JPS61282481A - Production of water-proofing fiber sheet material - Google Patents

Abstract

PURPOSE:To obtain a water-proofing sheet having excellent durability, by emulsifying a water-repellent composed of a wax, a specific addition reaction product and a paraffinic hydrocarbon with an alkaline agent, applying the produced emulsion to a fibrous substrate cloth, and coating both surface of the substrate cloth with polymer films. CONSTITUTION:A water-repellent emulsion is produced by emulsifying a mixture of (A) a wax (e.g. low-molecular weight polyethylene, polypropylene, etc.), (B) an addition reaction product of an unsaturated carboxylic acid or its anhydride, preferably an addition product of maleic anhydride and a wax and (C) a paraffinic hydrocarbon having a melting point of 40-85 deg.C with (D) a water-soluble alkaline agent (e.g. alkali metal hydroxide). The emulsion is applied to a fibrous substrate cloth made of natural, regenerated, semisynthetic or synthetic fiber and solidified by drying. Both surfaces of the treated substrate cloth are coated with coating films of a hydrophobic synthetic resin such as polyvinyl chloride, polyurethane, etc. When a melamine adhesive, etc., is interposed between the substrate cloth and the resin layer, the adhesivity of the coating layer to the substrate cloth can be improved remarkably to prevent the lowering of the durability caused by the peeling of the coating layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for manufacturing a waterproof fiber sheet material. Specifically, it relates to a method for manufacturing a waterproof fiber sheet material in which the fibrous base fabric has extremely low water absorption and the adhesion between the base fabric and the waterproof polymer film formed thereon is extremely strong. It is.

[Conventional technology]

Conventionally, waterproof fibrous sheet materials have been produced by forming a coating made of a waterproof polymer on the surface of a fibrous base fabric. However, in waterproof fiber sheet materials formed by forming coatings on both sides of a fibrous base fabric, the intermediate layer of fibrous base fabric sandwiched between the waterproof coatings may crack or tear even if the coating is slightly In some cases, water can be absorbed through the cracks or tears, or even in the absence of such phenomena, through the cut edges of the sheet material.

If the fibers in the base fabric are dense, this water absorption is further increased by capillary action. Then, due to the absorption of water,
The waterproof fibrous sheet material is bulky and heavy, and the adhesion between the fibrous base fabric and the coating is reduced. In addition, the absorbed water is difficult to release from the fibrous base fabric, and furthermore, there is a drawback that, for example, sewage or discolored water that has grown mold bacteria is absorbed, spoiling the appearance of the sheet.

In order to eliminate such drawbacks, conventionally, a fibrous base fabric is treated with a water repellent and then a polymer coating is formed on both surfaces thereof. In this case, the fibrous base fabric is treated with a water repellent, which prevents water from penetrating into the fibrous base fabric, but on the other hand, if the water repellent effect increases, the water repellent becomes a type of It acts as a mold release agent, and therefore has poor adhesion between the coating and the fibrous base fabric, which is undesirable in practical terms. Efforts have also been made to improve adhesion by adding adhesive substances such as incyanate to water repellents and film-forming agents, but no satisfactory results have been obtained. is the current situation.

[Problem that the invention seeks to solve]

The present invention solves the problems of conventional waterproof fiber sheet materials, namely, the fibrous base fabric absorbs water, and the adhesive strength between the fibrous base fabric and the waterproof polymer coating layer is low and gradually decreases. It is an object of the present invention to provide a method for manufacturing a waterproof fiber sheet material that can solve the problems such as:

[Means for Solving the Problems and Their Effects] The method for producing a waterproof fiber sheet material of the present invention includes the addition reaction product of wax, an unsaturated carboxylic acid or anhydride thereof, a paraffinic hydrocarbon, A fibrous base fabric is impregnated with a water repellent emulsion containing a water-soluble alkaline substance for emulsifying these, and after drying and solidifying the impregnated water repellent aqueous emulsion, the fibrous base fabric is It is characterized by forming a waterproof polymer coating on both surfaces of the cloth.

Another method for producing a waterproof fiber sheet material of the present invention is to use an addition reaction product of a wax and an unsaturated carboxylic acid or its anhydride, a mother rough-in hydrocarbon, and a water-soluble material for emulsifying these. A fibrous base fabric is impregnated with a mixture of a water repellent aqueous emulsion containing an alkaline substance and an aqueous emulsion of at least one film-forming/rimer, and the impregnated mixture is dried. After solidification, a waterproof polymer coating is formed on both surfaces of this fibrous base fabric.

Fibrous base fabrics useful in the present invention include natural fibers such as cotton, linen, inorganic fibers such as glass fiber, carbon fiber, etc.
Asbestos fibers, metal fibers, etc., recycled fibers, such as viscose rayon, cuzora, etc., semi-synthetic fibers, such as no- and tri-acetate fibers, and synthetic fibers, such as nylon 6, nylon 66, polyester (
(polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, ? It is made of at least one kind selected from lyolefin fibers and polyvinyl alcohol fibers made insoluble or hardly soluble in water. The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, sugerit yarn, chive yarn, etc., and the base fabric may be woven, knitted, nonwoven, or a composite fabric of these. It's okay. Generally, the fibers used in the waterproof fiber sheet material according to the present invention are preferably polyester fibers and glass fibers, and considering that they have little elongation under stress, the fibers are in the form of long fibers (filaments). It is preferable that the material is a plain woven fabric. However, the weaving structure and its form are not particularly limited. The fibrous base fabric is useful for maintaining the mechanical strength of the resulting waterproof fibrous sheet material at a high level.

In the method of the present invention, an addition reaction product of a wax and an unsaturated carboxylic acid or an anhydride thereof, a mother rough-in hydrocarbon, and a water-soluble alkaline substance for emulsifying these are added to a fibrous base fabric. or by an aqueous emulsion of a water repellent containing and at least one film-forming emulsion of ? It is impregnated with a mixture of remer and an aqueous emulsion and then dried and solidified.

In other words, the waxes used in the water repellent aqueous emulsion include low molecular weight polyethylene, low molecular weight polypropylene,
Polyolefin waxes such as low molecular weight ethylene-propylene copolymers or mixed waxes of these polyolefin waxes and petroleum distillate waxes are used.

In addition, unsaturated carboxylic acids include maleic acid, fumaric acid,
and itaconic acid.

As the addition reaction product, a maleic anhydride-wax addition reaction product is preferred in view of its operability and performance. This addition reaction product has an acid value of 15 to 120. More preferably, the melting point is 35 to 90°C, and the melting point is 40 to 140°C, and even more preferably 40 to 80°C. acid value is 1
If it is smaller than 5, the emulsifying property in water may be insufficient and the resulting emulsion may become unstable. Furthermore, if the acid value is higher than 120, the resulting waterproof fiber sheet material may have insufficient waterproof properties and durability.

The 9 rough-in hydrocarbon used in the method of the present invention is 4
It is preferable that it has a melting point of 0°C to 100°C, and more preferably that it has a melting point of 40°C to 85°C.

Examples of water-soluble alkaline substances used in the method of the present invention include hydroxides and carbonates of alkali metals (eg, sodium, potassium, lithium), ammonia, water-soluble amines (eg, ethanolamine), and the like. The water-soluble alkaline substance is effective in emulsifying the addition reaction product and the graphene hydrocarbon in water.

The wax addition reaction product and the mother rough-in hydrocarbon are mixed at a weight ratio of preferably 3:97 to 60:40, more preferably 3:97 to 35:67.

Generally, the alkaline substance is a wax addition reaction product and
・0.1 to 4 relative to the total weight of rough-in hydrocarbons
It is preferable to use a blending ratio of 5.0%.

A suitable amount of natural rosin, rosin ester, plastic wax, high acid value or regular montan wax, etc. may be added to the water repellent aqueous emulsion to improve the film forming properties and adhesion of the water repellent. good.

In the present invention, no surfactant is required in the water repellent aqueous emulsion; however, depending on the application, such as the mechanical stability of the emulsion during ultra-high-speed stirring and further miniaturization of the particle size, saturation may occur. 6 weight of the total amount of addition reaction wax product of polyhydric carboxylic acid or its anhydride and paraffinic hydrocarbon, and even 3
．． Addition of 5 or less surfactants is permissible depending on the application. Even so, surfactants are usually 20 to 30 times heavier than paraffinic hydrocarbons! However, sometimes even more is added, so if it is less than 3.5% by weight, it is very small, and this addition hardly causes any problems. What can be considered as these nonionic surfactants? Liolefin oxide alkyl ethers, esters thereof, sorbitan esters, etc., and anionic surfactants include higher fatty acids and other alkali salts (including amine salts and ammonium salts), which are available upon request. It is necessary to combine them appropriately. however,
The amount added must be kept within the above-mentioned limits, and it is preferable to use as little as possible.

In order to produce the water repellent aqueous emulsion of the present invention, strong stirring or shearing strength is required using an autoclave (pressure vessel) or a pressurized homomixer.
Emulsification while providing h) is most suitable for the purpose, but any method may be used as long as a uniform emulsion can be obtained.

The waterproof polymer emulsion is particularly effective in improving the water-resistance effect and adhesion effect of the water-repellent aqueous emulsion, and the film strength such as the readability and abrasion resistance of the resulting water-repellent film.

Preferably, the waterproof polymer has good film-forming properties in the temperature range of -15°C to 185°C.

Therefore, it is important to adjust the copolymerization composition, degree of polymerization, particle size, etc. of the waterproof polymer so as to exhibit the above performance.

Waterproof I remers include polymers and copolymers of acrylic esters, methacrylic esters, vinyl ethers, acrylonitrile, styrene, acrylic acid, methacrylic acid, etc. As acrylic esters, methyl , ethyl, butyl esters, 2-ethylhexyl acrylate, etc., and methacrylic acid-based methyl, ethyl, butyl esters, 2-ethylhexyl methacrylate, etc. These may be used singly or in combination of two or more. It may also be a copolymer. This polymer emulsion needs to have good compatibility with the water-repellent emulsion sb, and for this reason, the HLBI of both needs to be as close as possible.

In addition to HLB, it is important for polymer emulsions to have similar particle sizes as much as possible, and for this reason, nonionic surfactants, anionic surfactants, reactive emulsifiers such as unsaturated acid-containing sulfonates, or The purpose can be achieved by using sulfuric esters alone or in combination, and protective colloids such as polyvinyl alcohol and polyacrylamide can also be used, but it is necessary to be careful about the amount added.

In addition, natural or synthetic rubber latex, if compatible as a polymer emulsion, or if a protective colloid thickener is added.
Urethane emulsions, polyesters, and epoxy resin emulsions can also be used. 5B as synthetic rubber latex
There are R (styrene-butadiene rubber), MBR (methyl methacrylate-butadiene rubber), etc., and these are thick because they contribute to readability. Acrylic acid ester,
When preparing a single or copolymer emulsion of methacrylic acid ester, acrylic acid, methacrylic acid, acrylonitrile, styrene, etc., use a compatible surfactant as described above, and use persulfate or peroxide as a catalyst. Redox polymerization can also be carried out at low temperatures by emulsifying in water at high temperatures using peroxides such as hydrogen, or by adding a reducing agent.

In the present invention, the weight composition ratio of the water repellent emulsion and the polymer emulsion is most preferably 9515 to 75/25.

To be more precise, a ratio of 80/20 to 75/25 is most effective in preventing ice and absorption of the treated substance.

Since this water repellent emulsion uses an addition reaction wax of unsaturated polyhydric carbic acid or its anhydride, the cargexyl group (-COOH) contained is oxidized 9, which is obtained by simply oxidizing /claffin. Cal from Laugh-in? Since the xyl group is not directly connected to the main chain and has stronger functionality, the reactivity is also higher and the adhesion to the corresponding treatment body is further strengthened. Moreover, the surfactant content is zero or reduced, so it does not interfere with the effect, and furthermore, due to the presence and reduction of these strong cal xyl groups or the absence of surfactants, it has an excellent water repellent effect. ing.

Another feature is that organic solvents such as alcohols, ketones, and esters can be stably added to wax emulsions made with this water repellent, but conventional wax emulsions contain large amounts of surfactants. When mixed with these organic solvents, it coagulates immediately and the emulsion is destroyed. This fact is very important in practical applications. That is, this is a problem of cold resistance.

In general, wax emulsions begin to lose their emulsion stability when the temperature drops below 5°C. At 0°C, most of the emulsions coagulate in the cold, and at -5°C, they all coagulate and break down. However, it does not become an emulsion again and becomes waste. Therefore, it is unavoidable to use it as a cold resistance agent.
Ethylene glycol, polyethylene glycol, chrycerin, etc. are added, but this seriously impairs the repellency and water resistance that are characteristic of wax emulsions, creating a vicious cycle in which the lower the temperature resistance, the worse the repellency and water resistance. are doing.

Therefore, all conventional wax emulsions are not suitable for use in cold regions, and are generally not used in such regions due to their stability.

However, as mentioned above, alcohols can be stably added to the water repellent emulsion of the present invention. Approximately 70% of water repellent emulsion
~80 g volume of alcohol can be added. It has been a long-cherished desire of water repellent emulsions to be able to use alcohols, which do not cause any deterioration in repellency or water resistance, and have excellent cold resistance effects. The water repellent emulsion successfully solved this problem. For example, for the total volume of this water repellent emulsion, add 5 inglobil alcohol.
H.Three parts of methyl alcohol added thereto does not impede the repellency or water resistance in the slightest, and is actually stable even at -20°C.

In addition, due to the carfoxyl group of its unique addition reaction product, metal crosslinking occurs quickly, so crosslinking with polyvalent aluminum, zirconium, etc. promotes repellency, water resistance, and their lasting effects. In fact, zirconyl ammonium carbonate, ammoniacal aluminum, zinc salts, sodium aluminate, etc., which are soluble in alkaline water, are particularly effective as adjuncts for this purpose. The combined use of these does not violate the present purpose in any way.

As can be easily inferred from the above, the present water repellent emulsion and its composition have water resistance and water absorption inhibitors,
It has excellent adhesion, repellency, and water resistance.

In the method of the present invention, the fibrous base fabric can be treated with the water repellent aqueous emulsion by an impregnation method, a coating method, a spraying method, or other methods, but the impregnation method is simple and effective. .

The base fabric treated with the water repellent aqueous emulsion in this manner is dried. The drying temperature is preferably 150°C or lower, more preferably 60 to 140°C, and 80 to 1
More preferably, the temperature is within the range of 20°C. The adhesion amount of the water repellent aqueous emulsion to the fibrous base fabric is 1.0 to 5.0%.
owf (solid content), but the amount of adhesion can be adjusted as appropriate depending on the water repellent effect.

The thus treated base fabric is then subjected to a step of forming a waterproof polymer film on both surfaces thereof. Examples of waterproof polymers include hydrophobic synthetic resins, synthetic rubbers, and natural rubbers. Preferred synthetic resins include, for example, polyvinyl chloride (PVC), polyurethane, ethylene-vinyl acetate copolymer, isotactic polypropylene, polyethylene,? Liacrylonitrile, polyester, moon?
Examples include lyamide, fluororesin, silicone resin, and other known materials. Examples of preferred synthetic rubbers include styrene-butadiene rubber (SBR), chlorosulfonated polyethylene rubber, I-urethane rubber, butyl rubber, Inglene rubber, silicone rubber, fluororesin, and other known materials. In particular, polyvinyl chloride,
Fluorine and silicone rubbers and resins, and acrylic resins are preferred polymers for this invention. These polymers may contain plasticizers, fillers, colorants, various stabilizers, flame retardants, etc., as long as they do not impede the purpose of the present invention.

In particular, in order to strengthen the adhesiveness between the fibrous base fabric and the waterproof polymer layer, it is more preferable to interpose an adhesive substance at the interface between the fibrous base fabric and the polymer. Examples of useful adhesive materials include melamine adhesives, phenolic adhesives, epoxy adhesives, polyester adhesives, I
Polyethyleneimine adhesives, polyisocyanate adhesives, polyurethane adhesives, acrylic adhesives, polyamide adhesives, and copolymer adhesives such as vinyl acetate vinyl chloride adhesives and vinyl acetate-ethylene adhesives, etc. However, without being limited thereto, any known adhesive can be used. The adhesive substance may be used by being mixed into the polymer, or may be applied to the interface.

The surface coating can be formed by a conventional method, such as a calendar method, an extrusion method, a coating method, or a dipping method.

The waterproof fiber sheet material obtained by the method of the present invention not only exhibits virtually no water absorption, but also exhibits a completely unexpectedly high peel strength. That is, when a conventional water repellent was used, the peel strength between the waterproof polymer coating layer and the fibrous base fabric was at most about 6 to 73 cm, but with the sheet material obtained by the method of the present invention, ,
A completely unexpected high peel strength of 14-20 kg and 73 cm was obtained.

〔Example〕

The present invention will be further explained below with reference to Examples.

Examples 1 and 2 and Comparative Examples 1 and 2 Polyester fiber base fabrics: basis weight 300117 m2 and thickness 0.35 mm were scoured, dried, and impregnated with the following water repellent aqueous emulsion.

Water repellent A (Example 1) ■Melting point 60℃t'? 5 Fin wax 22 parts ■ Aqueous ammonia 0.3 parts Wax solid content 30% pH 8.3 Does the above addition reaction product have a low molecular weight? It was an addition reaction product of a mixture of lyolefin wax and petroleum distillate wax and maleic anhydride.

The above J? Rough-in wax and addition reaction product
Melt and mix at 10°C, add ammonia water to this, cool to 100°C, and gradually add boiling water to increase the viscosity and continue stirring while maintaining the temperature at 97°C throughout. A stable ψ-type pore-forming liquid was obtained which underwent emulsion inversion (from W2O type to φ type).

Water Repellent B (Example 2) Water Repellent B was prepared by mixing Water Repellent A with the following polymer emulsion at a ratio of 3:1.

(Polymer emulsion) Butyl acrylate 50 parts Ethyl acrylate 28 parts Methyl acrylate 22 Subsaturated sodium sulfonate 1 part Ammonium persulfate
0.8 Viscosity (cp x 25℃) 40 pH 3.8 (Add water and ammonia water to the above primer emulsion to adjust the pH.
A polymer emulsion (adjusted to 40% solid content) was prepared as follows.

Pour a specified amount of water into a 500 cc four-piece Rokol pen, fix it in a hot water bath, and equip it with a stirrer, a reflux condenser, and a thermometer.
The whole was made airtight, and nitrogen gas was fed until the reaction was completed, but it was discharged through a cooling pipe. Set the water bath temperature to 40
The temperature was kept at about ℃, and a separate separating funnel was attached to the mouth of the funnel with a plug, being careful to keep it airtight. Next, 50 parts of butyl acrylate, 28 parts of ethyl acrylate, and 22 parts of methyl methacrylate were thoroughly mixed and placed in the separatory funnel. Separately, 70.8 parts of ammonium persulfate and 1 part of unsaturated sodium sulfonate were added to water in a Locolpen and mixed uniformly. Keep the external temperature at 60 to 65°C, drop the polymer (acrylic acid butyl ester, etc.) from the separating funnel, and add 65R
Polymerization of PM was carried out while stirring. In this case, since the internal temperature was an exothermic reaction, water was added to the external temperature so as not to exceed 75° C., and the reaction was carried out while cooling so as not to interfere with the reaction, and the polymerization reaction was completed after about 6 hours. It was confirmed that there was no monomer dripping from the reflux condenser while stirring for 30 minutes while keeping the internal temperature at 80° C. or higher and around 85° C. If there was no dripping, this indicates that the reaction was completed. A stable emulsion with fine particles was obtained. In both cases, the yield was close to 100%.

・Water repellent C (Comparative Example 1) / Mother fin wax with melting point of 60°C 30 parts Polyethylene oxide stearyl 8.5 parts Ether () ILB: 13) Caustic potash 0.04
Department water 61.
5 parts Wax solid content 30
%pH7,8 Viscosity (25℃) (100ep
Water Repellent D (Comparative Example 2) As a reaction catalyst, 25% by weight of Catalyday RB (product of C1ha-Geigy) was added to Hopotex FTC (product of C1ha-Geigy, amino resin derivative water repellent) based on all Tex FTC products. They were mixed and used in the following proportions.

The base fabric was immersed in each water repellent treatment solution at the above concentration, and then dried with a mangle at a fi of 120° C. to make the base fabric water repellent. The adhesion amount (solid content) of each water repellent agent was adjusted to be 3% based on the weight of the base fabric. 3105 and 15
Coronet) L (all manufactured by Nippon Polyurethane Industries Co., Ltd./urethane adhesive) was diluted with ethyl acetate to make a 50% solution, which was applied in an amount of 30117 m2 and dried. Next, a PVC film (0,
1■) was attached by heating.

PVC 100 parts DOP (plasticizer) 75 parts Titanium dioxide 8 parts Antimony trioxide (
Flame retardant) 5 parts zinc stearate (stabilizer)
Three copies of these waterproof fiber sheet materials were measured for peel strength and water absorption of the coating.

Measurement method Peeling strength crab JIS-6328-19775, 3,
Compliant with 7 peel test.

Take a sample with a length of 20 mm and a width of 3 mm from a water-absorbent double-sided coated cloth, fix the upper part in the length direction, and place a 0.5 cm point on the lower end in an immersion container with commercially available red ink diluted to 5 mm. Soak it in the dipping liquid in the water for 24 hours at room temperature, take it out, wipe the dipping liquid attached to the bottom with a piece of filter paper, and measure the height at which the red ink has risen (the higher the height, the more water it absorbs). gender).

The results are shown in Table 1. The water pressure resistance was 2000 square meters or more in all cases.

The practical guideline for water absorption in Table 1 is that it should be at least 10 ml, preferably 5 m+ or less, preferably 0. In general, a practical guideline for peel strength is 6 kg/3 cm or more, preferably 8 to 9 kg/3 cm or more. As can be seen from Table 1, the peel strengths of the products of Comparative Examples 1 and 2 are close to the lower limit of practical products, and are not always practically satisfactory.

The products of Examples 1 and 2 exhibited excellent peeling strength and water repellency, and therefore the method of the present invention could be applied under stable processing conditions.
It is possible to stably supply products with excellent performance.

Example 3 Polyester spun yarn fabric: heavy fil 19011/m2 thickness 0.3 pieces was scoured, dried and treated with a water repellent according to the procedure described in Example 1. This water-repellent fabric was subjected to waterproofing under the following conditions.

PVC 100 parts DOP 60 parts CaCO, 20 parts Cd-Ba stabilizer 3 parts Toluene 100 parts Nippon 2-3105 10 parts Coronate L 2 parts Soak the fabric in the solution with the above composition, squeeze it with a mangle, 19 parts
The PvC resin was dulled and fixed by heat treatment at 0° C. for 3 minutes. The amount of the waterproof polymer coating layer thus applied was 20,017 m2 in terms of solid content. The water pressure resistance of the obtained waterproof sheets was all 2000 or more water columns. Furthermore, the adhesion (peel strength) of the waterproof polymer coating layer to the base fabric was extremely strong.

Example 4 Truck hoods were prepared using each of the sheet materials of Examples 1 to 3 and Comparative Examples 1 to 2 described above, and subjected to a practical test.

In the case of the truck hoods made from the sheets of Examples 1 to 3, they could be used continuously for four years without any abnormality. However, after about one year of practical testing, the coating of the truck hood made from the sheet of Comparative Example L2 deteriorated due to abrasion or peeling, resulting in decreased water resistance, and after two years, it was no longer practical.

Example 5 Glass fiber base fabric: Area weight: 29017m2 The same operation as in Example 1 was performed using the gray fabric.

Almost the same results as in Example 1 were obtained.

〔Effect of the invention〕

In the waterproof fiber sheet material obtained by the method of the present invention, water does not penetrate or absorb into the fibrous base fabric at all, and the adhesion of the coating is much better than expected, so it has excellent waterproof performance. It also has excellent waterproof performance and durability. Further, in the method of the present invention, it is possible to stably produce waterproof fiber sheet materials, and the performance of the product is also stable. Therefore, the present invention provides a method for manufacturing a waterproof fiber sheet material that is industrially extremely advantageous.

Claims (1)

[Claims] 1. Aqueous water repellent containing an addition reaction product of a wax and an unsaturated carboxylic acid or its anhydride, a paraffinic hydrocarbon, and a water-soluble alkaline substance for emulsifying them. A waterproof fiber in which a fibrous base fabric is impregnated with an emulsion, and the impregnated aqueous water repellent emulsion is dried and solidified, and then a polymer film is formed on both surfaces of the fibrous base fabric. Method of manufacturing sheet materials. 2. The fibrous base fabric is natural fiber, inorganic fiber, recycled fiber,
The method according to claim 1, which comprises at least one kind selected from semi-synthetic fibers and synthetic fibers. 3. The method according to claim 1, wherein the wax comprises at least one member selected from low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight ethylene-propylene copolymer, and petroleum distillate wax. 4. The unsaturated carboxylic acid is maleic acid, fumaric acid,
and itaconic acid. 5. Claim 1, wherein the addition reaction product has an acid value of 15-120 and a melting point of 40°C-140°C.
The method described in section. 6. The method according to claim 1, wherein the paraffinic hydrocarbon has a melting point of 40°C to 85°C. 7. The weight ratio of the addition reaction product and the paraffinic hydrocarbon in the water-repellent aqueous emulsion is 3:9.
7. The method of claim 1, wherein the ratio is within the range of 7 to 60:40. 8. The method according to claim 1, wherein the water-soluble alkaline substance is selected from alkali metal hydroxides, alkali metal carbonates, ammonia, and water-soluble amine compounds. 9. The method according to claim 1, wherein the water repellent aqueous emulsion adhesion treatment is performed by an impregnation method, a coating method, or a spraying method. 10. The method according to claim 1, wherein the waterproof polymer is selected from hydrophobic synthetic resins, synthetic rubbers, and natural rubbers. 11. Claims in which the hydrophobic synthetic resin is selected from polyvinyl chloride, polyurethane, ethylene-vinyl acetate copolymer, isotactic polypropylene, polyethylene, polyacrylonitrile, polyester, polyamide, fluororesin, and silicone resin. The method according to item 10. 12. The method according to claim 10, wherein the synthetic rubber is selected from styrene-butadiene rubber, chlorosulfonated polyethylene rubber, polyurethane rubber, butyl rubber, isopropylene rubber, silicone rubber, and fluorine rubber. 13. The method according to claim 1, wherein the waterproof polymer coating is formed by a calendering method, an extrusion method, a coating method, or a dipping method. 14. The method according to claim 1, wherein the amount of the water repellent aqueous emulsion attached to the fibrous base fabric is 1.0 to 5.0% OWF (solid content). 15. A water repellent aqueous emulsion containing an addition reaction product of wax and an unsaturated carboxylic acid or its anhydride, a paraffinic hydrocarbon, and a water-soluble alkaline substance for emulsifying these, and at least A fibrous base fabric is impregnated with a mixture of one type of film-forming polymer and an aqueous emulsion, and after this impregnated mixture is dried and solidified, a waterproof coating is applied on both surfaces of the fibrous base fabric. A method for producing a waterproof fiber sheet material, which forms a waterproof polymer film. 16. The method according to claim 15, wherein the fibrous base fabric is made of at least one selected from natural fibers, inorganic fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers. 17. The method according to claim 15, wherein the wax comprises at least one member selected from low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight ethylene-propylene copolymer, and petroleum distillate wax. 18. The method of claim 15, wherein the unsaturated carboxylic acid is selected from maleic acid, fumaric acid, and itaconic acid. 19. The method of claim 15, wherein the addition reaction product has an acid number of 15 to 120 and a melting point of 40C to 140C. 20. The method according to claim 15, wherein the paraffinic hydrocarbon has a melting point of 40°C to 85°C. 21. The weight ratio of the addition reaction product and the paraffinic hydrocarbon in the water-repellent aqueous emulsion is 3:
Claim 1 falling within the range of 97 to 60:40
The method described in Section 5. 22. The method according to claim 15, wherein the water-soluble alkaline substance is selected from alkali metal hydroxides, alkali metal carbonates, ammonia, and water-soluble amine compounds. 23, the film-forming polymer is polyacrylic ester, polymethacrylic ester, polyvinyl ether, polyacrylonitrile, polystyrene, polyacrylic acid,
Claim 15 selected from polymethacrylic acid
The method described in section. 24. The method according to claim 15, wherein the mixing weight ratio of the water repellent aqueous emulsion and the film-forming polymer aqueous emulsion is within the range of 95:5 to 75:25. 25. The method according to claim 14, wherein the liquid mixture adhesion treatment is performed by an impregnation method, a coating method, or a spraying method. 26. The method according to claim 14, wherein the waterproof polymer is selected from hydrophobic synthetic resins, synthetic rubbers, and natural rubbers. 27. Claims in which the hydrophobic synthetic resin is selected from polyvinyl chloride, polyurethane, ethylene-vinyl acetate copolymer, isotactic polypropylene, polyethylene, polyacrylonitrile, polyester, polyamide, fluororesin, and silicone resin. The method according to paragraph 26. 28. The method according to claim 26, wherein the synthetic rubber is selected from styrene-butadiene rubber, chlorosulfonated polyethylene rubber, polyurethane rubber, butyl rubber, isopropylene rubber, silicone rubber, and fluorine rubber. 29. The method according to claim 15, wherein the waterproof polymer coating is formed by a calendering method, an extrusion method, a coating method, or a dipping method. 30. The amount of the mixed liquid attached to the fibrous base fabric is 1.
16. The method according to claim 15, wherein the solid content is within the range of 0 to 5.0% owf (solid content).