JPH07292576A - Moisture-permeable waterproof coating cloth having soft feeling - Google Patents

Abstract

PURPOSE:To produce moisture-permeable waterproof soft cloth by wet-coating textile cloth with a solution of a synthetic polymer composed mainly of a polyurethane resin and containing inorganic fine particles having a specific particle diameter and a plasticizer at a specific ratio. CONSTITUTION:A highly moisture-permeable and waterproofing coated cloth having a moisture permeability of 26,000g/m<2>/24hr, a waterpressure resistance of >=0.6kg/cm<2> and soft feeling is-produced by coating textile cloth composed of a blended synthetic fiber, semisynthetic fiber or natural fiber with a solution of a synthetic resin composed mainly of a polyurethane resin and containing 1-40wt.% of inorganic fine powder (preferably silicon dioxide fine powder) having an average particle diameter of >=1mum and an N,N-dimethylformamide adsorption of >=200mL/100g and 1-25wt.% of a plasticizer (preferably a phthalic acid ester derivative) and coagulating the applied layer in wet state. The peeling resistance between the resin and the textile cloth can be improved by adding an isocyanate compound to the treating liquid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture permeable and waterproof coated cloth having a soft texture and excellent moisture permeability and waterproof performance, which is used for various kinds of clothes such as sports cold rain clothes, general rain clothes, and cold clothes. Is.

[0002]

2. Description of the Related Art Conventionally, it has been known that a coated cloth obtained by a wet or dry coating method has a resin layer with a hole and a resin layer without a hole. Generally, when the resin layer is perforated, excellent moisture permeation performance is easily obtained, but waterproof performance tends to be insufficient. Conversely, when the resin layer is non-perforated, excellent water permeation performance is easily obtained. Wetting performance tends to be insufficient. For example, the coated fabric obtained by the wet coating process of polyurethane resin is originally excellent in waterproof performance, but insufficient in moisture permeability,
Anionic surfactants, nonionic surfactants, hydrophilic polymers, etc. are usually used together to improve the moisture permeability. However, even though the moisture permeability of the obtained coated fabric is sufficient, the waterproof performance is considerably reduced, and as a result, both cannot satisfy the sufficient performance.

In recent years, for the purpose of compensating for both defects, a highly moisture-permeable resin layer having pores is first formed on a fiber cloth, and then a resin layer having no pores is formed on the resin layer to obtain excellent permeability. Attempts have been made to obtain wet performance and waterproof performance, but in this method, a highly moisture-permeable resin layer having pores is at most 5000-6000 g even by the wet method.
Since only a moisture permeability of about / m ² / 24hrs is obtained, even if a non-porous resin layer is applied thinly next time, the moisture permeability is extremely reduced, resulting in excellent moisture permeability. At present, it is difficult to achieve both waterproof performance. Further, in this case, coating is performed twice, which is also disadvantageous in terms of processing cost.

On the other hand, in Japanese Patent Laid-Open No. 58-4873 and Japanese Patent Publication No. 62-53632, the average particle diameter of which the main component is silicon dioxide is 2 to 50 μm and the total pore volume is 0.2 to 0.2.
A processing method has been proposed in which a polyurethane resin film containing 5 ml / g of porous particles is formed, and then a water repellent having a perfluoroalkyl group is added to obtain a moisture-permeable waterproof fabric. However, even in this method, the moisture permeability is at most 3000g / m ² / 24hrs approximately, sufficient moisture permeability can not be obtained.

Further, in Japanese Patent Laid-Open No. 2-251672, there are fine holes smaller than 150Å and a surface area of 20
A method for processing a polyester-coated cloth having a resin layer in which inorganic porous particles of 0 m ² / g or more, such as silicon dioxide and titanium oxide, are layered and dispersed at a high concentration has been proposed. It only prevents migration of the dye, and does not have sufficient moisture permeability. Therefore, the inventors of the present invention previously disclosed in JP-A-5-222677 that a perforated resin layer made of a synthetic polymer mainly composed of a polyurethane resin was provided on a fiber cloth, and the resin layer was substantially free from the resin layer. Contains 1% or more of inorganic fine powder with an average particle size of 0.1 μm in the pores,
Water vapor transmission rate of 6000g / m ² / 24hrs or more and 0.6 kg / cm
We proposed a moisture-permeable and waterproof coating fabric with a water pressure resistance of ² or more. Although this coated fabric has excellent moisture permeability and waterproof properties, it has the drawback of having a slightly hard texture because it contains inorganic fine powder in the coating resin layer.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent moisture permeability and waterproof performance, and a moisture permeable waterproof having a soft texture. The purpose of the present invention is to obtain a functional coating fabric.

[0007]

The present invention achieves the above object and has the following structure. That is,
The present invention has a perforated resin layer made of a synthetic polymer mainly composed of polyurethane resin on a fiber cloth, and the average particle diameter is 1 μm or less in the resin layer and the adsorption amount of N, N-dimethylformamide is the inorganic fine powder of more than 200 ml / 100 g 1 to 40 wt%, and a plasticizer containing 1 to 25 wt%, 6000g / m ² / 24hrs or more moisture permeability and 0.
The gist of the present invention is a moisture-permeable waterproof coating fabric having a soft texture, which has a water pressure resistance of 6 kg / cm ² or more.

The present invention will be described in detail below.

The fiber cloth used in the present invention includes polyamide synthetic fibers represented by nylon 6 and nylon 66, polyester synthetic fibers represented by polyethylene terephthalate, polyacrylonitrile synthetic fibers,
Woven and knitted fabrics made of polyvinyl alcohol synthetic fibers, semi-synthetic fibers such as triacetate, or mixed fibers such as nylon 6 / cotton, polyethylene terephthalate / cotton, etc.
Nonwoven fabrics and the like can be mentioned.

In the present invention, the above-mentioned fiber cloth treated with a water repellent may be used. This is one means for preventing the penetration of the resin solution into the fabric during manufacturing. In this case, the water repellent may be a known one such as a paraffin water repellent, a polysiloxane water repellent, or a fluorine water repellent, and the treatment thereof is also a commonly used padding method, spray method, or the like. The known method may be used. When particularly good water repellency is required, a fluorine-based water repellent is used. For example, Asahi Guard 730 (Asahi Glass Co., Ltd., fluorine-based water repellent emulsion) is padded (squeezed) with a 5% aqueous dispersion. The heat treatment at 160 ° C. for 1 minute, and the like.

In the present invention, a perforated resin layer made of a synthetic polymer mainly composed of a polyurethane resin is provided on the above-mentioned fiber cloth, and the average particle diameter is 1 μm or less and N, N -Containing 1 to 40% by weight of an inorganic fine powder having an adsorption amount of dimethylformamide of 200 ml / 100 g or more and 1 to 25% by weight of a plasticizer.

The inorganic fine powder used here is an inorganic fine powder pulverized by a usual wet pulverization method or a ball mill pulverization method, a gas phase oxidation method of a metal halide, a combustion hydrolysis method, an electric arc method, etc. The metal oxide fine powder obtained by the dry method can be mentioned, and the silicon dioxide fine powder produced by these methods can be mentioned as a representative. The fine powder obtained by these methods generally has a particle size of 0.05 μm or less and at the same time has a very large amount of N, N-dimethylformamide adsorbed, and can be added to a synthetic polymer resin solution. It is suitable as an inorganic fine powder. Furthermore, if the surface of the fine powder is modified to be hydrophobic, it is more preferable from the viewpoint of water leakage, and it is preferable that the fine powder is substantially ineffective.

As used herein, the amount of N, N-dimethylformamide adsorbed means that 5 g of inorganic fine powder is placed on a glass plate,
Every time one drop of N, N-dimethylformamide was dropped, the work of kneading was repeated using a spatula made of stainless steel, and N, N-dimethyl required until just before one drop of N, N-dimethylformamide suddenly became soft. It means the volume of formamide (unit: milliliter).
This is the one in which N, N-dimethylformamide was used instead of the oil of SK-5101 boiled linseed.

The inorganic fine powder used in the present invention is required to have an average particle size of 1 μm or less, and N, N-
Adsorption amount of dimethylformamide is 200ml / 1
It is necessary to be more than 00g, the average particle size is less than 0.1μm, and 250ml / 10
A substance having an adsorption amount of N, N-dimethylformamide of 0 g or more is more preferable in terms of the effect of the present invention. If the average particle size exceeds 1 μm, the fine pore size of the moisture permeable membrane of the resulting coated fabric becomes too large and the waterproof performance deteriorates, which is not preferable, and the amount of N, N-dimethylformamide adsorbed is 200 ml / 100.
If it is less than g, the number of fine pores in the moisture permeable membrane decreases, and high moisture permeability cannot be obtained, which is not preferable.

It is necessary that the inorganic fine powder used in the present invention is uniformly contained in an amount of 1 to 40% by weight, more preferably 3 to 30% by weight, based on the resin layer composed of a synthetic polymer mainly composed of polyurethane resin. It is better to contain%. When it is less than 1% by weight, the number of fine pores of the moisture permeable membrane of the obtained coated fabric is small and high moisture permeability cannot be obtained. When it exceeds 40% by weight, the resin membrane becomes weak and cannot be practically used.

The fine inorganic powder does not necessarily have to be highly pure, and may contain other inorganic substances such as pigments and fillers as impurities.

Examples of the plasticizer usable in the present invention include phthalic acid ester type plasticizers such as dimethyl phthalate, dibutyl phthalate and dioctyl phthalate, and aromatic carboxylic acid ester type plasticizers such as trioctyl trimellitate and diethylene glycol dibenzoate. Plasticizer, dioctyl succinate,
Fatty acid dibasic acid ester plasticizer such as dioctyl adipate, fatty acid ester derivative such as butyl oleate, pentaerythritol ester, tricresyl phosphate, phosphate ester plasticizer such as triphenyl phosphate, butyl epoxy stearate, epoxy Epoxy plasticizer such as octyl stearate, polypropylene adipate,
Polyester plasticizer such as polypropylene sebacate,
Although there are chlorine-containing plasticizers such as chlorinated diphenyl and methyl chlorinated fatty acid, the phthalate derivative compound represented by the following chemical formula 1 is most effective in the present invention.

[0018]

[Chemical 1]

As the phthalate derivative compound,
As mentioned above, dimethyl phthalate, dibutyl phthalate,
Dioctyl phthalate and the like can be mentioned. However, in the above chemical formula 1, when n is 11 or more, the affinity for the polyurethane resin is lowered and the plasticizing efficiency is also deteriorated. Therefore, n is required to be 10 or less. The phthalate ester derivative compound is 1 to the polyurethane resin layer.
It is desirable to use it in a proportion of 25% by weight. When the amount used is less than 1% by weight, the plasticizing effect on the polyurethane resin is poor, and when it is 25% by weight or more, good microcells are not formed during the formation of the polyurethane resin film and the moisture permeability is impaired.

In the coated cloth of the present invention, a solution of a synthetic polymer mainly composed of a polyurethane resin containing inorganic fine powder and a plasticizer is applied onto the above-mentioned fiber cloth by a wet coating method. The term "polyurethane resin-based synthetic polymer" as used herein means a polyurethane component of 50 to 100% by weight.
Other synthetic polymers include, for example, polyacrylic acid, polyvinyl chloride, polystyrene,
It suffices that the content of polybutadiene, polyamino acid or the like or a copolymer thereof be less than 50% by weight, and of course, a compound modified with fluorine or silicon can be used in the present invention.

The polyurethane resin is a copolymer obtained by reacting an isocyanate with a polyol, and aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate are used alone or as a mixture thereof as an isocyanate component. 2,4
-Diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexanediisocyanate, 1,4-cyclohexanediisocyanate, etc. are used, and as the polyol component, polyether polyol or polyester polyol is used, and the polyether polyol is polyethylene. Glycol, polypropylene glycol, polytetramethylene glycol, etc. are used. 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 ring-opening polymers such as caprolactone. To use.

The polyurethane polymer-based synthetic polymer solution containing the inorganic fine powder and the plasticizer is prepared by a conventional coating method such as knife coater, comma coater,
It may be coated appropriately using a reversing machine, but in order to obtain the desired water pressure resistance of 0.6 kg / cm ² or more, the smoothness of the coated surface of the fiber cloth and the air permeability (JIS L-1096 method) ), But generally the resin film weight is 5 g / m ² or more, preferably 10 g
It is advisable to adjust the coating amount so that the coating amount is not less than / m ² and perform coating.

In the present invention, for the purpose of improving the peel resistance between the resin layer and the fiber cloth, a compound having a high affinity with the resin or the fiber cloth may be used in combination, and an isocyanate compound may be used in combination as the compound. . As the isocyanate compound, 2,4-tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate or a compound containing 3 mol of these diisocyanates and active hydrogen (eg, trimethylolpropane, glycerin, etc.) 1
Triisocyanates obtained by addition reaction with moles can be used. The above isocyanates may be in a form in which the isocyanate group is free, or may be in a form in which the block is dissociated by the subsequent heat treatment, which is stabilized by adding phenol, methylethylketoxime and the like, It may be properly used depending on workability and purpose.

The amount of the isocyanate compound used is preferably 0.1 to 10% by weight based on the synthetic polymer mainly composed of the polyurethane resin.
If the amount used is less than 0.1% by weight, the adhesive strength of the resin layer to the fabric is low, and if it exceeds 10% by weight, the texture tends to harden, which is not preferable.

In the present invention, after the resin liquid consisting of the synthetic polymer mainly composed of polyurethane as described above is applied to the fiber cloth, it is immersed in water at 0 to 30 ° C. for 0.5 to 10 minutes to wet solidify the resin. To do. Below, in warm water of 40-60 ° C
After washing for 15 minutes, it is dried by a usual method.

In the present invention, for the purpose of further improving the waterproof property, the coated cloth may be subjected to a water repellent treatment after the wet coating. For the water repellent treatment, the well-known water repellent treatment method that is generally carried out as described above may be adopted. Further, when it is desired to further improve the waterproof performance, a dry film thickness of 0.5 on the wet coating layer of the present invention.
A non-porous polyurethane resin layer or the like having a thickness of about 2 μm may be formed. Since the wet coating layer has high water pressure resistance, the waterproof performance is synergistically improved even with a thin film, and the moisture permeability is not significantly reduced.

The present invention is constituted as described above. According to the present invention, there is provided a moisture permeable and waterproof coating fabric having excellent moisture permeability and waterproof performance and having a soft texture. Obtainable.

[0028]

[Working] The moisture-permeable and waterproof coating cloth of the present invention has an average particle size of 1 μm or less and an N, N-dimethylformamide adsorption amount of 200 ml / in a resin layer of a synthetic polymer mainly composed of polyurethane resin. By containing 100 g or more of inorganic fine powder and a plasticizer, excellent moisture permeability and waterproof performance and a soft texture are imparted.

The reason is that the average particle size is 1 μm or less, and N,
Although it has not been clearly clarified whether excellent moisture permeability and waterproof performance can be obtained at the same time by containing an inorganic fine powder having an adsorption amount of N-dimethylformamide of 200 ml / 100 g or more, the present inventor Have speculated as follows.

That is, a cloth is coated with a synthetic polymer solution mainly composed of a polyurethane resin in which an inorganic fine powder having an average particle diameter of 1 μm or less and an adsorption amount of N, N-dimethylformamide of 200 ml / 100 g or more is uniformly dispersed. When wet coagulation is carried out, water as a coagulating liquid and N, N-dimethylformamide as a resin solvent are mixed, and the resin is coagulated due to the rapid separation of the solvent from the resin liquid. The average particle size is 1 μm or less, and N,
When the inorganic fine powder having an adsorption amount of N-dimethylformamide of 200 ml / 100 g or more is uniformly dispersed in the resin solution, the surface of the inorganic fine powder is more likely to have N, N in the resin solution than other portions. -The concentration of dimethylformamide is high, in other words, the concentration of the synthetic polymer mainly composed of polyurethane resin is low. Therefore, in the wet coagulation process, the water as the coagulating liquid first becomes N,
It replaces N-dimethylformamide and solidifies rapidly around the inorganic fine powder, after which the entire resin solidifies, resulting in a faster solidification rate, and in addition to the honeycomb structure peculiar to urethane resin, fine particles of 1 μm or less It is speculated that it will be a very porous morphology with numerous holes.

In the present invention, excellent waterproofness is exhibited due to the fineness of the formed fine pores, and high moisture permeability is exhibited due to the innumerable minute pores, which is characteristic of a highly moisture-permeable waterproof fabric. However, it is also very effective for water leakage, which tends to cause problems when pressure is applied during wearing. Further, since the inorganic fine powder of the present invention is present uniformly from the surface layer to the lower layer of the resin layer, the resin layer surface eliminates the slimy feeling peculiar to the polyurethane resin to give a dry touch and the abrasion resistance of the entire resin layer. And improves the adhesive strength.

Further, when the plasticizer is uniformly dispersed in the polyurethane resin film as in the present invention, the polar portion of the plasticizer molecule is strongly oriented to the polar portion of the polyurethane resin molecular chain, the polar point is shielded, and the polyurethane resin It is speculated that the distance between the molecular chains widens and the movement of the molecular chains becomes easier, resulting in flexibility and soft texture.

[0033]

EXAMPLES The method for producing the coated fabric of the present invention will be specifically described below with reference to Examples. The performance of the coated fabric in the Examples was measured by the following method. (1) Water pressure resistance JIS L-1092 (high water pressure method) (2) Water vapor permeability JIS L-1099 (A-1 method) (3) Water repellency JIS L-1096 (spray method) (4) Texture Bending by KES method Rigidity measurement By handling, the texture was evaluated relatively in the following three stages. ○ Flexible △ Slightly hard × Hard

Example 1 First, a plain fabric (taffeta) having a warp density of 120 / inch and a weft density of 90 / inch using nylon multifilament 70 denier / 34 filaments for both warp and weft was prepared as a base fabric. Then, after performing scouring and dyeing with an acid dye (manufactured by Mitsubishi Kasei Co., Ltd., acid dye Diacid Fast Red 3BL 2% owf) by a conventional method, a fluorine-based water repellent emulsion Asahi Guard 710 (Asahi Glass Co., Ltd. Padding with a 5% water dispersion (made by the company) (squeeze ratio 35
%) And dried, and then heat-treated at 160 ° C. for 1 minute. Next, using a calendering machine having a mirror surface roll, calendering was performed under the conditions of a temperature of 160 ° C., a pressure of 30 kg / cm, and a speed of 20 m / min to obtain a base fabric for coating.

Here, a polyurethane resin solution having a resin solid content concentration of 26% shown in the following Formulation 1 was applied to the calendar surface of the above-mentioned base cloth by using a knife over roll coater in an amount of 10
Immediately after application at 0 g / m ²
The resin component was solidified by immersing for 2 seconds, followed by washing in warm water at 50 ° C. for 10 minutes and drying to form a resin layer containing 9% by weight of inorganic fine powder and 9% by weight of plasticizer. Prescription 1 Lax Skin 1740-29B 100 parts (Seiko Chemical Co., Ltd., ester type polyurethane resin) Resamine X-100 1 part (Dainichi Seika Chemicals Co., Ltd., isocyanate compound) N, N-dimethylformamide 25 parts Aerosil R- 972 3 parts (manufactured by Nippon Aerosil Co., Ltd., average particle size 0.016 μm,
N, N-dimethylformamide adsorption amount 350 ml / 100 g of hydrophobic silicon dioxide fine powder) Dibutyl phthalate 3 parts

Here, the solvent type fluorine-based water repellent A is applied to the cloth.
A 5% mineral terpene solution of G-570 (manufactured by Asahi Glass Co., Ltd.) is padded (squeeze ratio of 40%), dried, and then finished set at 170 ° C. for 40 seconds in a tenter to give a moisture-permeable waterproof coating of the present invention. A cloth was obtained.

For comparison with the present invention, a moisture-permeable waterproof coated fabric for comparison (Comparative Example 1) was prepared in the same manner as in Example 1, except that dibutyl phthalate was omitted from Formulation 1 in Example 1. I got).

The performances of the present invention and the coated fabric for comparison were measured and evaluated, and the results are also shown in Table 1.

[Table 1]

As is clear from Table 1, the moisture-permeable and waterproof coating fabric of the present invention had excellent water pressure resistance and moisture permeability, and also had a soft texture.

Example 2 A plain fabric having a warp density of 110 yarns / inch and a weft yarn density of 95 yarns / inch was prepared by using a polyester multifilament 75 denier / 72 filaments capable of dyeing a cationic dye for both the warp yarns and the weft yarns. Scouring and dyeing (Kayacryl Blue GSL-E manufactured by Nippon Kayaku Co., Ltd., basic dye)
D 1.5% owf), followed by padding with a 5% aqueous dispersion of a fluorine-based water repellent emulsion Asahi Guard 710 (manufactured by Asahi Glass Co., Ltd.) (squeezing rate 40%), and after drying, 160 ° C.
Was heat-treated for 1 minute. Next, using a calendering machine with a mirror surface roll, the temperature was 180 ° C and the pressure was 30 kg /
Calendering is performed under the conditions of cm ² and speed of 35 m / min.
A base fabric for coating was obtained.

Here, a polyurethane resin solution having a resin solid content of 26% having the composition shown in the following Formulation 2 was applied to the calendar surface of the above-mentioned base cloth at a coating amount of 100 g / m ² using a knife over roll coater. Immediately after, immerse in 15 ℃ water for 40 seconds to solidify the resin component, then 50 ℃
Was washed in warm water for 10 minutes and dried to form a resin layer containing 11% by weight of inorganic fine powder and 11% by weight of a plasticizer. Prescription 2 LUX SKIN 1740-29B 100 parts (Seiko Chemical Co., Ltd., ester type polyurethane resin) Resamine X-100 1 part (Dainichi Seika Chemicals Co., Ltd., isocyanate compound) N, N-dimethylformamide 30 parts Alumina AKP- G015 4 parts (Sumitomo Chemical Co., Ltd., average particle size 0.03 μm, N,
N-dimethylformamide adsorption amount 310 ml /
100 g of hydrophobic dialuminum trioxide fine powder) Dioctyl phthalate 4 parts

Here, the solvent type fluorine-based water repellent A is applied to the above cloth.
A 5% mineral terpene solution of G-570 (manufactured by Asahi Glass Co., Ltd.) is padded (squeeze ratio of 40%), dried, and then finished set at 180 ° C. for 40 seconds with a tenter to give a moisture-permeable waterproof coating of the present invention. A cloth was obtained.

For comparison with the present invention, the amount of dioctyl phthalate in formulation 2 in this example was 0.1 parts, except that
Using the same method as in this example, 0.3% by weight of plasticizer was added.
A moisture-permeable and waterproof coating fabric for comparison (containing Comparative Example 2) was obtained. Also, for comparison with the present invention, a formulation containing 31% by weight of a plasticizer was prepared in the same manner as in this example except that the amount of dioctyl phthalate in Formulation 2 in this example was 15 parts. A moisture-permeable waterproof coating fabric (referred to as Comparative Example 2) was obtained.

The performances of the present invention and the coated fabric for comparison were measured and evaluated, and the results are also shown in Table 2.

[Table 2]

As is clear from Table 2, the moisture-permeable and waterproof coating fabric of the present invention had excellent water pressure resistance and moisture permeability, and also had a soft texture.

[0046]

According to the present invention, it is possible to obtain a moisture-permeable waterproof coated fabric having excellent moisture permeability and excellent waterproof performance, and yet having a soft texture. According to the present invention, since high performance can be obtained in terms of both moisture permeability and waterproof property only by wet coating, it can be manufactured at low cost and is industrially very advantageous. The excellent performance of the coated fabric of the present invention makes it a material suitable for clothing such as rain clothing and outdoor sportswear.

Claims (1)

[Claims] 1. A fiber cloth having a perforated resin layer made of a synthetic polymer mainly composed of a polyurethane resin, wherein the resin layer has an average particle diameter of 1 μm or less, and an adsorption amount of N, N-dimethylformamide. 1 to 40% by weight of inorganic fine powder of 200 ml / 100 g or more, and 1 to 25 of plasticizer
Containing by weight%, 6000g / m ² / 24hrs or more moisture permeability and 0.6 kg / cm ² or more moisture-permeable waterproof coating fabric soft feeling characterized by having a water pressure resistance.