JPS6163777A - Production of hygroscopic water-proof cloth - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a moisture permeable waterproof fabric with excellent adhesive strength between a coating resin layer and a fiber layer. Generally, moisture permeability and waterproofness are contradictory functions, but waterproof fabrics with excellent moisture permeability form continuous micropores that allow water vapor to escape in the coating resin film during dry or wet coating processing. It is obtained by letting Polyurethane elastomers are generally preferably used as coating resins during these dry or wet coating processes 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 is
IS L-1096 water pressure measurement: 1.500mm
(below the water column) for fabrics with a moisture permeability of 4.000
~5.000glrd・24hrs (JIS
At present, only the same level as Z-0208 measurement) has been obtained. This moisture permeability level is 7,000g/d・
If I can improve it to 24hrs or more.

It has almost the same moisture permeability as non-coated fabric, which is simply a high-density fabric using ultra-fine filaments in the warp and warp that is water-repellent and calendered, so it can be used when working in the rain or exercising. The humidity inside the clothes due to sweating becomes smoother, making it possible to perform even more strenuous exercise or work comfortably. n
? - The reality is that a fabric with a moisture permeability of 24 hours or more has not yet been obtained to this day. Also,
Coated fabric consists of a base fabric and a resin layer,
Especially when the base fabric is made of polyester synthetic fiber.

It has the disadvantage that the base fabric and the resin layer tend to peel off due to "scratching" when worn or when washed. The present invention was developed in view of the current situation, and has a water pressure resistance of 1,500 m.
Moisture permeability is 7,000g/d・24hr even though it is more than m
The purpose of this invention is to obtain a fabric that has high moisture permeability of s 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-permeable waterproof fabric, which is characterized by applying a resin solution, followed by immersion in water, hot water washing, and drying, and applying a water-reducing agent as a final step following the above configuration. The gist of this paper is a method for manufacturing a moisture-permeable waterproof fabric.

Two aspects of the present invention will be described 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. A textile mainly made of

It refers to knitted fabrics, non-woven fabrics, etc., and also includes those obtained by blending or interweaving the above-mentioned polynis-chill synthetic fibers with other natural fibers and 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, as a first step, a resin solution mainly containing a polyester resin, a polyamino acid urethane resin, and a polar organic solvent is applied to a fiber fabric such as a knitted fabric,
Soak this in water and wash with hot water.

dry.

The polyester resins used here include diols such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, and polytetramethylene glycol, and isophthalic acid, terephthanic acid, adipic acid, sebacic acid, etc. Examples include polymerization reaction products with aromatic dicarboxylic acids and aliphatic dicarboxylic acids, ring-opening polymers of lactone, etc. The diol component and acid component are selected so that the polymer is amorphous, and a polar organic solvent is used. prepared in such a way that it dissolves in For example, polyester having a molecular weight of 20,000 to 30,000 is preferably used, which is obtained by polymerizing terephthalic acid and sepathic acid as acid components and ethylene glycol and neopentyl glycol as diol components.

Polyamino acid urethane resin (hereinafter referred to as PAU) used in the present invention
It's called resin. ) is a copolymer consisting of amino acids and polyurethane, and the amino acids include OL-alanine 1
L-aspartic acid, L-cystine, L-glutamic acid, glycine, L-lysine.

Examples include 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) obtained from amino acids and phosgene is used.
Carboxylic acid anhydride is called NCA. ) is commonly used. The isocyanate component of polyurethane is aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate, singly or in combination. Examples include 4-cyclohexane diisocyanate. In addition, the polyol component is polyether polyol.

Polyester polyols are used. 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 sepatic 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.

As described above, PAD resins are obtained by adding amines to the reaction system of various amino acids NC^ and urethane prepolymers having isocyanate groups at the terminals. The PAD
As the amino acid component constituting the resin, optically active γ-alkyl-glutamate-NCA is preferably used from the viewpoint of film performance, and among the optically active T-alkyl-glutamates, γ-methyl-L-glutamate-NCA is preferably used from the viewpoint of price and film properties. Alternatively, T-methyl-D-glutamate is often freely selected as the amino acid component of the PAD resin. 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 optically active γ-alkyl glutamic acid)-NCA and a urethane prepolymer among PAD resins is preferably used. Solvent system, for example, a mixed solvent system of dimethylformamide and dioxane, with a weight ratio of amino acid and urethane of 90:10 to 10:
This is because the above-mentioned weight ratio can be freely selected while taking into consideration the physical properties of the film required to obtain a uniform resin solution over a wide range of 90%.

Examples of the polar organic solvent used in the present invention include N-N-dimethylformamide and dimethylacetamide.

Examples include N-methylpyrrolidone and hexamethylenephosphonamide.

In the first step in the method of the present invention, the above-mentioned polyester resin, PAD resin, and polar organic solvent are mixed and used.

The blending ratio of polyester resin to PAD 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, making it unsuitable for practical use, and vice versa. If the amount is too high, the resin film will be deformed by heating, causing a practical problem. The most desirable blending ratio is 100:5-10
This is the case in the range of 0:50. 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. This step forms a PAU resin film having countless pores.

The water temperature when immersing the fabric 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 will become large (and the water pressure resistance will be 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 PAIJ resin film will not be obtained.

After coagulating 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.
It may be carried out for 3 minutes or more at a temperature of °C.

After washing with hot water, dry.

Next, in the method of the present invention, as a second step, a polyurethane resin, a nonionic surfactant,
At least one of anionic surfactants, hydrophilic polymers, isocyanate compounds, and inorganic fillers and PA
A resin solution consisting mainly of U resin and a polar organic solvent is applied, and this is 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 aliphatic and aromatic polyisocyanates can be used, such as hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and xylene diisocyanate.

and reaction products of excess thereof and polyhydric alcohols. 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.

Examples include polypropylene glycol and polytetramethylene glycol.

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 alcohol. Examples include fatty acid esters, fatty acid sucrose esters, alkylo-doamides, and any 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. .

Alternatively, any mixture of these can be fried.

Polyvinylpyrrolidone is a hydrophilic polymer.

Polymers that can be dissolved, dispersed, or emulsified in a polar organic solvent and can be dissolved in water, such as polyacrylic acid, polyacrylic ester, carboxyvinyl polymer organic amine, and polyethyleneimine, can be used.

Further, as the isocyanate compound, known fatty acids and aromatic isocyanates can be used.

Inorganic fillers include powders of silicic acid, mica, talc, calcium silicate, diatomaceous earth, and kaolin.

Generally known fillers such as clay such as bentonite, shirasu balloons, glass balloons, 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, a, aqueous polymer, isocyanate compound, and inorganic filler, PAυ resin and polar A resin solution made of an organic solvent is used as the coating solution, and the PAD resin and polar organic solvent used here may be the same as those used in the first step of the present invention.

The above-mentioned nonionic surfactants, 2 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 0.1-1 for PAD resin
0%, in the case of urethane resin, 0.3 to PAU resin
6%, 0.05 for PAU resin in case of hydrophilic polymer
It is desirable that it be in the range of ~5%. If the amount of these micropore-forming agents used is less than the above range relative to the PAD resin, the pores of the PAU resin film will become too small, making it difficult to obtain interconnected microcells, resulting in poor moisture permeability. In addition, if the amount exceeds the above range, the pores will generally become too large, although it will also be affected by the coagulation bath temperature during wet film formation.
Water pressure resistance of 00 mm or more cannot be obtained.

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, the PAU resin solidifies faster than the urethane resin, so a space is created at the boundary between the PAD resin and the urethane resin, and this space forms a part of the resin film. Determine the size of the pores inside. When the amount of urethane is small, the space is small and therefore the pores are 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 hydrophilic polymer component exists 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.

As a result, water pressure resistance becomes low. In the present invention, a PAD resin film having countless pores can be formed by applying the above-mentioned mixed resin solution to a fiber fabric and then immersing it in water. Due to the action of the forming agent, pores with an interconnected microcellular structure are obtained.

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 advantages of the combined effect. For example, by using a nonionic surfactant or an anionic surfactant together with a urethane resin, the stability of the PAtl resin and the urethane resin is increased, coating properties are improved, and a smooth coated 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 by a conventional coating method to a thickness of 10 to 200 μm.
The resin was applied to a thickness of 100 ml, 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, it is possible to obtain a peel-resistant, moisture-permeable waterproof fabric that is the object of the present invention.

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 triisocyanates obtained by an addition reaction between 3 moles of these diisocyanates and 1 mole of a compound containing active hydrogen, such as trimethylolpropane or glycerin, are used. be done. These isocyanates can be used either in the form in which the isocyanate group is free or in the form in which it is stabilized by adding phenol, methyl ethyl ketoxime, etc. and the block is thermally dissociated by subsequent heating. 3 Workability It may be selected as appropriate depending on the purpose and purpose.

In the present invention, in order to obtain even better waterproof performance, an internal water agent is applied to the fabric as a third step following the second step. By applying the tΩ solution, it becomes possible to impart water repellency to the surface of the fabric and obtain a moisture-permeable waterproof fabric with a water pressure resistance of 2,000 m+ or more, far exceeding 1,500 mm. There are various types of water clearing agents such as paraffin type, silicone type, and fluorine thread, and in the present invention, the agent may be selected as appropriate depending on the application. When particularly good I8 water resistance is required, a fluorine-based water repellent is used, and a heat treatment is performed after applying and drying an IΩ water agent.

Further, in order to increase the durability of the tΩ aqueous resin, a resin such as a melamine resin may be used in combination. The water clearing agent may be applied by the commonly used puffing method, coating method, or spraying method.

In the present invention, in order to further improve the water repellency of the fabric, before applying the resin solution consisting of PAU resin, polyester resin, and polar organic solvent to the fabric, a T8 water agent is applied to the fabric in advance. 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 1.500 mr or more, and the moisture permeability is 7.000 mr or more. It is possible to obtain a waterproof fabric with high moisture permeability of g/rd・24hrs or more. 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 resistance JIS-L-1041 (low water pressure method) (
2) Moisture permeability JIS-Z-0208 (3) Peeling resistance
100 at a load of 200g using a Gakushin type friction fastness tester
After 0 rubbings, the appearance of the fabric was observed, and the following two-level evaluation was performed.

O: No peeling at all ×: Peeling observed Example 1 First, PAD resin (polyamino acid urethane resin) used in the 9 Examples was manufactured by the following method.

Polytetramethylene glycol (011 value 56.9) 1
970 g and 1-6-hexamethylene diisocyanate)
504g was reacted at 90℃ for 5 hours to obtain a urethane prepolymer having isocyanate groups at the end (1t2 per NGO).
340) was obtained. 85g of this urethane prepolymer and r
-Methyl-L-glutamate-NCA 85g was dissolved in 666g of a mixed solvent of dimethylformamide/dioxane (weight ratio) = 7/3, 50g of 2% triethylamine solution was added while stirring, and the reaction was carried out at 30°C for 5 hours. A yellow-brown emulsion-like PAII resin A resin liquid with good fluidity was obtained at 32,000 cps (25° C.). This P
AD resin This resin is used in formulations 1 to 5 described below.

In addition, as a polyester resin, a copolymer of 6:4 molar ratio of terephthalic acid and sepathic acid and 5:5 molar ratio of ethylene glycol and neopentyl glycol is used, and the molecular weight is 30,000 polyester resin Z was prepared. This polyester resin Z is used in formulation 1 described below. Here, a plain woven fabric (taffeta) with a warp density of 120 threads/inch and a weft thread density of 90 threads/inch using polyester 75 denier/36 filament for both the warp and weft is prepared, and this is scoured and disperse dyed in the usual manner. After dyeing, heat treatment was performed at 160°C for 1 minute. Next, using a calendering machine with mirror-finished rolls, the temperature was 170°C, the pressure was 30kg/cm, and the speed was 2.
Calendar processing was carried out under the conditions of 0 m/min, and then a resin liquid with a resin solid content concentration of 20% shown in the following recipe 1 was applied using a knife over roll coater at ff130.
After application at 15 g/rd in a water bath at 15 °C.
The resin was immersed for a second to solidify. 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 I PAU resin A 100 parts Polyester resin 2 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 coated surface in the previous step using a knife over roll coater. Coating ff1
After coating at 80 g/m, the resin was immersed in a 15°C water bath for 20 seconds to solidify the resin.

Formulation 2: 100 parts of PAD resin A, 71 parts of CRISVON ASSISTOR5D (nonionic surfactant; Dainippon Ink Chemical Industry Ia chicken product); 20 parts of dimethylformamide; Formulation 3: 100 parts of PALI resin A; 10 parts of CRISVON AW-7H (polyurethane resin, Dainippon Ink Chemical Co., Ltd.) Chemical Industry Product) Dimethylformamide 20 parts Formula 4 PAu resin resin 100 parts Polyvinylpyrrolidone 3 parts Dimethylformamide 12 parts Formula 5 PAU Resin A 100 parts CRISVON ASSISTOR 5D-112 parts (Anionic surfactant, Dainippon Ink Chemical Product) CRISVON AW-7H 5 parts (urethane resin, Dainippon Ink Chemical Industry ■ product) Parnock BL-50 2 parts (urethane resin crosslinking agent, Dainippon Ink Chemical Industry 1m product) CaCO, 10 parts Here, 10 parts in 50℃ hot water After soaking for a minute and then drying, the third step is 5% Asahi Guard 710 (product of Asahi Glass Co., Ltd.), a fluorine-based T8 water emulsion.
Perform padding with aqueous solution (squeezing ratio 30%) and
A heat treatment was performed at .degree. C. for 1 minute to obtain four moisture-permeable waterproof fabrics of the present invention.

For comparison with the method of the present invention, two comparative samples were prepared using the same method as in the present embodiment except that the first step in the present embodiment was omitted, and the performance was compared with the nine products 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 has a water pressure resistance of 2.0.
Even though it is over 00mm, its moisture permeability is 7.5
00 g/n? -Recorded over 24 hrs, showing 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 1 ・5″: Example 2 The third step (water repellent treatment) in Example 1 was omitted.

Instead of this, the fabric to be processed (taffeta) after dyeing is treated with water repellency in advance (Asahi Glass (11), after padding with a 5% aqueous solution (squeezing ratio 35%) of Asahi Guard 730, a futsuso type 1B water emulsion, 160 The fabric was processed in exactly the same manner as in Example 1, except that it was subjected to a heat treatment (heat treatment at ℃ for 1 minute) to obtain four fabrics of the present invention and four fabrics for comparison.

The resulting fabric had moisture permeability as shown in Table 2.

Both waterproofness and peeling resistance were good.

Table 2

Claims (4)

[Claims] (1) A fiber fabric mainly composed of polyester synthetic fibers is coated with a resin solution mainly composed of polyester resin, polyamino acid urethane resin, and polar organic solvent, then immersed in water, washed with hot water, and dried. A resin 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 on the coating surface. A method for producing a moisture-permeable waterproof fabric, which comprises applying a solution, immersing it in water, rinsing it in hot water, and drying it. (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 polyester resin, polyamino acid urethane resin, and 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. A resin 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 on the coating surface. A method for producing a moisture-permeable waterproof fabric, which comprises applying a solution, immersing it 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.