JPH055948B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a moisture-permeable waterproof fabric with excellent adhesive strength between a coating resin layer and a fiber layer. In general, moisture permeability and waterproofness are contradictory functions, but waterproof fabrics with excellent moisture permeability form continuous fine pores that allow water vapor to escape in the coating resin film during dry or wet coating processing. It is obtained by letting In these dry or wet coating processes, polyurethane elastomers are generally preferably used as coating resins in terms of film strength, rubber elasticity, and flexibility. However, in the case of breathable waterproof fabric made from polyurethane elastomer, it is made based on a balance between waterproof performance and moisture permeability, so its waterproof performance exceeds 1500 mm (under the water column) according to JIS L-1096 water pressure measurements. The fabric has a moisture permeability of 4000 to 5000g/ ^m2・24hrs (JIS Z
-0208 measurement) is currently only available. This moisture permeability level is 7000g/ ^m2 .
If it can be improved to 24hrs or more, it will have almost the same moisture permeability as a non-coated fabric, which is simply a water-repellent and calendared high-density fabric using ultra-fine filaments for warp and warp yarns. , the humidity inside the clothes due to sweating when working in the rain or exercising can be smoothly controlled, making it possible to perform even more strenuous exercise or work comfortably, but only if the water pressure resistance is 1500 mm or more. The reality is that to date, a fabric with a moisture permeability of 7,000 g/m ² ·24 hours or more has not yet been obtained. Additionally, the coated fabric is made up of a base fabric and a resin layer, but especially when the base fabric is made of polyester synthetic resin, the base fabric and the resin layer are likely to separate due to "abrasion" during wearing or washing. It had drawbacks. The present invention was made in view of the current situation, and the water pressure resistance is
Although it is over 1500mm, the moisture permeability is 7000g/ ^m2 .
The purpose of this invention is to obtain a fabric that has high moisture permeability of 24 hours or more and also has good adhesiveness between the base fabric and the resin layer. In order to achieve this object, the present invention has the following configuration. That is, in the present invention, a resin solution mainly composed of a polyester resin, a polyamino acid urethane resin, and a polar organic solvent is applied to a fiber fabric mainly composed of polyester synthetic fibers, and then immersed in water, washed with hot water, and dried. The coated surface is coated with at least one of a polyurethane resin, a nonionic surfactant, an anionic surfactant, a hydrophilic polymer, an isocyanate compound, and an inorganic filler, a polyamino acid urethane resin, and a polar organic solvent. A method for producing a moisture permeability-preventing water fabric, which is characterized by applying a resin solution, followed by immersion in water, washing with hot water, and drying, and applying a water repellent as a final step following the above configuration. The gist of this paper is a method for manufacturing a moisture-permeable waterproof fabric. The present invention will be explained in detail below. The fiber fabric mainly composed of polyester synthetic fibers used in the present invention refers to fibers made of polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene terephthalate isophthalate, polyethylene terephthalate adipate, and copolymers thereof. textiles mainly based on
It refers to knitted fabrics, nonwoven fabrics, etc., and also includes fabrics obtained by blending or interweaving the above polyester-based synthetic resin with other natural fibers or synthetic fibers. Furthermore, these fiber fabrics include those subjected to various treatments such as crushing treatment and water repellent treatment. In the method of the present invention, the first step is to apply a resin solution mainly composed of a polyester resin, a polyamino acid urethane resin, and a polar organic solvent to a fiber fabric such as a knitted fabric, and then immerse it in water and wash it with hot water. ,dry. The polyester resins used here include ethylene glycol, diethylene glycol, propylene glycol, 1.4-butanediol, 1.
Polymerization reaction products of diols such as 6-hexanediol and polytetramethylene glycol with aromatic dicarboxylic acids and aliphatic dicarboxylic acids such as isophthalic acid, terephthanic acid, adipic acid, and sebacic acid, ring-opening polymers such as lactones, etc. The diol component and the acid component are prepared so that the polymer is washed amorphous and dissolved in a polar organic solvent. For example, polyester having a molecular weight of 20,000 to 30,000 is preferably used, which is obtained by polymerizing terephthalic acid and sebacic acid as acid components and ethylene glycol and neopentyl glycol as diol components. The polyamino acid urethane resin (hereinafter referred to as PAU resin) used in the present invention is a copolymer consisting of amino acids and polyurethane, and as an amino acid,
Examples include DL-alanine, L-aspartic acid, L-cystine, L-glutamic acid, glycine, L-lysine, L-methionine, L-leucine and their derivatives, and when synthesizing polyamino acids, amino acids obtained from amino acids and phosgene. N-carboxylic anhydride (hereinafter referred to as N-carboxylic anhydride)
It's called NCA. ) is commonly used. Polyurethane uses aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates singly or in mixtures thereof as isocyanate components, such as tolylene 2,4-diisocyanate,
4,4'-diphenylmethane diisocyanate,
Examples include 1,6-hexane diisocyanate and 1,4-cyclohexane diisocyanate.
Moreover, polyether polyol and polyester polyol are used as the polyol component.
Polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., and polyester polyols include reaction products of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and sebacic acid; Examples include ring-opening polymers such as caprolactone. The amines used in the copolymerization of amino acids and polyurethane include ethylenediamine, diethylamine,
Triethylamine, ethanolamine, etc. are used. In this way, PAU resin is made of various amino acids, NCA
It is obtained by adding amines to the reaction system of urethane prepolymer and urethane prepolymer having an isocyanate group at the end. Optically active γ-alkyl-glutamate-NCA is preferably used as the amino acid component constituting the PAU resin from the viewpoint of film performance, and among the optically active γ-alkyl-glutamates, γ-methyl-L is preferred from the viewpoint of price and film properties. -Glutamate-NCA or γ-methyl-D-glutamate is often washed free as an amino acid component of PAU resins. In order to obtain the porous membrane of the present invention, it is advantageous to use a uniform resin composition made of a water-soluble solvent system from the viewpoint of both coating properties and wet film forming properties. Such resin compositions include:
Among PAU resins, optically active γ-alkyl-
A reaction product of glutamate-NCA and a urethane prepolymer is preferably used, but this is because the above reaction product is a solvent based mainly on a polar organic solvent, such as a mixed solvent system of dimethylformamide and dioxane, and a mixture of the amine acid and urethane. in weight ratio
This is because the above-mentioned weight ratio can be freely selected while taking into consideration the required physical properties of the film so that a uniform resin solution can be obtained over a wide range of 90:10 to 10:90. The polar organic solvent used in the present invention includes N.N.
-dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylenephosphonamide and the like. In the first step of the method of the present invention, the above-mentioned polyester resin, PAU resin, and polar organic solvent are mixed and used. The blending ratio of polyester resin to PAU resin should be in the range of 100:1 to 100:100 by weight; if the amount of polyester resin is too small, the adhesion of the resin to the polyester synthetic fiber will be insufficient and it will not be practical. If the amount is too high, the resin film will be deformed by heating, causing a practical problem. The most desirable blending ratio is in the range of 100:5 to 100:50. The above-mentioned blended resin solution is coated on a fabric mainly composed of polyester synthetic fibers to a thickness of 10 to 100 μm using a conventional coating method, and then immersed in water. Through this step, a PAU resin film containing countless pores is formed. The water temperature when the fabric is immersed in water is preferably in the range of 0 to 30°C; if the water temperature exceeds 30°C, the pores of the resin film become large and the water pressure resistance becomes poor. Further, the dipping time must be at least 10 seconds; if it is less than 10 seconds, the resin will not solidify sufficiently and a satisfactory PAU resin film will not be obtained. After solidifying the PAU resin in water, the fabric is washed with hot water to remove any remaining solvent. The conditions for hot water washing are 30 to 80°C for 3 minutes or more. After washing with hot water, dry. Next, in the method of the present invention, as a second step, the first
The surface coated in the process contains at least one of polyurethane resin, nonionic surfactant, anionic surfactant, hydrophilic polymer, isocyanate compound, and inorganic filler, PAU resin, and polar organic solvent. A resin solution is applied, immersed in water, washed, and dried. The polyurethane resin used here is a polymer obtained by reacting isocyanate and polyol, and compounds used in the production of ordinary polyurethane resins can be used. As the isocyanate, known resinous and aromatic polyisocyanates can be used, such as hexamethylene diisocyanate, triene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, and the reaction product of an excess of these with a polyhydric alcohol. Polyester polyols, polyether polyols, etc. are used as polyols, and examples of polyester polyols include reaction products of diols such as ethylene glycol and propylene glycol with dibasic acids such as adipic acid and sebacic acid, and open polymers such as caprolactone. Examples include ring polymers. Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Examples of nonionic surfactants used in the method of the present invention include polyoxyethylene alkyl ether, polyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, and polyoxyethylene polyhydric ester. Examples include alcohol fatty acid esters, fatty acid sucrose esters, alkyrodamides, and arbitrary mixtures thereof. Examples of the anionic surfactant used in the method of the present invention include conventionally known alkyl sulfate salts, alkylbenzene sulfonate salts, α-olefin sulfonate salts, alkyl sulfonate salts, fatty acid amide sulfonate salts, dialkyl sulfosuccinate salts, etc. , or any mixture of these can be fried. Hydrophilic polymers include polyvinylpyrrolidone,
Polymers such as polyacrylic acid, polyacrylic ester, carboxyvinyl polymer organic amine, polyethyleneimine, etc. that can be dissolved, dispersed, or emulsified in polar organic solvents and that are soluble in water can be used. Further, as the isocyanate compound, known resin acids and aromatic isocyanates can be used.
Inorganic fillers include powders such as silicic acid, mica, talc, calcium silicate, diatomaceous earth, kaolin,
Generally known fillers such as clay such as bentonite, Sicas balloon, glass balloon, etc. can be used.
It can also be colored with organic, inorganic, or pigments. In the second step of the present invention, at least one of the above-mentioned polyurethane resin, nonionic surfactant, anionic surfactant, hydrophilic polymer, isocyanate compound, and inorganic filler is used.
A resin solution consisting of a PAU resin and a polar organic solvent is used as a coating solution.
What is used in the process may be used as is. The above-mentioned nonionic surfactants, anionic surfactants, urethane resins, and hydrophilic polymers are called micropore-forming agents, and the amount used is the same as that of nonionic surfactants and anionic surfactants. case
It is desirable that the content be in the range of 0.1 to 10% with respect to PAU resin, in the case of urethane resin 0.3 to 6% with respect to PAU resin, and in the case of hydrophilic polymer with 0.05 to 5% with respect to PAU resin. If the amount of these micropore-forming agents used is less than the above range relative to the PAU resin, the pores of the PAU resin film will become too small, making it difficult to obtain interconnected microcells, resulting in poor moisture permeability. Furthermore, if the amount exceeds the above range, the pores will generally become too large and a water pressure resistance of 1500 mm or more cannot be obtained, although this will also be affected by the coagulation bath temperature during wet membrane formation. When nonionic surfactants and anionic surfactants are used in large amounts, they promote the diffusion of dimethylformamide into water, which increases the size of pores in the resin film, which improves moisture permeability but reduces resistance. Water pressure decreases. In the case of urethane resin, when a mixture of urethane resin and PAU resin is immersed in water, PAU resin solidifies faster than urethane resin, so a space is created at the boundary between PAU resin and urethane resin, and this space is filled with resin. Determine the size of the pores in the film. When the amount of urethane is small, the space is small and the pores are therefore small, which improves water pressure resistance but lowers moisture permeability. On the other hand, when the amount of urethane resin is large, the pores become large and the moisture permeability improves, but the water pressure resistance becomes low. In the case of hydrophilic polymers, the hydrophilic polymer components are extracted during the coagulation and washing steps, resulting in the formation of microcells in the film. When a large amount of the hydrophilic polymer component is present in the resin component, the volume occupied by the microcells becomes large, and the pore size on the surface of the resin film also becomes large, resulting in a low water pressure resistance. In the present invention, after applying the above-mentioned mixed resin solution to a fiber fabric, it is immersed in water to form a PAU having countless pores.
A resin film can be formed, and pores having an interconnected microcell structure can be obtained by the action of a micropore-forming agent such as the above-mentioned nonionic surfactant. The mechanism of action of the micropore-forming agent is as described above, but it is also possible to use two or more of these micropore-forming agents in combination. In this case, since the mechanisms of action of the various micropore forming agents are different, it is difficult to discuss all combinations, but the following can be said as the merits of the combined effect. For example, by using a nonionic surfactant or anionic surfactant together with a urethane resin, the stability of the PAU resin and the urethane resin increases, and the coating properties improve.
A smooth coating surface can be obtained. Furthermore, when a hydrophilic polymer and a urethane resin are used in combination, a moisture-permeable waterproof fabric with a good balance between moisture permeability and water pressure resistance can be obtained with a smaller amount than when each is used alone due to the synergistic effect of the effects of the two. When a nonionic surfactant and an anionic surfactant are used together, the diffusion rate of dimethylformamide into water differs between the nonionic and anionic surfactants. Wet film formation is possible under speed conditions (microcell formation conditions), and a porous structure having dense microcells can be obtained. Apply the above-mentioned blended resin solution to the film surface coated in the first step using a normal coating method for 10 to 30 minutes.
The resin was applied to a thickness of 200 μm, and then immersed in water in the same manner as in the first step to solidify the resin.
Dry after washing with hot water. In this way, a moisture-permeable waterproof fabric with good peeling resistance, which is the object of the present invention, can be obtained. It is also possible to use an isocyanate compound in the composition of the coating solution in this second step for the purpose of further improving the adhesion of the film. As an isocyanate compound, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and addition reaction of 3 moles of these diisocyanates and 1 mole of a compound containing active hydrogen, such as trimethylolpropane, glycerin, etc. The triisocyanates thus obtained are used. These isocyanates can be used either in the form in which the isocyanate group is free or in the form in which the block is stabilized by adding phenol, methyl ethyl ketoxime, etc., and the block is then thermally dissociated by heating. It may be selected as appropriate depending on the purpose and purpose. In the present invention, in order to obtain even better waterproof performance, a water repellent agent is applied to the fabric as a third step following the second step. Adding a water repellent agent makes the fabric surface water repellent and has a water pressure resistance of 1500 mm.
It will be possible to obtain moisture-permeable waterproof fabrics with a thickness of 2000 mm or more. There are various types of water repellent such as paraffin type, silicone type and fluorine type, and in the present invention, the water repellent may be selected as appropriate depending on the application.
When particularly good water repellency is required, a fluorine-based water repellent is used, and heat treatment is performed after applying the water repellent and drying. Further, in order to increase the durability of water repellency, a resin such as melamine resin may be used in combination. The water repellent may be applied by a commonly used padding method, coating method, spraying method, or the like. In the present invention, in order to further improve the water repellency of the fabric, a water repellent agent is applied to the fabric in advance before applying a resin solution consisting of PAU resin, polyester resin, and a polar organic solvent to the fabric. Good too. The present invention has the above configuration, and according to the present invention, not only the adhesiveness between the base fabric and the resin layer is good, but also the water pressure resistance is 1500 mm or more, and the moisture permeability is 7000 g/m ² · 24 hrs. The above highly moisture permeable waterproof fabric can be obtained. The moisture-permeable waterproof fabric of the present invention is a material suitable for sports clothing and the like. The present invention will be further explained below with reference to Examples.
Performance measurements and evaluations in Examples were performed in the following manner. (1) Water pressure JIS-L-1041 (low water pressure method) (2) Moisture permeability JIS-Z-0208 (3) Peeling resistance Tested 1000 times with a load of 200g using a Gakushin type friction fastness tester. The appearance of the fabric was observed and evaluated in the following two stages. ○...No peeling at all x...Example in which peeling is observed 1 First, the PAU resin (polyamino acid urethane resin) used in this example was manufactured by the following method. Polytetramethylene glycol (OH value 56.9)
1,970 g of 1-6-hexamethylene diisocyanate and 504 g of 1-6-hexamethylene diisocyanate were reacted at 90°C for 5 hours to obtain a urethane prepolymer (NCO equivalent: 2340) having isocyanate groups at the ends. 85g of this urethane prepolymer and γ-methyl-L-glutamate
When 85g of NCA was dissolved in 666g of a mixed solvent of dimethyformamide/dioxane (weight ratio) = 7/3, 50g of 2% triethylamine solution was added while stirring, and the reaction was carried out at 30℃ for 5 hours, resulting in a viscosity of 32000 cps.
(25°C) A solution of PAU resin A in the form of a yellowish brown emulsion with good fluidity was obtained. This PAU resin A is used in formulations 1 to 5 described below. In addition, as a polyester resin, it is a copolymer of terephthalic acid and sebacic acid in a molar ratio of 6:4 and ethylene glycol and neopentyl glycol in a molar ratio of 5:5, and the molecular weight is 30,000 polyester resin Z was prepared. This polyester resin Z is used in formulation 1 described below. Here, polyester 75 denier / 36 on both warp and weft
Warp density 120/inch using filament,
A plain woven fabric (taffeta) with a weft density of 90 threads/inch was prepared, and after being refined and dyed with a disperse dye in a conventional manner, it was heat-treated at 160° C. for 1 minute. Next, calendering was performed using a calendering machine with mirror-finished rolls at a temperature of 170°C, a pressure of 30 kg/cm, and a speed of 20 m/min. Using a knife over roll coater, coating amount 30
After coating at g/m ² , the resin was immersed in a 15°C water bath for 15 seconds to solidify the resin. Subsequently, it was immersed in warm water at 50° C. for 5 minutes, thoroughly washed with hot water, and then dried to complete the first step. Formulation 1 PAU resin A 100 parts Polyester resin Z 4 parts Dimethylformamide 10 parts Next, as a second step, the resin liquids shown in the following formulations 2 to 5 were applied separately to the surface coated in the previous step using a knife over roll coater. Coating amount 80g/ ^m2
After coating, the resin was immersed in a 15°C water bath for 20 seconds to solidify the resin. Formulation 2 PAU resin A 100 parts CRISVON ASSISTOR SD-7 (nonionic surfactant; Dainippon Ink & Chemicals Co., Ltd. product) 1 part dimethylformamide 20 parts Formulation 3 PAU resin A 100 parts CRISVON AW-7H (polyurethane resin) , Dainippon Ink & Chemicals Co., Ltd.) 10 parts dimethylformamide 20 parts Formulation 4 PAU Resin A 100 parts Polyvinylpyropidone 3 parts Dimethylformamide 12 parts Formulation 5 PAU Resin A 100 parts CRISVON ASSISTOR SD-11 (Anionic surfactant) 2 parts CRISVON AW-7H (urethane resin, Dainippon Ink Chemical Co., Ltd. product) 5 parts Burnock BL-50 (crosslinking agent for urethane resin, Dainippon Ink Chemical Co., Ltd.) Co., Ltd. product) 2 parts Ca _C O3 10 parts Here, after immersing in warm water at 50℃ for 10 minutes and then drying, the third step is asahi guard 710 (Asahi Glass Co., Ltd. product), a futsuso-based water repellent emulsion. Company product) Padding with 5% aqueous solution (squeezing rate 30%)
The fabrics were heat-treated at 160° C. for 1 minute to obtain four moisture-permeable waterproof fabrics of the present invention. For comparison with the method of the present invention, a comparative sample was prepared by the same method as in this example except that the first step in this example was omitted, and the performance was compared with the product of the present invention. The results are shown in Table 1 together with the performance of the product of the present invention. As is clear from Table 1, the moisture permeable waterproof fabric according to the present invention has good adhesion between the fiber base fabric and the resin layer, and although the water pressure resistance is 2000 mm or more, its moisture permeability is 7500 g/m ² · 24 hrs or more. It can be seen that it has both outstanding moisture permeability and waterproof performance. All of the comparative examples in which the first step was removed had poor peeling resistance.

【table】

[Table] Example 2 The third step (water repellent treatment) in Example 1 was omitted, and instead of this, the dyed fabric (taffeta) was treated with a water repellent treatment (futsuso-based manufactured by Asahi Glass Co., Ltd.). 5% water repellent emulsion Asahi Guard 730
The fabric of the present invention and the comparative fabric were processed in exactly the same manner as in Example 1, except for padding with an aqueous solution (squeezing ratio of 35%, followed by heat treatment at 160°C for 1 minute), and the fabric of the present invention and the comparative fabric each obtained 4 points. Ta. The obtained fabric had good moisture permeability, waterproofness, and peeling resistance as shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1 A fiber fabric mainly composed of polyester synthetic fibers is coated with a resin solution mainly composed of a polyester resin, a polyamino acid urethane resin, and a polar organic solvent, and then immersed in water, washed with hot water, and dried. Next, on the coating surface, at least one of a polyurethane resin, a nonionic surfactant, an anionic surfactant, a hydrophilic polymer, an isocyanate compound, and an inorganic filler, a polyamino acid urethane resin, and a polar organic solvent are applied. A method for producing a moisture-permeable waterproof fabric, which comprises applying a resin solution containing the fabric as a main ingredient, followed by immersion in water, washing with hot water, and drying. 2. The method for producing a moisture-permeable waterproof fabric according to claim 1, wherein the fiber fabric is a fiber fabric that has been subjected to water-repellent treatment. 3. A resin solution mainly composed of a polyester resin, a polyamino acid urethane resin, and a polar organic solvent is applied to a fiber fabric mainly composed of polyester synthetic fibers, and then immersed in water, washed with hot water and dried, and then the coated surface is A resin solution mainly consisting of at least one of a polyurethane resin, a nonionic surfactant, an anionic surfactant, a hydrophilic polymer, an isocyanate compound, and an inorganic filler, a polyamino acid urethane resin, and a polar organic solvent. A method for producing a moisture-permeable waterproof fabric, which comprises applying, immersing in water, washing with hot water, drying, and then applying a water repellent. 4. The method for producing a moisture-permeable waterproof fabric according to claim 3, wherein the fiber fabric is a fiber fabric that has been subjected to water-repellent treatment.