JPH0450937B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for manufacturing a moisture permeable waterproof fabric having excellent cold resistance properties by a lamination method. (Prior Art) Generally, the performance of a laminated moisture-permeable waterproof fabric is often influenced by the moisture-permeable waterproof performance and cold resistance properties of the laminated resin film. by the way,
As a resin film with such excellent performance, polyurethane elastomer, in which countless continuous micropores are formed to allow water vapor to escape during the production of the film, has traditionally been preferably used in terms of film strength, rubber elasticity, and flexibility. However, in the case of moisture-permeable waterproof fabrics laminated with polyurethane elastomer resin films, the film is made with a balance between waterproof and moisture permeability, and the adhesive used during lamination Due to this, there is also a slight decrease in moisture permeability, so for laminate fabrics with waterproof performance of 2000mm (under the water column) or more as measured by water pressure resistance according to JIS L-1096, the moisture permeability is at most 3500g/ ^m2・24hrs.
(JISZ-0208 measurement), and even with a laminate fabric with a water pressure resistance of 1500mm, which has a lower waterproof performance, the moisture permeability is only about 4000g/ ^m2・24hrs. Moreover, when used in extremely cold areas with temperatures below -20°C, the fabric had the disadvantage of being extremely hardened and the film being damaged by bending fatigue, resulting in a decrease in waterproof properties. The inventors of the present invention have greatly improved the level of moisture permeability of conventional polyurethane elastomer-based moisture-permeable waterproof fabrics, making it possible to smoothly control the humidity inside the clothes due to sweating when working in the rain or exercising. A patent application was filed in 1984 for a method for manufacturing a moisture-permeable waterproof fabric.
- Proposed in No. 10853. That is, this method uses a polyamino acid urethane resin and a special micropore-forming agent to control the microcells and pore diameter of a porous membrane to produce a highly moisture-permeable waterproof fabric using a wet coating method. However, when the moisture-permeable waterproof fabric obtained by this method is used in extremely cold regions, it hardens significantly at low temperatures and is susceptible to film damage due to bending fatigue, similar to conventional moisture-permeable waterproof fabrics made from polyurethane elastomers. It had the disadvantage of reduced waterproofness. (Problems to be Solved by the Invention) The present invention has been made in view of the above-mentioned current situation, and has a well-balanced waterproof property and moisture permeability, and has moisture permeability with good cold resistance properties in extremely cold regions. The purpose is to obtain waterproof fabric using a lamination method. (Means and effects for solving the problem) As a result of intensive research, the present inventors discovered that there is a correlation between cold resistance characteristics and the ratio of absorbance at a specific wavelength of an infrared absorption spectrum, and based on this knowledge, As a result of further investigation, the present invention was arrived at. In other words, the present invention is based on ``the ratio of absorbance at wave numbers 3290 cm <sup>-1</sup> and 2950 cm <sup>-1</sup> in the infrared absorption spectrum.
A resin solution consisting of a polyamino acid urethane resin in the range of 0.4 to 2.0, an isocyanate compound, a micropore forming agent, and a polar organic solvent is applied to a sheet material, then immersed in water, washed with hot water, dried, and then the above-mentioned ``A method for producing a moisture-permeable waterproof fabric with excellent cold resistance, which comprises bonding a fiber fabric to the coated surface with an adhesive, then peeling off the sheet-like material, and treating the obtained laminate fabric with water repellency'' and `` The ratio of absorbance at wave numbers 3290 cm ^-1 and 2950 cm ^-1 in the infrared absorption spectrum is
A resin solution consisting of a polyamino acid urethane resin in the range of 0.4 to 2.0, an isocyanate compound, a micropore forming agent, and a polar organic solvent is applied to a sheet material, then immersed in water, washed with hot water, dried, and then the above-mentioned A method for producing a moisture-permeable waterproof fabric with excellent cold resistance, characterized by bonding a water-repellent fiber fabric to the coated surface with an adhesive and then peeling off the sheet-like material.'' . The present invention will be explained in detail below. In the present invention, first of all, on one side of the sheet-like material described below, a wave number in the infrared absorption spectrum is applied.
Polyamino acid urethane resin (described below) whose absorbance ratio at 3290 cm ^-1 and 2950 cm ^-1 is in the range of 0.4 to 2.0.
It is called PAU resin. ), a resin solution consisting of an isocyanate compound, a micropore-forming agent, and a polar organic solvent is applied, followed by immersion in water, hot water washing, and drying to form a PAU resin film for lamination. The sheet-like material used in the present invention has a smooth surface, such as taffeta fabric, film, or paper, and is made of a material that has at least a poor affinity with PAU resin. If the surface of the sheet-like material
If it has a high affinity with the PAU resin, it will be impossible to peel off the sheet-like material after lamination with the fiber fabric, making it impossible to obtain the moisture-permeable waterproof fabric that is the object of the present invention. Substances that have poor affinity with PAU resins include polyester resins that are polycondensates of diols and dibasic acids such as polyethylene terephthalate, polyolefin resins such as polyethylene and polypropylene, polydimethylsiloxane, and methyl hydrogen. Silicone resins made of polysiloxane and fluorine resins typified by polytetrafluoroethylene can be used. Further, the sheet-like material may be made of 100% of the above-mentioned material, or only the surface layer thereof may be treated with the above-mentioned material (for example, release paper), It can be fully used as long as it does not break during wet film formation. The infrared absorption spectrum referred to in the present invention is obtained by using an infrared spectrophotometer to separate the wavelengths from the near-infrared region to the far-infrared region using a prism, etc., and then applying the separated light to a substance. Many relatively narrow absorption bands based on molecules appear, and it is useful for qualitative and quantitative analysis of functional groups when immobilizing compounds, and is mainly used for qualitative and quantitative analysis of organic substances. PAU resin is a copolymer of amino acids and urethane, and the present inventors have found that the copolymer composition greatly affects the physical properties of the film, particularly the temperature characteristics, hand feel, strength and elongation characteristics, and moisture permeability. First, the copolymerization composition ratio of amino acid and urethane is determined by adjusting the film thickness of 3290 cm ^-1 A, which is attributed to the stretching vibration of the NH group, as shown in Figure 1, which shows the infrared absorption spectrum of a typical PAU resin. This can be done by determining the ratio of the absorbance at 2950 cm ^-1 B attributed to the CH asymmetric stretching vibration used in the band. (The above absorption positions A and B are 10 to 20 depending on the composition ratio and the type of amino acid and urethane.)
There may be a difference of about cm ^-1 , but in such a case, the absorbance ratio can be found at the position where the maximum absorption occurs. ) Therefore, various PAU resins with a composition ratio (weight fraction) of amino acids and urethane of 10 to 90: to 10 were synthesized and their infrared absorption spectra were taken.
The ratio of absorbance at ⁻¹ and 2950 cm ⁻¹ was determined. Next, when we evaluated the texture of the moisture-permeable waterproof fabric coated with these PAU resins in the temperature range of -30℃ to +20℃, we found a correlation between the above absorbance ratio and cold resistance properties. . That is, the ratio of absorbance is
When it is less than 0.4, cold resistance properties are poor and texture hardening becomes noticeable. On the other hand, when the absorbance ratio exceeds 2.0, the amino acid ratio becomes high, and the film has excellent cold resistance and moisture permeability, but the film has low elongation and poor elastic recovery, resulting in a hard texture and poor adhesion to the base fabric. It also gets worse. Therefore, it is necessary to use a PAU resin having an absorbance ratio in the range of 0.4 to 2.0 in terms of cold resistance and film properties. Next, the same tendency as the cold resistance property was observed for heat resistance, and the above absorbance ratio was
For PAU resins in the range of 0.4 to 2.0, the thermal adhesion temperature increases, unlike polyurethane elastomers. This prevents the porous membrane from being deformed or causing a decrease in moisture permeability during a normal heat treatment process. Further, in the case of conventional polyurethane elastomers, transfer printing has been impossible due to problems of heat curing and decreased moisture permeability, but this transfer printing is also possible with the moisture permeable waterproof fabric of the present invention. The reason why PAU resin exhibits good thermal behavior even at low temperatures and constant temperatures is thought to be due to the α-helical structure of poly-α-amino acids. In other words, it is presumed that in the α-helical structure, α-amino acids form intramolecular hydrogen bonds, making the rod-shaped molecules thermally stable. The PAU resin used in the present invention is a copolymer consisting of amino acids and polyurethane, and the amino acids include DL-alanine, L-aspartic acid, L-
-cystine, L-glutamic acid, glycine, L-
These include lysine, L-methionine, L-leucine and their derivatives, and when synthesizing polyamino acids, the amino acid N-carboxylic anhydride (hereinafter referred to as N-carboxylic anhydride) is obtained from amino acids and phosgene.
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, and the like. In this way, PAU resin can be used for various amino acids.
It is obtained by adding amines to the reaction system of NCA and a urethane prepolymer having an isocyanate group at the end. As the amino acid component constituting the PAU resin, optically active γ-alkyl-glutamate-NCA is preferably used from the viewpoint of film performance, and among the optically active γ-alkyl-glutamates, γ-methyl-NCA is preferably used from the viewpoint of price and film properties.
L-glutamate-NCA or γ-methyl-D-
Glutamate is often advantageously selected as the 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. As such a resin composition, a reaction product of an optically active γ-alkyl-glutamate-NCA and a urethane prepolymer among PAU resins is preferably used, but this is because the above-mentioned reaction product is a solvent system mainly composed of a polar organic solvent. For example, in a mixed solvent system of dimethylformamide and dioxane, the weight ratio of amino acid and urethane can be a uniform resin solution over a wide range of 90:10 to 10:90. This is because the ratio can be freely selected. The PAU resin constitutes the film part of the laminated fabric after lamination, and the amount used is preferably 5 g/m ² or ^more in pure terms. is difficult to obtain. The reason why high water pressure resistance and high moisture permeability can be obtained through wet processing of PAU resin is not obvious, but when observing the cross section of the film of the obtained moisture-permeable waterproof fabric, it is found that the PAU resin film has a higher resistance to water than a polyurethane film. The microcells are small, large in number, and uniformly distributed, which is thought to be a factor in providing high moisture permeability and high water pressure resistance.
Furthermore, PAU resin's own high affinity for water vapor may be one of the driving forces behind its high moisture permeability. Considering the molecular structure of the PAU resin used in the present invention, the PAU resin is composed of block copolymerization of amino acids and urethane, and as mentioned above, the amino acid component mainly forms an α-helical structure; The urethane component forms a random coil structure. This is the attribution of the amide band in the infrared absorption spectrum (amide V615cm ^-1 ; key band of α-helical conformation of poly-γ alkyl-L-glutamate) in the porous membrane produced by the wet coagulation method of the present invention. Confirmed by. In general, in the case of amino acid resins, the driving force behind their high moisture permeability is their high diffusion coefficient, and this is thought to be due to the α-helical structure of the amino acid resins, which have large side chains. Taken together, it is highly conceivable that PAU resin has two structures, an α-helical structure and a random coil structure, and has a looser packing structure at the interface between the two. It is thought that the loose packing state of the molecular structure and the hydrogen bonds between amide bonds give the polymer its own high moisture vapor permeability, unlike that of polyurethane elastomers. Isocyanate compounds used in combination with the above-mentioned PAU resins include 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, or compounds containing 3 moles of these diisocyanates and active hydrogen (for example, trimethylolpropane). , glycerin, etc.) are used. The above-mentioned isocyanates may be in the form where the isocyanate group is free, or may be stabilized by adding phenol, methyl ethyl ketoxime, etc., and the block may be dissociated by subsequent heat treatment.
Either type can be used, and it can be used appropriately depending on workability, purpose, etc. The amount of the isocyanate compound to be used is preferably 0.1 to 5%, preferably 0.5 to 3%, based on the PAU resin. If the amount used is less than 0.1%, the adhesion of the resin to the sheet material for film formation will be poor, and the film may peel off during wet film formation.On the other hand, if the amount exceeds 5%, the adhesion of the resin will be poor. is undesirable because it becomes too high and it becomes difficult to peel off the sheet-like material after lamination and the texture becomes hard. In the present invention, a micropore-forming agent is used in combination to reduce the size of microcells in the PAU resin film and to ensure that a large number of pores exist uniformly on the surface. Examples of the micropore-forming agent used here include anionic surfactants, nonionic surfactants, hydrophilic polymers, and polyurethane elastomers. The amount used is 0.5 to 10% for anionic surfactants and nonionic surfactants, 0.3 to 20% for hydrophilic polymers, and 1.5 to 1.5% for polyurethane elastomers based on the solid content of the PAU resin used in combination. It is desirable to be in the range of 30%. If the amount of these micropore-forming agents used is less than the above range, the pores of the PAU resin film will become too small, making it difficult to obtain interconnected microcells and resulting in poor moisture permeability. Moreover, when it is higher than the above range, the pores become too large and high water pressure resistance cannot be obtained. The anionic surfactants used as the above-mentioned micropore-forming agents include conventionally known alkyl sulfate ester salts, alkylbenzene sulfonates, α-olefin sulfonates, alkyl sulfonates, fatty acid amide sulfonates, and dialkyl sulfosuccinic acids. Salt, etc. or any mixture thereof. In addition, nonionic surfactants include polyoxyethylene alkyl ether, polyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid amide ether, polyhydric alcohol fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, It refers to fatty acid sucrose ester, alkyrodamide, etc., or any mixture thereof. Hydrophilic polymers include holivinylpyrrolidone, polyacrylic acid, polyacrylic ester, carboxyvinyl polymer organic amine, and polyethyleneimine, and are substances that can be dissolved, dispersed, or emulsified in polar organic solvents and soluble in water. It refers to a polymer that has a Polyurethane elastomer is a polymer obtained by reacting polyisocyanate and polyol, and known aliphatic and aromatic polyisocyanates can be used as the polyisocyanate.
Examples include hexamethylene diisocyanate, toluene diisocyanate, xylene diisocyanate, and reaction products of excess thereof with polyhydric alcohols. As the polyol, known polyethers, polyesters, and other polyols used in the production of ordinary polyurethane resins can be used. Examples of polyesters include polyhydric alcohols such as ethylene glycol, diethylene glycol or 1,4-butanediol, and adipic acid;
Examples include reactants of polybasic carboxylic acids such as oxalic acid or sebacic acid. Examples of polyether include polyhydric alcohols such as ethylene glycol and propylene glycol to which one or more alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are added. In the present invention, the above-mentioned PAU resin, isocyanate compound, micropore forming agent, and polar organic solvent are used in combination, and the polar organic solvent used here includes dimethylformamide, dimethylacetamide,
Examples include N-methylpyrrolidone and hexamethylenephosphonamide. These substances are highly soluble in water, and when a polar organic solvent solution of a water-insoluble resin is immersed in water, only the polar organic solvent dissolves in the water, and the resin coagulates in the water. A resin coagulation method using such a method is generally called a wet coagulation method. When a resin is coagulated by a wet coagulation method, a trace amount of the polar organic solvent present in the resin is eluted into water, so a resin having countless micropores can be obtained. Further, in the present invention, a water repellent may be mixed in advance into the coating solution for forming the porous membrane in order to improve the water resistance of the porous membrane formed by the wet coagulation method. There are various types of water repellents such as fluorine-based, silicon-based, and zirconium-based, but in the present invention, those that are compatible with polar organic solvents are preferred, and acrylate-based solvent-based water repellents containing fluoroalkyl groups are preferred. Water repellents such as tetrafluoroethylene, vinylidene fluoride resins, or silicone water repellents such as methylhydrogen polysiloxane and dimethyl polysiloxane are preferably used. The resin solution consisting of the PAU resin, isocyanate compound, micropore-forming agent, and polar organic solvent may be applied to the sheet-like material by a conventional coating method. Generally, the coating thickness of resin is 10 to 300 μm due to machine performance. After applying the resin solution to a sheet-like object, this sheet-like object is immersed in water as it is. This immersion in water makes it possible to form a PAU resin film with countless micropores, and the action of the micropore forming agent makes it possible to obtain micropores of an appropriate size that provide good moisture permeability and water pressure resistance. can. Water temperature during immersion is 0-30℃
It is sufficient if the dipping time is within the range of 10 seconds or more. After solidifying the PAU resin in water, wash it with hot water,
Remove remaining solvent. Conditions for hot water washing
Although it varies depending on the amounts of the PAU resin, isocyanate compound, and micropore forming agent used, it may be carried out at a temperature of 30 to 80°C for 3 minutes or more. After washing with hot water, dry. Next, in the method of the present invention, a water-repellent fiber fabric is bonded to the resin-coated surface using an adhesive. The fiber fabrics mentioned here include polyamide synthetic fibers such as nylon 6 and nylon 66, polyester synthetic fibers such as polyethylene terephthalate, polyacrylonitrile synthetic fibers, polyvinyl alcohol synthetic fibers, and even triacetate. Examples include woven fabrics, knitted fabrics, nonwoven fabrics, etc. made of semi-synthetic fibers or mixed fibers such as nylon 6/cotton, polyethylene terephthalate/cotton, etc. In particular, since the method of the present invention is based on a lamination method, it is difficult to coat fiber fabrics that generally cannot be coated, such as fabrics with uneven surfaces, coarse fabrics, fabrics with high air permeability, fabrics with high elasticity, etc. The method of the present invention can also be applied to fabrics. In the present invention, processing is performed using these fiber fabrics treated with a water repellent agent. The water repellency of the fabric
It is desirable that the water repellency is 90 or higher as determined by the JIS L-1096 spray method. The water repellent used may be a known one such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment may be carried out by a commonly known method. If particularly good water repellency is required, use a fluorine-based water repellent, such as Asahi Guard 730 manufactured by Asahi Glass Co., Ltd.
This may be carried out by padding (fluorine-based water repellent emulsion) with a 5% aqueous solution (squeezing ratio: 35%), followed by heat treatment at 160° C. for 1 minute. For the purposes of the present invention, the adhesive used for joining the fabrics needs to have a polymer with good flexibility, and it is preferable to use an adhesive that has a degree of adhesiveness that will not peel off when rubbed or washed. It will be done. For example, polyacetal resins such as polyvinyl butyral and polypynyl formal, polyurethane resins, polyester resins, esters of acrylic acid and methacrylic acid such as isobutyl, n-butyl, and propyl, and their copolymers, natural rubber, and NBR.
Examples include latex, etc. When bonding fiber fabrics with an adhesive, dotted partial bonding is preferably used so as not to impede the moisture permeability of the laminated fabric as much as possible. In addition, as a method for applying the adhesive, a gravure roll method is suitable from the viewpoints of coating amount, texture of the fabric after lamination, adhesive strength, workability, etc. The lamination method may be either a dry lamination method or a wet lamination method depending on the type of adhesive used. The moisture permeable waterproof fabric of the present invention having a PAU resin film on the surface of the fiber fabric can be obtained by bonding the fiber fabric with an adhesive and then peeling off the sheet. In the above-mentioned method, a water-repellent treated fabric was used as the fiber fabric, but this fiber fabric does not necessarily have to be subjected to a water-repellent treatment in advance, and the fabric obtained after lamination may be subjected to a water-repellent treatment. In this case, after bonding the fiber fabric to the PAU resin coating surface on the sheet-like object with an adhesive, the sheet-like object is peeled off and the obtained laminate fabric is treated to make it water repellent. A moisture permeable waterproof fabric can be obtained. Regarding the water repellent agent and water repellent treatment method used here, the padding method, the padding method,
Water repellent treatment may be performed by a spray method, a coating method, or the like. Furthermore, in order to increase the durability of water repellency, water repellent treatment can be performed using a resin such as melamine resin in combination. In the method of the present invention, there is no problem even if the water repellent treatment is performed both before and after lamination, and in this case, a product with even better water pressure resistance can be obtained. Further, in order to improve the smoothness and flexibility of the fabric, a polysiloxane resin may be further applied to the fabric. As the polysiloxane to be applied,
Dimethylpolysiloxane, phenyl group-containing polysiloxane, modified silicone oil such as amino-modified or olefin-modified silicone oil, methylhydrogen polysiloxane or a mixture of dimethylpolysiloxane and methylhydrogen polysiloxane, etc. can be used, and they may be selected as appropriate depending on the application. In the present invention, dimethylpolysiloxane having a molecular weight of 5,000 to 30,000 is preferably used. This polysiloxane treatment
First of all, it can impart smoothness to the fabric and reduce wear and tear on the film due to friction between the fabrics.
This smoothing effect also has the advantage of making it easy to put on and take off without using a lining. Second, the silicone resin adheres between the fabric structures and reduces the friction between the threads that make up the fabric, resulting in a softer texture. This polysiloxane treatment may be applied in the form of an aqueous dispersion, emulsion, etc., but in order to prevent treatment spots, 1.1.1. It may also be applied as a solution in a solvent such as mineral turpentine. The polysiloxane resin may be applied by a commonly used padding method, coating method, spraying method, or the like. The amount of polysiloxane deposited is preferably 0.1% or more in terms of solid content based on the weight of the fiber. (Example) Next, the present invention will be further explained with reference to an example.
Performance measurements and evaluations in this example were performed in the following manner. (1) Water pressure resistance JIS L-1096 (low water pressure method) (2) Water repellency JIS L-1096 (spray method) (3) Moisture permeability JIS Z-0208 (4) Peel strength JIS K-6328 (5) Washing durability The quality was determined by the presence or absence of peeling after repeated washing 10 times according to JIS L-0842 (method A-2). (6) Elongation rate Measure the elongation rate at a load of 1.5Kg according to JIS L-1080 (Method A). (7) Infrared absorption spectrum Consists of a specific composition ratio of amino acids and urethane
PAU resin was diluted with dimethylformamide to an appropriate concentration, poured onto a glass plate, and
Dry at 80°C to form a film with a thickness of 3 to 5μ. 2950cm ^-1 attributed to asymmetric CH stretching vibration
The absorbance of 2950 cm is proportional to the film thickness.
^-1 absorption band is used as the thickness correction band. Regarding the absorption intensity, read the BC and AC of the specific absorption band using the baseline method shown in Figure 2,
The absorbance D is determined by the following formula. D= _1og10 -AC/BC- In the present invention, the absorbance ratio= _D3290 / _D2950 is determined. (8) Cold resistance characteristics Change in texture due to temperature Changes in texture due to temperature are examined in an atmosphere of -30℃ and +20℃, and evaluated on a 10-rank scale from 10 for flexibility to 1 for rigidity. Evaluation of waterproofness by rubbing during cold resistance After rubbing the sample 100 times by hand after leaving it at -30°C for 2 hours, the water pressure resistance is measured and compared with the water pressure resistance at 20°C. Example 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)
985g and 222g of isophorone diisocyanate at 110℃
The mixture was reacted for 5 hours to obtain a urethane prepolymer (NCO equivalent: 1233) having an isocyanate group at the end. 51 g of this urethane prepolymer and 119 g of γ-methyl-L-glutamate-NCA were dissolved in 666 g of a mixed solvent of dimethylformamide/dioxane (weight ratio = 7/3), and 2
When 102 g of a hydrated hydrazine solution was added and the reaction was carried out at 30°C for 3 hours, an emulsion-like PAU resin solution with a viscosity of 23,000 cps (25°C) and good fluidity was obtained. (PAU resin A) This PAU resin A is used in formulation 1 described below. Next, the resulting PAU resin solution was cast onto a glass plate and dried at 70°C to increase the film thickness.
A transparent film of 5μ was obtained. The infrared absorption spectra of this film were taken, and the wave numbers were 3290 cm ^-1 and 2950 cm.
^-1 absorbance ratio was found to be 1.90. Next, a biaxially stretched polyester film with a thickness of 25 μm was prepared, and a resin solution with a resin solid content concentration of 20% shown in Formulation 1 below was applied to the film at an amount of 100 g/m ² using a knife over roll coater. After coating, the resin was immersed in a water bath at 15°C for 20 seconds to solidify the resin, followed by washing in warm water at 50°C for 10 minutes and drying. Prescription 1 PAU resin A 100 parts Burnock BL-50 2 parts (Isocyanate compound, Dainippon Ink & Chemicals Co., Ltd. product) CRISVON AW-7H 8 parts (Pore forming agent; polyurethane elastomer, Dainippon Ink & Chemicals Co., Ltd. product) Dimethylformamide 5 parts A porous film was formed on the film as described above. Next, using a 30-mesh hexagonal gravure roll, apply the polyurethane adhesive of the following formulation 2 to the porous film surface at a coating amount of 10 g/m ² in dots. ^Circular knitted fabric (JIS
Water repellency 100 by L-1096 spray method; Air permeability
40cc/cm ² ·sec), and then dried at 120°C for 3 minutes. Prescription 2 CRISVON 4070 100 parts (polyurethane adhesive, Dainippon Ink & Chemicals Co., Ltd. product) CRISVON CL-2 18 parts (isocyanate crosslinking agent, Dainippon Ink & Chemicals Co., Ltd. product) CRISVON ACCEL HR 2 parts (isocyanate crosslinking agent) catalyst, product of Dainippon Ink & Chemicals Co., Ltd.) Thereafter, only the polyester film was peeled off to obtain a moisture-permeable and waterproof fabric A of the present invention using a lamination process. Next, in order to further clarify the effect of the present invention, PAU resins B to D described below were used in place of PAU resin A in the coating solution of formulation 1, and the isocyanate compound, micropore forming agent, and dimethylformamide were the same. Moisture-permeable waterproof fabrics B to D are laminated using the same composition as in Prescription 1.
I got it. Fabric B is a moisture permeable waterproof fabric according to the present invention, and Fabric C and Fabric D are comparative examples. [Production of PAU resin B] 111 g of the urethane prepolymer (NCO equivalent: 1233) used in Example 1 and 59 g of γ-methyl-L-glutamate-NCA were mixed with 666 g of a mixed solvent of dimethylformamide/dioxane (weight ratio = 7/3). Add 51g of 2% hydrated hydrazine solution to this solution while stirring, and react at 30°C for 2 hours to reduce the viscosity.
An emulsion-like PAU resin solution with good fluidity was obtained at 32,000 cps (25°C). (PAU resin B) Find the ratio of absorbance at wave numbers 3290 cm ^-1 and 2950 cm ^-1 according to the infrared absorption spectrum of this PAU resin B.
It was 0.61. [Manufacture of PAU resin C] 153 g of the urethane prepolymer (NCO equivalent: 1233) used in Example 1 and 17 g of γ-methyl-L-glutamate-NCA were mixed with 666 g of a mixed solvent of dimethylformamide/dioxane (weight ratio = 7/3). 13g of 2% hydrated hydrazine solution was added to this while stirring, and the reaction was carried out at 30°C for 5 hours.
A translucent PAU resin solution with good fluidity was obtained.
(PAU resin C) Find the ratio of absorbance at wave numbers 3290 cm ^-1 and 2950 cm ^-1 according to the infrared absorption spectrum of this PAU resin C.
0.2, the resin composition was flexible, but had a urethane-like texture and was tough. [Production of PAU resin D] 25.5 g of the urethane prepolymer (NCO equivalent: 1233) used in Example 1 and 144.5 g of γ-methyl-L-glutamate-NCA were mixed in dimethylformamide/dioxane (weight ratio = 7/3). mixed solvent
666 g, 120 g of a 2% aqueous hydrazine solution was added thereto with stirring, and the reaction was carried out at 30°C for 3 hours to obtain a resin solution in the form of a yellowish brown emulsion with a viscosity of 18,000 cps (25°C) and good fluidity. (PAU resin D) Find the ratio of absorbance at wave numbers 3290 cm ^-1 and 2950 cm ^-1 according to the infrared absorption spectrum of this PAU resin D.
2.3, the composition was rigid and brittle and exhibited low elongation. The performance of four moisture permeable waterproof fabrics (fabrics A to D) made of PAU resins A to D was measured and evaluated, and the results are shown in Table 1.

【table】

[Table] As is clear from Table 1, both Fabric A and Fabric B according to the present invention exhibit excellent moisture permeability and water pressure resistance, and furthermore, their texture changes even under extreme environmental changes with a temperature difference of 50°C. It was found that there was no change in water pressure resistance after bending, and that it could be used satisfactorily even in extremely cold conditions. On the other hand, comparative fabric C was a urethane-touch fabric that was resistant to changes in water pressure and temperature after bending, and was only comparable to conventional urethane laminated products. In addition, in the case of comparative fabric D, the texture and physical properties are similar to that of polyα-amino acids, and the texture is rigid and the water pressure resistance decreases greatly due to bending.Furthermore, when observing the film surface after hand-rubbing, The film had peeled off from the base fabric surface. (Effect of the invention) The present invention provides wave numbers in an infrared absorption spectrum.
Processing is carried out using the nate processing method using PAU resin whose absorbance ratio between 3290 cm ^-1 and 2950 cm ^-1 is in the range of 0.4 to 2.0, and the fabric obtained according to the present invention has good cold resistance properties and can be used at low temperatures. Unlike moisture-permeable waterproof fabrics produced by conventional lamination methods, it is possible to obtain moisture-permeable waterproof fabrics that can be used satisfactorily even in cold regions, since there is little hand hardening during the process. The moisture-permeable waterproof fabric of the present invention is a material that is well suited not only for sports clothing but also for survival use in extremely cold regions.

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectrum of the PAU resin (polyamino acid urethane resin) used in the present invention, and FIG. 2 is a diagram showing the absorption intensity at a specific wave number (cm ^-1 ) determined by the baseline method. A... Wave number 3290cm ^-1 NH stretching vibration band, B
...wave number 2950cm ^-1 film thickness correction band CH
Asymmetric stretching vibration band, XY...baseline, A...intersection of the perpendicular line passing through B and ^baseline ), C...The position of the perpendicular line passing through B where the transmittance is 0%.

Claims (1)

[Claims] 1. Wave number 3290 cm ^-1 in infrared absorption spectrum
A resin solution consisting of a polyamino acid urethane resin, an isocyanate compound, a micropore-forming agent, and a polar organic solvent having an absorbance ratio of 0.4 to 2.0 at ²⁹⁵⁰ cm A laminating process of a fiber fabric and a resin film, which consists of washing, drying, and then bonding the fiber fabric to the coated surface with an adhesive, and then peeling off the sheet-like material, and a water-repellent treatment of the fiber fabric to make it water-repellent. A method for producing a moisture-permeable waterproof fabric with excellent cold resistance, comprising the steps of: 2. The method for producing a moisture permeable waterproof fabric according to claim 1, wherein a water repellent step is performed after the lamination step. 3. The method for producing a moisture permeable waterproof fabric according to claim 1, characterized in that a lamination step is performed after the water repellent step.