JPH0457788B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for manufacturing a waterproof fiber sheet material. More specifically, it relates to a method for producing 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. be. [Prior Art] Conventionally, waterproof fiber 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 cross-section of the sheet material. If the fibers in the base fabric are dense, this water absorption is further increased by capillary action. and,
Water absorption not only increases the weight of the waterproof fibrous sheet material, but also reduces the adhesion between the fibrous base fabric and the coating. Further, the absorbed water is difficult to be released from the fibrous base fabric, and furthermore, there is a drawback that, for example, it causes the growth of mold, and it also absorbs sewage or water with a different color, which impairs 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 is treated with a type of water repellent. It acts as a mold release agent, and therefore the adhesion between the film and the fibrous base fabric deteriorates, making it undesirable for practical use. Efforts have also been made to improve adhesion by adding adhesive substances such as isocyanates to water repellents and film-forming agents, but no satisfactory results have been achieved. This is the current situation. [Problems to be Solved by the Invention] The present invention solves the problems of conventional waterproof fiber sheet materials, namely, the fibrous base fabric absorbs water, and the adhesion between the fibrous base fabric and the waterproof polymer coating layer. The object of the present invention is to provide a method for producing a waterproof fiber sheet material that can solve the problem of low strength and gradual decline. [Means for solving the problems and their effects] The method for producing a waterproof fiber sheet material of the present invention includes wax, an addition reaction product of an unsaturated carboxylic acid or its anhydride, 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 The cloth is characterized by having a waterproof polymer coating formed on both surfaces thereof. Another method for producing a waterproof fiber sheet material of the present invention is to use an addition reaction product of wax, an unsaturated carboxylic acid or its anhydride, a paraffinic hydrocarbon, and a water-soluble alkaline substance for emulsifying these. After impregnating a fibrous base fabric with a mixture of an aqueous emulsion of a water repellent agent containing the above and an aqueous emulsion of at least one film-forming polymer, and drying and solidifying the impregnated mixture, , on both surfaces of this fibrous base fabric,
It is characterized by forming a waterproof polymer film. Fibrous base fabrics useful in the present invention include natural fibers such as cotton, linen, etc., inorganic fibers such as glass fibers, carbon fibers, asbestos fibers, metal fibers, etc.
Regenerated fibers, e.g. viscose rayon, cupra, etc., semi-synthetic fibers, e.g.
Acetate fibers, synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, polyolefin fibers, and water-insoluble or poorly soluble polyvinyl alcohol It is made of at least one type selected from fibers, etc. The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, split yarn, or tape yarn, and the base fabric may be a woven fabric, a knitted fabric, a nonwoven fabric, or a composite fabric thereof. Good too. 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 wax, an unsaturated carboxylic acid or an anhydride thereof, a paraffinic hydrocarbon, and a water-soluble alkaline substance for emulsifying these are added to a fibrous base fabric. Impregnation and drying solidification treatment is carried out with an aqueous emulsion of a water repellent, or a mixture of the aqueous emulsion of a water repellent and an aqueous emulsion of at least one film-forming polymer. That is, waxes used in the water repellent aqueous emulsion include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and low molecular weight ethylene-propylene copolymers, or mixed waxes of these polyolefin waxes and petroleum distillate waxes. used. The unsaturated carboxylic acid can also be selected from 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 35 to 90, and a melting point of 40°C to
The temperature is preferably 140°C, more preferably 40 to 80°C. If the acid value is less than 15, emulsifying properties 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 paraffinic hydrocarbon used in the method of the present invention preferably has a melting point of 40°C to 100°C, and more preferably 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. Water-soluble alkaline substances are effective in emulsifying addition reaction products and paraffinic hydrocarbons in water. The wax addition reaction product and the paraffinic hydrocarbon are mixed in a weight ratio of preferably 3:97 to 60:40, more preferably 3:97 to 35:67. Generally, the alkaline substance is preferably used in a blending ratio of 0.1 to 5.0% based on the total weight of the wax addition reaction product and the paraffinic hydrocarbon. An appropriate amount of natural rosin, rosin ester, plastic wax, high acid value or ordinary montan wax, etc. is added to the water repellent aqueous emulsion to improve the film formation and adhesion of the water repellent. It's okay. In the present invention, no surfactant is required in the water repellent aqueous emulsion, but depending on the application, such as the mechanical stability of the emulsion during ultra-high-speed stirring and further ultrafine particle size, unsaturated Addition of a surfactant in an amount of up to 6% by weight, and even up to 3.5%, based on the total amount of the addition reaction wax product of a polyhydric carboxylic acid or its anhydride and the paraffinic hydrocarbon, is permissible depending on the application. Even so, surfactants are normally added to paraffinic hydrocarbons in an amount of 20 to 30% by weight, sometimes even more, so if it is less than 3.5% by weight, it is extremely small, and this addition can cause problems. There are almost no such things. Possible nonionic surfactants include polyolefin oxide alkyl ethers, esters thereof, and sorbitan esters, and examples of anionic surfactants include higher fatty acids and other alkali salts (including amino salts and ammonium salts). etc., and these need to be combined as appropriate according to requirements. However, the amount added must be kept within the above-mentioned limits, and it is preferable to avoid using it as much as possible. In order to produce the water repellent aqueous emulsion of the present invention, it is best to carry out the emulsification while applying strong stirring or shearing strength using an autoclave (pressure vessel), pressurized homomixer, etc. However, 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 flexibility 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 system, etc. of the waterproof polymer so as to exhibit the above performance. Examples of waterproof polymers include polymers and copolymers of acrylic esters, methacrylic esters, vinyl ethers, acrylonitrile, styrene, acrylic acid, methacrylic acid, etc. Examples of acrylic esters include methyl, Examples of methacrylic acid include ethyl and butyl esters, 2-ethylhexyl acrylate, etc., and methacrylic acid-based esters include methyl, ethyl, and butyl esters, 2-ethylhexyl methacrylate, etc.; It's okay. This polymer emulsion needs to have good compatibility with the water-repellent emulsion, and for this reason, the HLBs of both need 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, if the polymer emulsion has good compatibility, or if a protective colloid thickener is added, natural or synthetic rubber latex, urethane emulsion, polyester,
It is also possible to use an epoxy resin emulsion. Synthetic rubber latexes include SBR (styrene-butadiene rubber) and MBR (methyl methacrylate).
butadiene rubber), etc., and these greatly contribute to flexibility. When preparing emulsions of acrylic esters, methacrylic esters, acrylic acid, methacrylic acid, acrylonitrile, styrene, etc. alone or as a copolymer, use a suitable surfactant as described above, and use a surfactant as a catalyst. Redox polymerization can also be carried out at low temperatures by emulsifying at high temperatures in water using peroxides such as sulfates and hydrogen peroxide, 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 95/5 to 75/25.
To be more precise, a ratio of 80/20 to 75/25 is most effective for water resistance and water absorption control of treated substances. Since this water repellent emulsion uses an addition reaction wax of unsaturated polyhydric carboxylic acid or its anhydride, the carboxyl group (-COOH) contained therein is similar to oxidized paraffin obtained by simply oxidizing paraffin. Since the carboxyl group is not directly connected to the main chain, and the functionality is stronger, the reactivity is higher and the adhesion to the corresponding treatment body is further strengthened. Moreover, the surfactant content is either zero or reduced, so it does not interfere with the effect, and furthermore, due to the presence and reduction of these strong carboxyl groups or the absence of surfactants, it has an excellent water repellent effect. There is. 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 solidifies immediately,
The emulsion will be destroyed. This fact is very important in practical applications. That is, this is a problem of cold resistance. In general, wax emulsions start to lose their emulsion stability when the temperature drops below 5℃, and at 0℃, they almost freeze and coagulate.
At -5°C, everything coagulates and breaks down, and once it has solidified and breaks down, no matter if you heat it or stir it vigorously, it will not become an emulsion again and will become waste.
For this reason, it is unavoidable to add ethylene glycol, polyethylene glycol, glycerin, etc. as cold-resistant agents, but this seriously impairs the repellency and water resistance, which are the characteristics of wax emulsions. This creates a vicious cycle in which water resistance deteriorates. Therefore, all conventional wax emulsions are not suitable for 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 to 80% of the volume of alcohol can be added to the water repellent emulsion.
Alcohols do not cause any deterioration in repellency or water resistance, and are excellent in cold resistance, and it has been a long-held desire to be able to use alcohols in water repellent emulsions. The water repellent emulsion successfully solved this problem. For example, for the total volume of this water repellent emulsion, add 5% isopropyl alcohol.
%, and those containing 3% methyl alcohol are repellent.
It is actually stable even at -20℃ without impeding its water resistance in the slightest. In addition, due to the carboxyl 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 salt, sodium aluminate, etc., which are water-soluble on the alkaline side, 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 the effects of water resistance and water absorption inhibitor, excellent adhesion, and repellency and water resistance due to their compositional characteristics. 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 within the range of 60 to 140°C, and even more preferably within the range of 80 to 120°C. The amount of water repellent aqueous emulsion applied to the fibrous base fabric is preferably 1.0 to 5.0% owf (solid content), but the amount can be adjusted as appropriate depending on the water repellent effect. The base fabric thus treated is then subjected to a step of forming a waterproof polymer coating on both surfaces thereof. Waterproof polymers include hydrophobic synthetic resins,
There are synthetic rubbers and natural rubbers, and preferred synthetic resins include, for example, polyvinyl chloride (PVC),
polyurethane, ethylene-vinyl acetate copolymer,
Examples include isotactic polypropylene, polyethylene, polyacrylonitrile, polyester, polyamide, fluororesin, silicone resin, and other known materials. Examples of preferable synthetic rubbers include styrene-butadiene rubber (SBR), chlorosulfonated polyethylene rubber,
Examples include polyurethane rubber, butyl rubber, isoprene rubber, silicone rubber, fluorine rubber, and other known materials. In particular, polyvinyl chloride, fluorine-based and silicone-based rubbers and resins, and acrylic resins are preferred polymers for the present 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 adhesives include melamine adhesives, phenolic adhesives, epoxy adhesives, polyester adhesives, polyethyleneimine adhesives, polyisocyanate adhesives, polyurethane adhesives, and acrylic adhesives. adhesives, polyamide adhesives, and vinyl acetate-vinyl chloride adhesives, vinyl acetate adhesives, and vinyl chloride adhesives.
Examples include, but are not limited to, copolymer adhesives such as ethylene adhesives,
Any known adhesive can be selected and 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 conventional methods such as
This can be carried out by a calendering method, an extrusion method, a coating method, a dipping method, or the like. The waterproof fiber sheet material obtained by the method of the present invention not only exhibits substantially no water absorption;
It shows a completely unexpectedly high peel strength. That is, when conventional water repellents were used, the peel strength between the waterproof polymer coating layer and the fibrous base fabric was at most about 6 to 10 kg/3 cm, but the sheet material obtained by the method of the present invention So, 14~20Kg/3cm
A completely unexpected high peel strength was obtained. In addition, when the treatment of the present invention is applied to a base fabric made of inorganic fibers, especially a base fabric made of glass fibers, in addition to the above-mentioned effects, the drawbacks of the glass fiber base fabric, namely, that it easily breaks during repeated bending and is not strong. This can cover the drawback of low bending resistance, which is a decrease in flex resistance. Therefore, the waterproof sheet of the present invention has the advantage that it can be used for a long period of time in applications that involve repeated folding, folding, and vibration. [Example] Hereinafter, the present invention will be further explained with reference to Examples. Examples 1-2 and Comparative Examples 1-2 Polyester fiber base fabric: 1000d x 1000d/32 pieces/inch x 32 pieces/inch plain weave 300g/ ^m2 thickness 0.35mm was scoured and dried, and the following water repellent water-based Impregnated with emulsion. Water repellent A (Example 1) Paraffin wax, melting point 60°C 22 parts Wax-carboxylic acid addition reaction product with acid value 70 and melting point 72°C 8 parts Aqueous ammonia 0.3 parts Water 70 parts Wax solid content 30% PH 8.3 Viscosity (25°C) <100 cp The above addition reaction product was an addition reaction product of a mixture of a low molecular weight polyolefin wax and a petroleum distillate wax, and maleic anhydride. The above paraffin wax and the addition reaction product are melt-mixed at 110°C, ammonia water is added thereto, then cooled to 100°C, and boiling water is gradually added to increase the viscosity and lower the temperature. The emulsion was inverted (W/
(from O type to O/W type), a stable O/W type emulsion was obtained. 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) Acrylic acid butyl ester 50 parts Acrylic acid ethyl ester 28 parts Methacrylic acid methyl ester 22 parts Unsaturated sodium sulfonate 1 part Ammonium persulfate 0.8 Water 136 Solid content (%) 42.5 Viscosity (cp) (25 ℃) 40 PH 3.8 (Water and aqueous ammonia were added to the above polymer emulsion to adjust the pH to 7.4 and solid content to 40%.) The polymer emulsion was prepared as follows. Pour the specified amount of water into a 500c.c. four-necked kolben,
The reactor was fixed in a hot water bath, equipped with a stirrer, a reflux condenser, and a thermometer, and the entire reactor was airtight. Nitrogen gas was fed until the reaction was completed, but this gas was discharged through a cooling tube. The water bath temperature was set to around 40°C, and a separate separating funnel was attached to the remaining opening with a rubber stopper, taking care to keep it airtight. Next, 50 parts of butyl acrylate, 28 parts of ethyl acrylate, and methyl methacrylate.
22 parts of the mixture was mixed well and placed in the separatory funnel. Separately, 0.8 part of ammonium persulfate and 1 part of unsaturated sodium sulfonate were added to water in a four-necked Kolben and mixed uniformly. The external temperature was kept at 60 to 65°C, and a polymer (acrylic acid butyl ester, etc.) was added dropwise from a separating funnel, and polymerization was performed while stirring at 65 RPM. In this case, since the internal temperature was an exothermic reaction, water was added to the external bath to prevent the reaction from exceeding 75° C., and the reaction was carried out while cooling to prevent the reaction, and the polymerization reaction was completed after about 6 hours. Confirm that there is no monomer dripping from the reflux condenser while stirring for 30 minutes at an internal temperature of 80°C or higher and around 85°C. If there is no dripping, this indicates that the reaction is complete. A stable emulsion with fine particles was obtained. In both cases, the yield was close to 100%. Water repellent C (Comparative Example 1) Paraffin wax with melting point of 60℃ 30 parts Polyethylene oxide stearyl 8.5 parts Ether (HLB: 13) Caustic potash 0.04 parts Water 61.5 parts Wax solid content 30% PH 7.8 Viscosity (25℃) <100cp Repellent Water agent D (Comparative Example 2) Catalyzer RB (product of Ciba-Geigy) was added as a reaction catalyst to Hobotex FTC (product of Ciba-Geigy, amino resin derivative water repellent) at a ratio of 25% by weight to Hobotex FTC. It was mixed and used. The base fabric was immersed in each water repellent treatment solution at the above concentration, squeezed with a mangle and dried at 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. For each of the fibrous base fabrics thus obtained, 100 parts of Nitsuporan 3105 were applied on both sides.
and 15 parts of Coronate L (both products of Nippon Polyurethane Industries Co., Ltd.: polyurethane adhesive) were diluted with ethyl acetate to make a 50% solution, and this was 30 g/m ²
The amount was applied and dried. Next, the following composition
A PVC film (0.1 mm) was attached by heating. PVC 100 parts DOP (plasticizer) 75 parts titanium dioxide 8 parts antimony trioxide (flame retardant) 5 parts zinc stearate (stabilizer) 3 parts Regarding these waterproof fiber sheet materials obtained, the peeling strength of the coating and Water absorption was measured. Measurement method Peeling strength: Compliant with JIS-K-6328-1977 5, 3, 7 peel test. Water absorption: Take a 20cm long and 3cm wide sample from the double-sided coated fabric, fix the upper part in the length direction, and lower the lower end by about 0.5 cm.
Immerse the cm point in an immersion solution containing commercially available red ink diluted to 5% in an immersion container, soak it at room temperature for 24 hours, then take it out, gently wipe the immersion solution adhering to the bottom edge with a filter paper, and remove the red ink. (The higher the height, the greater the water absorption.) The results are shown in Table 1. Water pressure resistance is 2000mm for both
It was above the water column.

[Table] The practical guideline for water absorption is that it should be at least 10 mm, preferably 5 mm or less, and preferably 0 mm.
It is. In general, the 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 exhibit extremely excellent peeling strength and water repellency, and therefore, the method of the present invention can stably supply products with excellent performance under stable processing conditions. Example 3 Polyester spun yarn fabric: 14S/1 x 14S/1/53 threads/inch x 50 threads/inch Plain weave weight 190 g/m ² thickness 0.3 mm was scoured, dried and water repellent by the procedure described in Example 1. Treated with agent. This water-repellent fabric was subjected to waterproofing under the following conditions. PVC 100 parts DOP 60 parts CaCO ₃ 20 parts Cd-Ba stabilizer 3 parts Toluene 100 parts Nituporan 3105 10 parts Coronate L 2 parts The fabric was soaked in the solution with the above composition, squeezed with a mangle, and heat-treated at 190℃ for 3 minutes. Then, the PVC resin was gelled and fixed. The amount of the waterproof polymer coating layer thus applied was 200 g/m ² in terms of solid content. The water pressure resistance of the obtained tarpaulins is
The water column was over 2000mm. Furthermore, the adhesion (peel strength) of the waterproof polymer coating layer to the base fabric was extremely strong. Example 4 Truck tops were prepared using each of the sheet materials of Examples 1 to 3 and Comparative Examples 1 to 2 described above, and were subjected to an example test. The truck tops made from the sheets of Examples 1 to 3 could be used continuously for four years without any abnormalities. However, comparative examples 1 and 2
Truck hoods made from sheets of
After 2 years, the coating wore out or peeled off, resulting in decreased water resistance, and after 2 years, it was no longer practical. Examples 5 to 6 and Comparative Examples 3 to 5 Glass fiber base fabric: DE150 1/2 3.3S/55 pieces/inch x 51 pieces/inch Turkish satin weave 290 g/m ² gray fabric was used. Examples 5-6 and Comparative Example 3-
In Example 4, the same operation as in Example 1 was performed.
However, the water repellent listed in Table 2 was used.
When the peel strength and water absorption strength of the obtained product were measured, almost the same results as in Table 1 were obtained. In Comparative Example 5, a resin-coated product was produced in the same manner as in Example 1 using a glass fiber base fabric without further pretreatment. JIS-P for each product
-8115 (1976), "Test method for folding strength of paper and paperboard using MIT type tester", and the results shown in Table 2 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. Furthermore, 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)

[Scope of Claims] 1. Water repellent aqueous emulsion comprising an addition reaction product of wax, an unsaturated carboxylic acid or its anhydride, a paraffinic hydrocarbon, and a water-soluble alkaline substance for emulsifying these. After impregnating the fibrous base fabric with the liquid and drying and solidifying the impregnated water repellent aqueous emulsion, the liquid is applied to both surfaces of the fibrous base fabric.
A method for producing a waterproof fiber sheet material forming a polymer film. 2. The method according to claim 1, 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. 3. 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 polymer, and petroleum distillate wax.
The method described in section. 4. The method of claim 1, wherein the unsaturated carboxylic acid is selected from maleic acid, fumaric acid, and itaconic acid. 5. The method of claim 1, wherein the addition reaction product has an acid number of 15 to 120 and a melting point of 40C to 140C. 6. The method according to claim 1, wherein the paraffinic hydrocarbon has a melting point of 40°C to 85°C. 7. The method according to claim 1, wherein the weight ratio of the addition reaction product to the paraffinic hydrocarbon in the water-repellent aqueous emulsion is in the range of 3:97 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 water repellent aqueous emulsion adhesion treatment is an impregnation method,
The method according to claim 1, which is carried out by a coating method or a spraying method. 10. The method of claim 1, wherein the waterproof polymer is selected from hydrophobic synthetic resins, synthetic rubbers, and natural rubbers. 11 The hydrophobic synthetic resin is polyvinyl chloride, polyurethane, ethylene-vinyl acetate copolymer, isotactic polypropylene, polyethylene,
11. The method according to claim 10, wherein the method is selected from polyacrylonitrile, polyester, polyamide, fluororesin, and silicone resin. 12 The synthetic rubber is styrene-butadiene rubber, chlorosulfonated polyethylene rubber, polyurethane rubber, butyl rubber, isopropylene rubber,
The method according to claim 10, wherein the method is selected from silicone rubber and fluorine rubber. 13 The waterproof polymer coating is prepared by a calendar method,
The method according to claim 1, which is formed by an extrusion method, a coating method, or a dipping method. 14. The amount of the water repellent aqueous emulsion attached to the fibrous base fabric is 1.0 to 5.0% owf (solid content).
A method according to claim 1. 15. A water repellent aqueous emulsion containing an addition reaction product of wax, an unsaturated carboxylic acid or its anhydride, a paraffinic hydrocarbon, and a water-soluble alkaline substance for emulsifying these, and at least one A fibrous base fabric is impregnated with a mixture of a seed 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 forming a 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 wax is made of low molecular weight polyethylene,
16. The method of claim 15, comprising at least one member selected from 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 Claim 15, wherein the paraffinic hydrocarbon has a melting point of 40°C to 85°C.
The method described in section. 21. The method according to claim 15, wherein the weight ratio of the addition reaction product to the paraffinic hydrocarbon in the water-repellent aqueous emulsion is in the range of 3:97 to 60:40. . 22 The water-soluble alkaline substance is an alkali metal hydroxide, an alkali metal carbonate, ammonia,
16. The method according to claim 15, wherein the method is selected from water-soluble amine compounds. 23. The method according to claim 15, wherein the film-forming polymer is selected from polyacrylic ester, polymethacrylic ester, polyvinyl ether, polyacrylonitrile, polystyrene, polyacrylic acid, and polymethacrylic acid. 24 The mixing weight ratio of the water repellent aqueous emulsion and the film-forming polymer aqueous emulsion is 95:5 to 75:2.
16. The method of claim 15 within the scope of Claim 5. 25. The method according to claim 15, wherein the liquid mixture adhesion treatment is performed by an impregnation method, a coating method, or a spraying method. 26. The method of claim 15, wherein the waterproof polymer is selected from hydrophobic synthetic resins, synthetic rubbers, and natural rubbers. 27 The hydrophobic synthetic resin is polyvinyl chloride, polyurethane, ethylene-vinyl acetate copolymer, isotactic polypropylene, polyethylene,
27. The method of claim 26, wherein the method is selected from polyacrylonitrile, polyester, polyamide, fluororesin, and silicone resin. 28 The synthetic rubber is styrene-butadiene rubber, chlorosulfonated polyethylene rubber, polyurethane rubber, butyl rubber, isopropylene rubber,
27. The method according to claim 26, wherein the method is selected from silicone rubber and fluorine rubber. 29 The waterproof polymer coating is prepared by a calendar method,
16. The method according to claim 15, which is formed by an extrusion method, a coating method, or a dipping method. 30. The method according to claim 15, wherein the amount of the mixed liquid attached to the fibrous base fabric is within the range of 1.0 to 5.0% owf (solid content).