JP4359818B2 - Coated fabric - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coated fabric excellent in wearing comfort. More specifically, the present invention relates to a coating fabric that maintains a comfortable temperature and humidity in clothes even when sweating and has a practically sufficient waterproof performance.
[0002]
[Prior art]
Many studies have been made on the main purpose of improving the water-resistant performance and moisture-permeable performance of coated fabrics mainly made of polyurethane resin by a wet coagulation method. As a typical example, there is a fabric (hereinafter referred to as a coating fabric) coated with a microporous film formed by a polyurethane resin, and a production method is also known (see, for example, Patent Document 1).
[0003]
Numerous studies have been conducted focusing on the moisture transfer characteristics of coated fabrics. As one of the ideal images of the coating layer structure, the skin side is designed as a hydrophobic net, the middle as a hydrophilic component, and the outside, that is, the fabric fabric side as hydrophobic. According to the document, a mixed solution of a hydrophilic polyurethane resin and a hydrophobic resin is coated on a water-repellent treated fabric, and then immersed in water and dried. It is stated that an ideal structure can be obtained. As the hydrophobic resin in this document, polyvinyl chloride resin, polyvinyl chloride-vinyl acetate copolymer resin, polyvinyl chloride-ethylene copolymer resin, and the like are disclosed. It is disclosed that a coated fabric having a water pressure resistance of 0.192 kgf / cm ² and a moisture permeability of about 12000 g / m ² · 24 hrs can be obtained by coating the solution, dipping in water and drying.
[0004]
Further, it is known that the dew condensation of the resin layer affects the comfort when worn. As a method for evaluating condensation, a beaker containing 40 ° C. hot water was sealed with the resin surface of the sample to be measured facing down and left in an atmosphere of 10 ° C. and 60% RH for a certain period of time, and adhered to the resin layer. A method for quantifying the amount of water droplets is disclosed (see, for example, Patent Document 3). In this method, since the hot water temperature and the temperature of the sample to be measured are lowered when left in an atmosphere of 10 ° C. and 60% RH, the dew condensation phenomenon in practical use cannot be sufficiently reproduced.
[0005]
In general, when considering the comfort of clothing, it is important to design products that take into account the "climate in clothes" based on moisture and heat transfer characteristics, the "stretchability" related to skin stretch, and the "touch" based on contact between skin and clothes. It becomes. In the case of the coated fabric, since it is designed to have a certain size, the climate in the clothes and the touch are important factors when considering the wearing comfort of the coated fabric. Although it is in a limited environment, it is known that the temperature inside the clothes that the human body feels comfortable when worn is 32 ° C. ± 1 ° C., the humidity is 50 ° C. ± 10% RH, and the air flow is 25 ± 15 cm / sec. (For example, refer nonpatent literature 1.). Since the coated fabric is mainly used in an environment where the outside air temperature is 15 ° C. or less, studies are being made to improve the heat retaining property in order to enhance the wearing comfort. For example, a method of kneading ceramics or metal fine particles into a fiber is disclosed (see, for example, Patent Document 4 and Patent Document 5). In addition, a method in which high moisture absorption / release moisture exothermic organic fine particles are contained in the coating resin layer is known (see, for example, Patent Document 6 and Patent Document 7). However, in the above-described prior art, although the temperature inside the garment is surely kept at a comfortable temperature, there is no description about maintaining water resistance performance and moisture permeability performance at a high level.
[0006]
Prior art document information related to the invention of this application includes the following.
[Patent Document 1]
Japanese Patent Publication No. 60-47955 (Claim 1 etc.)
[Patent Document 2]
JP-A-9-41275 (Claim 1 etc.)
[Patent Document 3]
Japanese Unexamined Patent Publication No. 7-9631 (paragraph number 0007, etc.)
[Patent Document 4]
JP-A-63-105107 (Claims (1) etc.)
[Patent Document 5]
JP-A-7-331584 (Claim 1 etc.)
[Patent Document 6]
JP 11-279953 A (Claim 1 etc.)
[Patent Document 7]
JP 2000-199180 A (Claim 1 etc.)
[Non-Patent Document 1]
Ryuji Harada, “Comfort and Science”, Hanabo, May 15, 1996, p. 19
[0007]
[Problems to be solved by the present invention]
In view of the present situation as described above, an object of the present invention is to obtain a coated fabric that maintains water resistance and moisture permeability at a high level and can realize a comfortable wearing feeling.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention.
That is, the present invention has the following configuration.
1. On the fiber fabric that has been subjected to water repellent treatment before the coating process , the ether polyurethane resin and the ester polyurethane resin are included, and the coagulation value of the ether polyurethane resin is smaller than the coagulation value of the ester polyurethane resin. Organic fine particles comprising two or more types of polyurethane resins, each polyurethane resin having a coagulation value in the range of 5 to 12, and each polyurethane resin having a coagulation value difference of 0.5 or more, and having moisture absorption and desorption exothermic properties there is formed a resin layer ing is contained in, and smoothness of the resin layer, a 0.42 a der Ru coated fabric less friction coefficient obtained by the friction tester, moisture permeability with potassium acetate method 15000g ^/ m 2 · 24hrs or more, water pressure resistance 5000mmH ₂ O or more, in clothes up by perspiration simulator measurement Coating fabric, characterized in that reaches temperatures and clothes in ultimate maximum humidity at 34 ° C. or less 30 ° C. or more is less than RH 65%.
2. Moisture absorption and desorption exothermic organic fine particles are introduced into the acrylonitrile-based polymer containing 50% by weight or more of acrylonitrile by introducing a crosslinked structure by hydrazine, divinylbenzene or triallyl isocyanurate treatment, and the remaining nitrile group is converted into a salt by hydrolysis. be those was allowed chemical converted to the type carboxyl group, the coating fabric of the first, wherein the organic fine particles der Rukoto having salt-type carboxyl group 1.0 mmol / g or more.
3. Moisture permeability with potassium acetate method is 15000 g ^/ m 2 · 24hrs or more 40000 g ^/ m 2 · 24hrs or less, water pressure resistance according to the first or second characterized by the following der Rukoto 10000MmH ₂ O or more 35000MmH ₂ O Coating fabric.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. The coated fabric of the present invention is a coated fabric comprising a fiber fabric and at least one type of polyurethane resin layer, having a moisture permeability of 15000 g / m ² · 24 hrs or more by a potassium acetate method and a water pressure resistance of 5000 mmH ₂ O or more. It is preferable that the maximum reachable temperature in the clothes measured by the sweating simulation apparatus is 30 ° C. or more and 34 ° C. or less and the maximum reachable humidity in the clothes is 65 % RH or less.
[0010]
Needless to say, the basic performance of the coated fabric is to prevent water leakage and to pass water vapor generated from the body. From this point of view, if the water pressure resistance is 5000 mmH ₂ O or more, sufficient water resistance can be achieved even in a severe wind and rain environment, and more preferably 10,000 mmH ₂ O or more. The higher the water pressure resistance, the better. However, if the water pressure is too high, it becomes difficult to make the water vapor transmission rate 15000 g / m 2 · hrs or more, so it may be about 35000 mmH ₂ O or less.
[0011]
Regarding moisture permeability, since ISO11092 is recognized as a practical comfort evaluation method, it is well known that the correlated JIS L-1099 B-1 method potassium acetate method is also effective. When this evaluation measure assumes, preferably to maintain the wear comfort is more 15000g / m ² · 24hrs, more preferably 17000g / m ² · 24hrs or more, more preferably 20000 g / m ² -It is 24 hrs or more. However, if the water vapor transmission rate is too high, it becomes difficult to make the water pressure resistant to 5000 mmH ₂ O or more, so it may be 40000 g / m 2 · 24 hrs or less.
[0012]
In order to obtain a method of measuring the amount of condensation that can appropriately evaluate comfort, we developed a sweating simulation device test method (skin model test method) in consideration of problems such as the conventional method of measuring the amount of condensation. The correspondence of was examined. This test method is a model evaluation method considering a practical environment in which constant water vapor and heat are always supplied to the resin layer.
According to this evaluation method, it is preferable that the dew condensation amount by this evaluation method is 10 g / m ² · hr or less in order to keep the skin separation between the resin layer described later and the skin in a good state. More preferably, it is 8 g / m ² · hr or less, and further preferably 5 g / m ² · hr or less. Clothes in maximum ultimate temperature is 30 ° C. or higher 34 ° C. or less, good Mashiku is 33 ° C. 31 ° C. or higher. When it exceeds 34 ℃, discomfort Ru appear. Clothes in maximum ultimate humidity is less than RH 65%, good Mashiku is less 60% RH or more RH 40%. Discomfort Ru appears when Ru exceed RH 65%.
[0013]
It is well known that the skin separation between the resin layer and the skin is an important performance for suppressing stickiness. The skin peelability is related to the adhesiveness of the resin layer, but as a result of our research, it was found that the skin peelability was dramatically improved by increasing the smoothness of the resin layer. The smoothness of the resin layer can be measured using a friction tester manufactured by Kato Tech Co., Ltd. In our research, if the friction coefficient obtained with a friction tester is 0.42 or less, a combination of the above-mentioned physical properties and a practically sufficiently comfortable coating fabric with no lining, which has little stickiness in practical use. Can be obtained . Good Mashiku is 0.35 or less.
[0014]
In the present invention, it is preferable to incorporate fine particles having moisture absorption / release properties into the coating resin layer adhered to the fiber fabric for the purpose of improving wearing comfort. When sweating when worn, if the fabric has a moisture absorption and release heat generation effect, the atmospheric temperature will rise and the relative humidity will fall, so it will be hard for the wearer to feel stuffiness at the time of wearing, as well as condensation on the coating film Can be prevented. If the fine particles having the moisture absorption and desorption exothermic property are fine particles made of an organic compound or fine particles obtained by coating an inorganic fine particle with an organic compound, the dispersibility in the resin layer is good, and absorption by selecting a treatment method for the fine particles is possible. The moisture release heat generation performance can also be controlled.
[0015]
Moreover, fine particles having moisture absorption and desorption exothermic properties are introduced into the acrylonitrile polymer containing 50% by weight or more of acrylonitrile by introducing a crosslinked structure by treatment with hydrazine, divinylbenzene or triallyl isocyanurate, and the remaining nitrile group is hydrolyzed to form a salt form. In order to obtain excellent moisture absorption and desorption heat generation performance, it is preferably chemically converted to a carboxyl group and having a salt-type carboxyl group of 1.0 mmol / g or more.
[0016]
Examples of the fiber include natural fibers such as cotton, hemp, and wool, and mixed or interwoven products thereof, but are not particularly limited. Moreover, those forms may be any form such as woven fabric, knitted fabric, and non-woven fabric.
[0017]
In addition, the coating resin layer of the present invention is segregated with a hydrophobic component on the skin side, a hydrophilic component in the middle, and a hydrophobic component on the outside (fiber fabric side). It is desirable to realize moisture permeability, and it is preferable to use a mixed solution of polyurethane resins having different coagulation values, that is, hydrophilicity / hydrophobicity. The coagulation value here is a numerical value indicating the degree of hydrophilicity and hydrophobicity, and its principle is described in Polymer Journal, Vol. 39, 535-542 Mitsugu, 1982. In the present invention, it is impossible to directly adopt the measurement method described in the above literature due to the limitation of the viscosity of the solution. Therefore, the following method was adopted as a simple method.
[0018]
The synthesized polyurethane solution is diluted with DMF to a solid content concentration of 1% by weight, and this diluted solution is kept at 30 ° C. While stirring, a mixed solution of water / DMF = 40/60 as a non-solvent is dropped into the solution with the naked eye. The intermediate point between the determined cloudy start point and end point was defined as the non-solvent dropping amount, and the coagulation value was determined using the following equation.
Coagulation value (% water) = | 0.4b / (a + b) | × 100
(In the above formula, a is the weight of the resin solution having a concentration of 1% by weight diluted with DMF, and b is the weight calculated from the dripping amount (ml) × 0.985).
[0019]
A preferred range for the coagulation value is from 5 to 12, more preferably from 9 to 11. By mixing polyurethane resin solutions with different coagulation values, that is, with different degrees of hydrophilicity / hydrophobicity, the hydrophobic polyurethane resin component is crushed on the skin side opposite to the fiber fabric during the process of coagulation in water, and hydrophilic polyurethane As a result, the resin component is located approximately in the middle. At this time, it is also preferable that the fiber fabric is subjected to water repellent treatment in advance to make the fiber fabric side hydrophobic. By setting it as the above structures, the coating fabric which maintains a wear comfort can be obtained, maintaining high water resistance and moisture permeation performance.
[0020]
As a specific component of the polyurethane resin, generally called a polyurethane resin or a polyurethane urea resin, a polyalkylene-ether glycol having a molecular weight of 400 to 4000, a polyester polyol having a hydroxyl group at a terminal, a poly ε-caprolactone polyol, Alternatively, it can be obtained by reacting a polycarbonate polyol or the like alone or with a mixture with an organic diisocyanate, and can be obtained by extending a chain with a compound having two active hydrogens if necessary.
[0021]
In the present invention, the polyurethane resin is mixed, but it is preferable to mix those having a difference in coagulation value of 0.5 or more, and two types of polyurethane resins having a difference in coagulation value of 1.0 or more are mixed. It is more preferable to mix the above. If the difference in coagulation value is less than 0.5, it becomes difficult to flatten the hydrophobic polyurethane resin on the skin side as described above, and it becomes difficult to obtain the intended coating fabric. At this time, the fiber fabric is preferably subjected to water repellent treatment.
[0022]
Examples of the polyalkylene ether glycol include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, glycerin propylene oxide adduct, polyether polyol having an ethylene end added to the terminal, and vinyl monomer grafted polyether polyol. Polyester polyols include ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol and other alkylene glycol acids and succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid It is preferable to give them by reacting with a carboxylic acid such as trimellitic acid so that the terminal is a hydroxyl acid, but there is no particular limitation.
[0023]
Next, organic diisocyanates include 2,4- and 2,6-toluylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate and other aromatic isocyanates, 1,6-hexamethylene. There are aliphatic isocyanates such as diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 3-isocyanate methyl-3,5,5′-trimethylcyclohexyl isocyanate, 2,6-diisocyanate methylcaproate, and these are used alone or You may mix and use.
[0024]
Chain extenders include hydrazine, ethylenediamine, tetramethylenediamine, water, piperazine, isophoronediamine, ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, or dimethylolpropionic acid, aminoethane. Glycols and diamines that can improve hydrophilicity, such as ethylene oxide adducts to sulfonic acid, can be used alone or in combination.
[0025]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited to these at all. In addition, the measurement of the characteristic value in an Example is as follows.
[0026]
(A) Moisture permeability Measured by JIS L 1099 B-1 method (potassium acetate method) and displayed in terms of 24 hours.
[0027]
(B) Water pressure resistance Measured by the JIS L 1092 B method.
[0028]
(C) Temperature / humidity perspiration simulation measuring device in clothes (manufactured by Toyobo Co., Ltd.), water supply: 245 g / m ² · h, hot plate temperature: 37 ° C., sample-hot plate distance: 1 cm, environmental temperature and humidity ： 15 ℃ × 50% RH, Sweating pattern: 10 minutes stable → 10 minutes sweat → Stop for 10 minutes, measure the temperature and humidity in the clothes with a sweat simulation device (skin model method) when sweating for 10 minutes The temperature reached and the maximum humidity reached in the clothes were determined.
[0029]
(D) Condensation amount Using the above sweating simulation measuring device, water supply amount: 560 g / m ² · h, hot plate temperature: 37 ° C., sample-hot plate distance: 3 cm, environmental temperature and humidity: 10 ° C. × 50% RH, Sweating pattern: Condensation measurement is performed with 5 minutes preliminary sweating → 15 minutes sample mounting sweating → 15 minutes sweating stop. The amount of condensation is determined by wiping the film surface with Kim Towel (R), measuring the weight of Kim Towel (R), and calculating from the increased weight. The unit is g / m ² · 15min, which is converted to 1 hour.
[0030]
(Example 1)
A raw material fine particle aqueous dispersion composed of 450 parts of acrylonitrile, 40 parts of methyl acrylate, 16 parts of p-styrene sulfonic acid soda and 118 parts of water was crosslinked with hydrazine and hydrolyzed with NaOH. Hygroscopic organic fine particles (Na salt type carboxyl group 5.4 mmol / g) having a swelling degree of 80% were obtained.
[0031]
Next, the following urethane resin solution was prepared.
Ester polyurethane resin (solid content 32%) 75 parts ether polyurethane resin (solid content 35%) 35 parts N, N'-dimethylformamide 20 parts Hygroscopic organic fine particles 10 parts Coronate HL 3 parts Ester polyurethane The coagulation value of the resin was 9.5, and the coagulation value of the ether polyurethane resin was 8.0.
[0032]
Using this urethane resin solution, a coated fabric was processed according to the following procedure. Nylon fabric (yarn use: 78 dtex, 96 filaments) with a density of 182 warps / inch and weft 110 feet / inch, refined, dyed, and water-repellent treatment (Fluorine water repellent Asahi Guard) LS375 was dipped at 160 ° C. and dried at 180 ° C.), and after the drying, the above urethane resin processing solution was coated using a knife over roll coater. This was introduced into water at 15 ° C., solidified for 3 minutes, and then dried in an oven at 130 ° C. to obtain a microporous film having a resin thickness of 70 μm. The resulting coated fabric had a water pressure resistance of 10,000 mmH ₂ O, a moisture permeability of 16000 g / m ² · 24 hrs, a dew amount of 5 g / m ² · hr, and a friction coefficient of 0.30. Further, the temperature inside the clothes by the sweating simulation apparatus was 33 ° C., and the humidity inside the clothes was 57% RH.
[0033]
(Comparative Example 1)
The following urethane resin solution was prepared.
Ester polyurethane resin (solid content 32%) 65 parts Low polymerization degree ester polyurethane resin (solid content 35%) 45 parts N, N'-dimethylformamide 15 parts Hygroscopic organic fine particles identical to those described in Example 1 10 parts Coronate HL 3 parts The solidification value of the ester polyurethane resin was 9.5, and the solidification value of the ether polyurethane resin was 9.8. The resulting coated fabric had a water pressure resistance of 7500 mmH ₂ O, a moisture permeability of 13000 g / m ² · 24 hrs, a condensation amount of 9 g / m ² · hr, and a friction coefficient of 0.70. In addition, the temperature in the clothes by the sweat simulation apparatus was 36 ° C., and the humidity in the clothes was 82% RH.
[0034]
【The invention's effect】
According to the present invention, it is possible to obtain a coated fabric that provides a comfortable wearing feeling having high moisture permeability that maintains a comfortable temperature and humidity in clothes even when sweating and water pressure that provides high waterproof performance. became.

Claims (3)

On the fiber fabric that has been subjected to water repellent treatment before the coating process , the ether polyurethane resin and the ester polyurethane resin are included, and the coagulation value of the ether polyurethane resin is smaller than the coagulation value of the ester polyurethane resin. Organic fine particles comprising two or more types of polyurethane resins, each polyurethane resin having a coagulation value in the range of 5 to 12, and each polyurethane resin having a coagulation value difference of 0.5 or more, and having moisture absorption and desorption exothermic properties there is formed a resin layer ing is contained in, and smoothness of the resin layer, a 0.42 a der Ru coated fabric less friction coefficient obtained by the friction tester, moisture permeability with potassium acetate method 15000g ^/ m 2 · 24hrs or more, water pressure resistance 5000mmH ₂ O or more, in clothes up by perspiration simulator measurement Coating fabric, characterized in that reaches temperatures and clothes in ultimate maximum humidity at 34 ° C. or less 30 ° C. or more is less than RH 65%. Moisture absorption and desorption exothermic organic fine particles are introduced into the acrylonitrile-based polymer containing 50% by weight or more of acrylonitrile by introducing a crosslinked structure by hydrazine, divinylbenzene or triallyl isocyanurate treatment, and the remaining nitrile group is converted into a salt by hydrolysis. be those was allowed chemical converted to the type carboxyl group, the coating fabric of claim 1, wherein the organic fine particles der Rukoto having salt-type carboxyl group 1.0 mmol / g or more. Moisture permeability with potassium acetate method is 15000 g ^/ m 2 · 24hrs or more 40000 g ^/ m 2 · 24hrs or less, coating of claim 1 or 2 water pressure is characterized by the following der Rukoto 10000MmH ₂ O or more 35000MmH ₂ O Fabric.