at resin. Reference example 14 (denaturation and - main chain of resin) l, 1,000 copies of 4-butane ethylene adipate (average molecule product about 1.000 hydroxyl value 112), The silicone compound ioo section of the following structure (A), 50 copies of fluoridation carbon compounds of the following structure (Ro), Added 31 copies of 1 and 4-butanediol, and 362 copies of diphenylmethane diisocyanate into 3,600 copies of methyl ethyl ketone, it was made to react by 70 degreeC for 8 hours, and the average molecular weight obtained the polyurethane resin solution of 30% of the solid content which is 64,000. Subsequently, 130 copies of ethylene glycol and 503 copies of diphenylmethane diisocyanate are added to the above-mentioned resin solution, After a 10-hour reaction and also methyl Ethyl keto 21, and 4 Giggle parts were added by 60 degreeC, and it equalized, it cooled to normal temperature, agitating, and the average molecular weight of polyurethane is 133,000 and the diameter of a particle of the particles which deposited obtained the polyurethane dispersion liquid (6) of the milk white of 30% of the solid content which is 1 micrometer or less. (n in a formula is a value from which a molecular weight is set to 5,000) (CF2) F a (C112) zOclI2 (:HCHJH (B) reference example 15 (denaturation-main chain of resin)) 1,000 copies of polytetramethylene glycols (average molecule Placement 1.000, hydroxyl value 112), 100 copies of silicone compounds of the following structure (C), 50 copies of fluoridation carbon compounds of the following structure (D), Added 24 copies of ethylene glycol, and 360 copies of diphenylmethane diisocyanate into 3,580 copies of methyl ethyl ketone, it was made to react by 70 degreeC for 9 hours, and the average molecular weight obtained the polyurethane resin solution of 30% of the solid content which is 53,000. Subsequently, 116 copies of ethylene glycol and 465 copies of diphenylmethane diisocyanate are added to the above-mentioned resin solution, 1,356 copies of methyl ethyl ketone was added after a 10-hour reaction by 60 degreeC, and it equalized, it cooled to normal temperature, agitating, and the average molecular weight of polyurethane is 107,000 and the diameter of a particle of the particles which deposited obtained the polyurethane dispersion liquid (7) of the milk white of 30% of the solid content which is 1 micrometer or less. (n in a formula is a value from which a molecular weight is set to 5.000) F (CFz) a (20(: Il□)C1bC1lCHz011 (D) O11 reference example 16 (denaturation and - main chain of resin)) 1.6 - 2,000 copies of Xamethylene adipate (average molecule Placement 2.OOQ, hydroxyl value 56), 200 copies of silicone compounds of the following structure (E), 50 copies of fluoridation carbon compounds of the following structure (F), Added 31 copies of 1.4-butanediol, and 346 copies of diphenylmethane diisocyanate into 6.135 copies of methyl ethyl ketone, it was made to react by 70 degreeC for 9 hours, and the average molecular weight obtained the polyurethane resin solution of 30% of the solid content which is 72,000. Subsequently, 390 copies of Trimethi roll propane and 1.047 copies of diphenylmethane diisocyanate are added to the above-mentioned resin solution, By 60 degreeC, 3,353 copies of methyl ethyl ketone is added after a 10-hour reaction, and it equalizes, It cools to normal temperature, agitating, and average molecule hl of polyurethane is 178,000, the polyurethane dispersion liquid (8) of the milk white of 30% of solid content are obtained (n in a formula is a value from which a molecular weight is set to 5,000), and it is P (CF2)+. (C112) 201111zC1lJCH2CIC112011 (F) O■ Reference examples 17 thru/or 24 The output, the emulsifier, the organic solvent, and water of reference examples 9 thru/or 16 were agitated by the gay mixer, and the following polyurethane emulsion was prepared. ! * 17.7 -- Ma -- Lettua - - 1 polyurethane fluid (1) The too section Uji Urethane system emulsifier Two-copy methyl ethyl ketone 20-copy xylene 20-copy water [ 85 copy / 18 degree ] Vo t k Kyu milk 1 Choking 1 Polyurethane fluid (2) loo section Uji Urethane system emulsifier Two-copy methyl ethyl ketone 20-copy toluene 20-copy water 80-copy valley 2JtL1SamuraiA (Likely" Jin-young J Throat m- Hmm n polyurethane M (3)) too section Uji Urethane system emulsifier Two-copy methyl ethyl ketone 150-copy toluene 20-copy water It is 9 >= Milky liquid J4 Likelihood polyurethane fluid (4) to 80-copy Shika side edge "" 2 Him. 4 copies of 100-copy PO/EO block co-polymer type emulsifier dioxane Ten-copy toluene Ten-copy xylene 20-copy water 7o section 31[i Me- A = [ ' 21 and ] - tortoise Carry out, and it is A -Nu~1 polyurethane fluid (5). 100-copy urethane system emulsifier One-copy methyl isobutyl ketone 20-copy toluene 20-copy water Evening 21 is taken for 75-copy Mouthfeel thinking-2""" Immediately 9, and it is liquid-proof""->-polyurethane (6). 1 copy of 100-copy PO/EO block co-polymer type emulsifier tetrahydro franc 20-copy toluene 20-copy water 60-copy A! d Ruins"-2 main force 2 -- Tk person <= second Rume IL-Jin Zl polyurethane fluid (7) 100-copy urethane system emulsifier Two-copy methyl ethyl ketone 20-copy xylene 20-copy water 85 copy I Retribution 1 is taken and it is point±J S L A long time y An animal bell Turbidity 1L Jin"Y polyurethane fluid (a). The ioo section Uji Urethane system emulsifier Two-copy methyl ethyl ketone 20-copy toluene 80 copies of 20-copy water comparative examples 1 thru/or 8 As the silicone segment in reference examples 17 thru/or 24, and fluoridation Charcoal segment content polyurethane system resin, Using the polyurethane system resin liquid as for which 41' Si is not about the silicone segment and fluoridation carbon segment which the product made from 'A made be the same as that of reference examples 9 thru/or 16, others prepared the polyurethane emulsion of comparative example 1 A Postcode8 like reference examples 17 thru/or 24. The character of the polyurethane emulsion of the above-mentioned reference examples 17 thru/or 24 and comparative examples 1 thru/or 8 is as in the 1st table of the following. 12 cost -- One - 1Axi - 4□-25! and a 111-H Astronaut-reference example 17 21 QOOcps 14.11 B +7,500cps 14 *4tL 9 140eps 9.2%20 22.0OOcps 14.9t21 20.00Ocpseye 4t22 14.600 c.p.s. +5.5%23 21.000 c.p.s. 14.2*24 +5,200eps 14.F4 comparative example 1 2 +, 0OOcps 14, 29F. 2 16 000 C.p.s. l 4, 4*3 +40cps 9.T%4 20.000cps 14.9'J5 19.000 c.p.s. 14. Cutting 6 16.000 c.p.s. 15.5!7 19.0OOcps 14.2 tortoises 8 17.0OOeps 14.5 main remarks Stability - - Various kinds of porous sheet materials which impregnate with and/or apply, dry all to various kinds of substrates on conditions given [ the polyurethane emulsion of three month / or more /-change-less Example 1 thru/or the 1st table of the account of 811rr ] in the 2nd table of the following, and have the characteristic of a statement in the 3rd table of the following were obtained. Comparison examples 1 thru/or 8 were also performed on the same conditions as people examples 1 thru/or 8. gammaJ2 -- a notice Example 1 One milk S Axillary-Mll! Paper pattern * Right = 'm'' 80 degrees of 200 (i cloth) Dry laboratory work CX 2m1n, and + 125"CX2+sin. Example 2 Two Tile noodles - M Mold release paper, l -- The 200 (application) 80 degrees of Same as dry cheese Cx 2m1n, and + 125"CX2m1n. Example 3 Three 9S liquid - M Nonwoven fabric - the right -- " (90 degrees of U sections of A go 1ooo (application) average Cx 3m1n, +140"ex 3m1n.) Example 4 Four 9 Courage-material Cheesecloth - t -- The 400 140 degrees of dry (application) Bean CX3m1n. Example 5 Five Tailoring-A seal Nylon taffeta Paint*'ITI"200 (application) It Float on the floor and is multi-A1. 80 °Cx 2 win-+ 1 25"Cx2mrn. Example 6 Six Perforation-A seal T/R nap-raising cloth'67 'rn"600(application)U section ■ 120 degreeCX4fflin. Example 7 Seven edited one by Big Rabbit-A seal Tetoron taffeta Paint 1- 140 degrees of 'Soft dry rice [ -rn"200 (application) ] Cx2 o+in. Example 8 Eight Holy character - M T/R nap-raising cloth t"i 120 degrees of 'Rolling action [ rn"600 (application) ] Cx4min. gamma 3~-Tooth - QOOcps 14.11 B +7,500cps 14 *4tL 9 140eps 9.2%20 22.0OOcps 14.9t21 20.00Ocpseye 4t22 14.600 c.p.s. +5.5%23 21.000c.p.s.14.2*24 +5,200eps 14.F4 comparative example 1 2 +, 0OOcps 14, 29F. 2 16 000 C.p.s. l 4, 4*3 +40cps 9.T%4 20.000cps 14.9'J5 19.000cps 14. Cutting 6 16.000cps 15.5!7 19.0OOcps 14.2 tortoises 8 17.0OOeps 14.5 main note stability - - Various kinds of porous sheet materials which impregnate with and/or apply, dry all to various kinds of substrates on conditions given [ the polyurethane emulsion of three month / or more /-change-less Example 1 thru/or the 1st table of the account of 811rr ] in the 2nd table of the following, and have the characteristic of a statement in the 3rd table of the following were obtained. Comparison examples 1 thru/or 8 were also performed on the same conditions as people examples 1 thru/or 8. gammaJ2 -- a notice Example 1 One milk S Axillary-Mll! Paper pattern * Right = 'm'' 80 degrees of 200 (i cloth) Dry laboratory work CX 2m1n, and + 125"CX2+sin. Example 2 Two Tile noodles - M Mold release paper, l -- The 200 (application) 80 degrees of Same as dry cheese Cx 2m1n, and + 125"CX2m1n. Example 3 Three 9S liquid - M Nonwoven fabric - the right [ ] -- " (90 degrees of U sections of A go 1ooo (application) average Cx 3m1n, +140"ex 3m1n.) Example 4 Four 9 Courage-material Cheesecloth -t -- The 400 (application) 140 degrees of dry Bean CX3m1n. Example 5 Five Tailoring-A seal Nylon taffeta Paint*'ITI"200 (application) It Float on the floor and is multi-A1. 80 °Cx 2 win-+ 1 25"Cx2mrn. Example 6 Six Perforation-A seal T/R nap-raising cloth'67 'rn"600(application)U section ■ 120 degreeCX4fflin. Example 7 Seven edited one by Big Rabbit-A seal Tetoron taffeta Paint 1- 140 degrees of 'Soft dry rice [ -rn"200 (application) ] Cx2 o+in. Example 8 Eight Holy character - M T/R nap-raising cloth t"i 120 degrees of 'Rolling action [ rn"600 (application) ] Cx4min. gamma 3~- Tooth - 3 580 0 9.150 - 100 702510 0 9.070 - 100 703 530 0 6.230 6.000 +00 504 450 0 8.360 fi, 50G 100 705 520 0 6.510 4.500 100 706 650 0 7.180 6,000 100 707630 0 7.080 5,000 100 508 660 0 7.590 6.500 100 70 Le -- a crest -- Drowning 1 30 0 6.270 - 0 02 25 0 5.820 - 0 03 35 Delta 4,050 4,500 0 04 40 x 5.800 5,000 0 05 30 X 2.960 3,500 0 06 28 delta 6.+00 5,000 0 07 37 X 6,890 3.500 0 08 31 X 5,120 5.000 0 Zero note I -.. surface slippage (surface endurance): -- the number of times until it rubs a resin layer with gauze by 500 g of load and a resin layer is destroyed ■ ... A feeling: -- O= software and △= -- a little -- Hardware and x= Nihard ... water-vapor-permeability (g/rn"2411rs, Jrs 7.0208B) ■--water resistance pressure (mmlho)