JPH01239174A - Production of moisture-permeable and waterproof fabric - Google Patents

Abstract

PURPOSE:To obtain the title high-grade fabric, by coating a fabric with a coating resin containing a polyamino acid urethane resin imparted with hydrophilicity, a polyurethane resin etc. followed by drying, and then by coating the resultant coated fabric with a second coating resin containing the same components as those for the former but differing in composition from the former followed by heat treatment. CONSTITUTION:A W/O emulsion type resin solution is prepared by mixing (A) a polyamino acid urethane resin imparted with hydrophilicity, (B) a polyurethane resin or its blend with the component A, (C) an isocyanate compound (for the purpose of improving peelability), (D) a hydrophobic organic solvent (e.g., benzene), (E) a hydrophilic organic solvent (e.g., acetone) and water. This resin solution is applied on a fabric followed by drying. The resultant coated fabric is further coated with a second resin solution is which the components A and B have been mixed with each other in the weight ratio A/B=10/0 to 2/8, followed by hot dry treatment to form a fine porous film. The fabric thus treated is put to water repellent treatment, thereby obtaining the objective high-grade moisture-permeable waterproof fabric, which is suitable for sporting clothes.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for manufacturing a moisture permeable waterproof fabric having high moisture permeability.

(Prior art) Coated fabrics, in which a non-porous film is formed by applying a polyamino acid urethane resin liquid to a fiber fabric, have been known for a long time, and are known to have considerable moisture permeability. The non-porous polyamino acid urethane resin coated fabric has a film thickness of 10 μm class, and its moisture permeability is at most 3.000 g/rd・24 hrs (J I
S Z 020B measurement) was obtained, and the texture was also hard.

In order to improve these shortcomings, the present inventors.

Although it is a non-porous polyamino acid urethane coated fabric, it has excellent moisture permeability that far exceeds the moisture permeability limit of conventional non-porous materials, and also has a good texture. No. 62-272163 describes [a moisture-permeable waterproof fabric having two resin layers on a fiber fabric, in which the first resin layer in contact with the fiber fabric is made of a synthetic polymer mainly composed of a polyurethane resin or a polyamino acid urethane resin. a porous membrane made of a synthetic polymer of proposed a manufacturing method.

This has a moisture permeability of 4,000 to 6. OOOg/g・
It was a moisture-permeable waterproof fabric that had a water pressure resistance of 2,000n water column (JIS Li096 low water pressure method) or more at about 24hrs (JIS Z-0208), but in recent years, moisture-permeable fabric with even higher moisture permeability has been developed. Demand for waterproof fabrics has increased, with moisture permeability of 7,000 g/m・24
There is now a demand for products with performance higher than hrs.

The above-mentioned non-porous membrane coated fabric has its limitations and can no longer meet such demands.

(Problem to be solved by the invention) The present invention was made in view of the above-mentioned current situation.

Moisture permeability 7.000 g with dry porous coating process
The object of the present invention is to obtain a moisture permeable waterproof fabric having an excellent moisture permeability of 24 hours or more.

(Means for Solving the Problems) The present invention achieves the above-mentioned objects and has a tertiary configuration.

In other words, 1 the present invention is based on the method of applying a resin solution consisting of a hydrophilized polyamino acid urethane resin, a polyurethane resin, or a mixed resin of both, an isocyanate compound, a hydrophobic organic solvent, a hydrophilic organic solvent, and water to a fiber fabric. After that, in the first step of drying, the coated surface is coated with a hydrophilized polyamino acid urethane resin, or a mixed resin with a mixed weight ratio of the resin and polyurethane resin of 1020 to 2:8, and an isocyanate compound. , a method for producing a moisture-permeable waterproof fabric, which comprises a second step of drying and heat-treating after discarding a resin solution consisting of a hydrophobic organic solvent, a hydrophilic organic solvent, and water. be.

The following two aspects of the present invention will be explained in detail.

In the present invention, a polyamino acid urethane resin, a polyurethane resin, or a mixed resin of both is used as the coating resin.

Polyamino acid urethane resin used in the present invention (hereinafter referred to as
It is called PAU resin. ) is a copolymer consisting of an amino acid and polyurethane, in which the amino acid component, the polyurethane component, or both the amino acid component and the polyurethane component have been treated to make them hydrophilic to the extent that they have an affinity for water.

Constituent amino acids include D, L-alanine, and L-
Examples include aspartic acid, L-cystine, L-glutamic acid, glycine, L-lysine, L-methionine, L-leucine and their derivatives, and when synthesizing polyamino acids, the amino acid N- obtained from three amino acids and phosgene is used. Carboxylic acid anhydrides (hereinafter N-carboxylic acid anhydrides are referred to as NCA) are generally used, but optically active γ-alkyl glutamate-NCA is particularly preferred from the viewpoint of film performance.
Among them, T-methyl-L-glutamate-NCA or T-methyl-L-glutamate-NCA is preferably used from the viewpoint of price and film properties.
Methyl-D-glutamate-NCA is often advantageously selected as the amino acid component of the PAU resin.

On the other hand, the polyurethane used is a urethane prepolymer having an isocyanate group at the end, which is obtained by reacting an isocyanate and a polyol under conditions where the equivalent ratio NGO10H>1.

As the isocyanate component, aromatic diisocyanates, aliphatic diisocyanates, and ring diisocyanates may be used alone or in mixtures thereof.
Examples include 4-tolylene diisocyanate, 4-4'-diphenylmethane diisocyanate, and 6-hexane diisocyanate and 4-cyclohexane diisocyanate. Further, as the polyol component, polyether polyol, polyester polyol, etc. are used.

Polyether polyols include 2-polyethylene glycol and polypropylene glycol.

Examples of polytetramethylene glycol include polyester polyols such as ethylene glycol,
Examples include reaction products of diols such as propylene glycol and dibasic acids such as adipic acid and cehatic acid, and ring-opening polymers such as caprolactone.

The amines used in the copolymerization of amino acids and polyurethane include hydrazine, ethylenediamine, diethylamine, and triethylamine.

Ethanolamine etc. are used.

As described above, PAU resins are obtained by adding amines to the reaction system of various amino acids NCA and urethane prepolymers having isocyanate groups at the ends.

A method for making the obtained polyamino acid urethane copolymer hydrophilic is to add a hydroxyl group, a quaternary ammonium salt, a sodium carboxylate, or a sulfonic acid to the amino acid component, polyurethane component, or both the amino acid and polyurethane components of the polyamino acid urethane copolymer. There is a method of introducing an aqueous group such as soda 2. For example, γ~methyl-L-glutamy)-NC
In the case of PAU resin synthesized using A, γ-methyl-L
- Glutamate component is 2-amino-1-ethanol, 3
Examples include a method of treating with an aminoalkyl alcohol such as -amino-1-propatol or 5-amino-1-pentanol to convert it into an N-hydroxyalkyl-glutamate component and making it hydrophilic.

As the polymerization solvent used during the synthesis of the PAU resin, a solvent is selected that satisfies two points: it is a polymerization solvent for the amino acid NCA and does not contain active hydrogen, and it can dissolve the urethane prepolymer having terminal isocyanate groups. Examples of such solvents include cyclic ethers such as dioxane and tetrahydrofuran, acetate esters such as ethyl acetate and butyl acetate, ketones such as acetone and methyl ethyl ketone, and polar amide solvents such as dimethylformamide and N-methylpyrrolidone. These can be used as a single solvent or as a mixed solvent. Particularly preferred among these solvent systems are those that dissolve or uniformly disperse the polymer composition to be produced, 9 such as dimethylformamide alone, a mixed solvent of dimethylformamide and dioxane, or a mixed solvent of methyl ethyl ketone and dimethyl formamide. can be mentioned.

The polyurethane resin used in combination with the polyamino acid urethane resin in the present invention can be easily prepared into a W10 type emulsion (water-in-oil emulsion) and can form a porous membrane simply by drying. For example, HEIMLEN
Examples include X-105 (product of Dainippon Ink and Chemicals Co., Ltd.).

PAU resin and polyurethane resin may be used alone, but when they are used together, the mixing ratio is as follows:
The ratio may be suitably determined depending on the purpose, in the range of lO:o-0:10 in the step and in the range of 10:0 to 2:8 in the second step.

For example, when coating a two-knit fabric, elasticity is required, so it is desirable to increase the blending ratio of polyurethane resin in both the first and second steps.The mixing weight ratio of PAU resin and polyurethane resin in the first step is 4:6
~0:10, and the mixing weight ratio in the second step is 4
:6 to about 2:8 is preferable. In particular, in the second step, when the mixing weight ratio is 228 to 0:10, the wear resistance becomes poor.

The higher the mixing ratio of the PAU resin, the better the abrasion resistance of the resulting resin coating.

In the present invention, a compound having high affinity with the fiber base fabric is used in combination with the resin solution for the purpose of improving the peeling resistance between the resin film and the fabric. In the present invention, an isocyanate compound is also used as the compound.

Isocyanate compounds include 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene isocyanate, or compounds containing 3 moles of these diisocyanates and active hydrogen (for example, trimethylolpropane, glycerin). etc.) Triisocyanate i obtained by addition reaction with 1 mol of triisocyanate i is used.

The above-mentioned isocyanates may be stabilized by adding phenol, methyl ethyl ketoxime, etc., even if the isocyanate group is in a free form.
Even if the block is dissociated by subsequent heat treatment, any one can be used, and it may be used appropriately depending on workability, usage, etc.

The amount of the isocyanate compound to be used is preferably 0.1 to 10%, preferably 0.5 to 5%, based on the PAU resin. If the amount used is less than 0.1%, the adhesion of the resin to the fabric will be poor;
If it exceeds 0%, the texture becomes hard, which is not preferable.

In the present invention, the above-mentioned hydrophilized PAU resin is used.

A polyurethane resin or a mixture of both resins, an isocyanate compound, a hydrophobic organic solvent, a hydrophilic organic solvent, and water are mixed to prepare a W10 emulsion type resin solution, which is applied onto a fiber fabric and then dried. Then, on the coating surface, PAU resin or a mixed resin of PAU resin and polyurethane resin, an isocyanate compound, and a hydrophobic organic solvent are applied.

After applying a resin solution consisting of a hydrophilic organic solvent and water,
Dry heat treatment.

The hydrophobic organic solvent used here is benzene.

Examples include aromatic hydrocarbons such as toluene and xylene, and ethers such as diethyl ether and petroleum ether. Examples of hydrophilic organic solvents include ketones such as acetone and methyl ethyl ketone, cyclic ethers such as dioxane and tetrahydrofuran, ethanol, Alcohols such as isopropyl alcohol.

Examples include acetic acid esters such as ethyl acetate and butyl acetate.

In the present invention, a fluorine-based ↑8 water agent may be added to the above-mentioned PAU resin for the purpose of improving waterproofness (furthermore, a silicone-based resin may be added for the purpose of improving wear resistance, The amount of these to be used may be appropriately determined depending on the purpose.

The fiber fabrics used in the present invention 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 triacetate synthetic fibers. Synthetic fiber or nylon 6/cotton, polyethylene terephthalate/
Examples include woven and knitted fabrics, non-woven fabrics, etc. made of blended fibers such as cotton.

In the present invention, these fiber fabrics may be treated with an iΩ solution. In this case, the water repellency of the fabric is J
It is desirable that the ↑ΩΩ variation is 90 or more using the IS L-1096 spray method.

The ↑θ liquid agent to be used may be a known one, such as a paraffin-based 1B liquid agent, a polypolyroxane-based 1 water agent, or a fluorine-based water repellent, and the treatment was carried out by a commonly used known method. Anything is fine.

If particularly good ↑Ω water resistance is required, use a fluorine-based water repellent.
This may be carried out by a method such as padding with an aqueous solution (squeezing ratio of 35%) followed by heat treatment at 160° C. for 1 minute.

A known method may be used to prepare PAU resin, polyurethane resin, or a mixed resin of both into a W10 type emulsion, and the resin viscosity should be 2,000 to 25,000 cps (in consideration of workability during coating). 2
5''C) and to further remove unemulsified resin particles, it is desirable to perform filtration using a filter cloth of 20 to 200 meshes.

Applying the above-mentioned resin solution to the fiber fabric in the first step,
In order to coat the coated surface in the second step, it may be carried out by a conventional coating method such as a coating method using a knife coater, comma coater, reverse coater, or the like.

The amount of the resin solution applied in the first step and the second step is the same as the thickness of the resin film to be obtained from 5 to 100 μm.
It may be determined appropriately according to m.

Regarding the drying conditions, it is important to consider the boiling point of the solvent in both the first and second steps and select the temperature and time so as to form a uniform porous layer. For example, when drying a PAD resin solution consisting of dioxane/methyl ethyl ketone/toluene/water mixed solvent, 50 to 10
Dry at 0°C for 0.5 to 10 minutes. Furthermore, in order to complete the crosslinking reaction of the isocyanate compound in the resin solution, it is desirable to heat-treat at 100 to 140°C for 0.5 to 5 minutes.

After drying the resin film in the second step, a water repellent treatment is performed as necessary.

As for the water repellent used here and the method of (0 water treatment), as mentioned above, the method of 18 water treatment of the sintered fiber fabric is used as appropriate, such as padding method, spray method, etc.
Water repellent treatment may be performed by a coating method or the like. Also,
In order to increase the durability of water repellency, water repellent treatment can also be performed using a resin such as melamine resin.

In the method of the present invention, it is even more convenient to perform 1Ω water treatment both before and after coating, 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 polyurethane 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. Although the dimethylpolysiloxane may be selected as appropriate, in the present invention, dimethylpolysiloxane having a molecular weight of 5,000 to 30,000 is preferably used.

This polysiloxane treatment first of all imparts smoothness to the fabric and can reduce frictional damage to the film due to friction between the fabrics. This smoothing effect also has the advantage of allowing smooth attachment and detachment without the use of 1M fabric. 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, It may also be applied as a solution in a solvent such as toluene, hexane, or 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.

The present invention has the above configuration.

(Function) The method of the present invention uses a PAU resin, a polyurethane resin, or a mixed resin of both, which has been made hydrophilic in the first step, an isocyanate compound, and a hydrophobic organic solvent.

After applying a resin solution consisting of a hydrophilic organic solvent and water to a fiber fabric, a dry heat treatment is performed, and in the subsequent second step, a hydrophilized PALI resin is applied to the applied surface.

Alternatively, a resin solution consisting of a mixed resin of the resin and a polyurethane resin, an isocyanate compound, a hydrophobic organic solvent, a hydrophilic organic solvent, and water is applied.

It is constructed by subjecting it to dry heat treatment, and by this construction, a moisture permeable waterproof fabric having a high degree of moisture permeability is manufactured.

The reason why the moisture-permeable waterproof fabric produced by the method of the present invention has a high moisture-permeability is as follows.The present inventors speculate as follows.

Hydrophilized PAU resin, polyurethane resin.

Alternatively, the mixed resin of both is a particulate resin that is not dissolved in an organic solvent, and if water is further dispersed in this and a W10 type emulsion is applied and dried, it forms a film as a single particle. is formed and a microporous resin film is obtained. On the other hand, the PAU resin itself that forms this film is composed of block copolymerization of amino acids and urethane, and the amino acid block mainly has an α-helical structure. The urethane block forms a random coil structure, and especially the former amino acid block has α
- Due to its wax structure, it has a tendency to promote water vapor diffusion, and as a result of the combination of the α-helical structure inherent in such PAU resins and the microporous nature of the resin described above, the present invention It is presumed that the moisture permeable waterproof fabric will exhibit a high level of moisture permeability.

(Example) Next, the present invention will be explained in more detail with reference to an example, and the performance measurement and evaluation in the example will be explained below.

It was done in the following way.

(1) Moisture permeability: Based on JIS Z-0208.

(2) Water pressure resistance: Based on JIS L-1096 (low water pressure method).

Example 1 First, PAU resin (polyamino acid urethane resin) used in this example was manufactured by the following method.

Polytetramethylene glycol (OH value 56.9) 19
70g and 50g of 1,6-hexamethylene diisocyanate
4g was reacted at 90°C for 5 hours to obtain a urethane prepolymer having isocyanate groups at the terminals (NCO etc.).
12340) was obtained. 85g of this urethane prepolymer
and 85 g of γ-methyl-L-glutamate NCA,
Dimethylformamide/dioxane (weight ratio -7/3)
was dissolved in 666 g of a mixed solvent, 50 g of a 2% triethylamine solution was added while stirring, and the reaction was carried out at 30° C. for 5 hours.

A PALI resin solution (hereinafter referred to as PAU resin X) having a viscosity of 32.0OOcps (25''C) and a yellowish brown emulsion with good fluidity was obtained.

Next, take 836g of PAU resin X and add toluene/
Add 524 g of a mixed solvent of methyl ethyl ketone (lff1 ratio = 515), add 34 g of 3-amino-1-propatol while stirring, and react at 30°C for 8 hours, resulting in a viscosity of 2.800 cps (25°C). A hydrophilized PAU resin solution (hereinafter referred to as PAU resin) in the form of a milky white slurry was obtained.

A moisture-permeable waterproof fabric of the present invention was produced by the following method using the above-mentioned hydrophilized PAU resin.

First, as a base fabric, the warp is made of nylon 70 denier/24 filaments, the weft is made of nylon 70 denier/34 filament, the warp density is 120 wood/inch, and the weft density is 9.
A plain woven fabric (taffeta) of 0 strands/inch is prepared, and after scouring and dyeing with acid dye in the usual manner, it is heated at a temperature of 170 using a calendering machine with mirror rolls.
Calendering was carried out under the conditions of "C", pressure of 30 kg/cm, and speed of 20 m/min.

Here, as the first step of the present invention, the following formulation 1 is shown in Table 1.
The resin solution shown in 1 was coated using a knife-over-roll coater, adjusting the coating amount so that the dry coating weight was 8 g/m, and then heated at 60°C.

After drying for 5 minutes, in the second step, the resin solution shown in the following formulation 4 was applied to the coated surface using a knife over roll coater in an amount such that the dry coating weight was 8 g/m. After adjusting and coating the fabric, it was dried at 60°C for 5 minutes, heat treated at 120°C for 11 minutes, and then coated with Asahi Guard 710 (a product of Asahi Glass Co., Ltd.), a fluorine-based water-loss agent emulsion. was padded with a 5% aqueous solution (squeezing ratio 30%) and heated to 160°C.
After heat treatment for 1 minute, continue with Shin-Etsu Silicon Oil K.
Padded with 4% mineral turpentine solution of F-96 (dimethylpolysiloxane, product of Shin-Etsu Chemical Co., Ltd.) (
Squeezing rate: 30%) after drying.

Heat treatment was performed at 130° C. for 3 minutes in a tenter to obtain a moisture permeable waterproof fabric of the present invention (invention A).

Table 1 (Note 1) Bo'J')shi'l :/Resin (Dainichiseika Kogyo ■
Crystallization) (Note 2) Isocyanate compound (same as above) 9 of the moisture-permeable waterproof fabric of the present invention A except that formulation 3 is used in place of formulation 1 in the first step when producing the moisture-permeable waterproof fabric of the present invention A. 1 Invention B by exactly the same method as the manufacturing method
A moisture-permeable waterproof fabric was manufactured.

Furthermore, when manufacturing the moisture-permeable waterproof fabric of the present invention, Formulation 2 is used in place of Formulation 1 in the first step, and Formulation 1 is used in place of Formulation 4 in the second step. 1 Invention C by exactly the same method as for producing a wet waterproof fabric.
A moisture-permeable waterproof fabric was manufactured.

For comparison with the present invention, when producing the moisture permeable waterproof fabric of the present invention A, formulation 5 was used instead of formulation 4 in the second step.
A comparative moisture-permeable waterproof fabric (hereinafter referred to as Comparative Example 1) was manufactured in exactly the same manner as in the manufacturing of the moisture-permeable waterproof fabric of Invention A except that the following was used.

The performance of the moisture-permeable waterproof fabrics of the present inventions A and -C and the moisture-permeable waterproof fabric of Comparative Example 1 obtained as described above was measured and evaluated, and the results are shown in Table 2.

Table 2 Comparing the performance of the moisture-permeable waterproof fabrics of the present invention A to C in Table 2 with the performance of Comparative Example 1, it is clear that the moisture-permeable waterproof fabric of the present invention was It can be seen that the moisture permeability is surprisingly improved while maintaining the same level of waterproof performance as the moisture permeable waterproof fabric of Comparative Example 1 in which a non-porous membrane was formed.

(Effects of the Invention) The present invention provides a hydrophilized polyamino acid urethane resin, a polyurethane resin, or a mixed resin of both, an isocyanate compound, and a hydrophobic organic solvent.

A first step of applying a resin solution consisting of a hydrophilic organic solvent and water to a fiber fabric and then drying it, and applying a hydrophilized polyamino acid urethane resin to the applied surface.

or a mixed resin in which the mixing weight ratio of the resin and the polyurethane resin is 1020 to 2:8, and an isocyanate compound,
According to the present invention, which has a second step of applying a resin solution consisting of a hydrophobic organic solvent, a hydrophilic organic solvent, and water and then subjecting it to a dry heat treatment, the present invention has a drastic structure. A moisture permeable waterproof fabric having moisture and waterproof performance can be produced.

The moisture permeable waterproof fabric of the present invention is a material particularly suitable for sports clothing due to its excellent performance.

Patent applicant: Uni-Tei Riki Co., Ltd.

Claims (1)

[Claims] (1) After coating a fiber fabric with a resin solution consisting of a hydrophilized polyamino acid urethane resin, a polyurethane resin, or a mixed resin of both, an isocyanate compound, a hydrophobic organic solvent, a hydrophilic organic solvent, and water, The first step of drying is to apply a hydrophilized polyamino acid urethane resin or a mixed resin in which the weight ratio of the resin and the polyurethane resin is 10:0 to 2:8, an isocyanate compound, and a hydrophobic compound. After applying a resin solution consisting of an organic solvent, a hydrophilic organic solvent, and water, a second process is performed in which a dry heat treatment is performed.
A method for producing a moisture-permeable waterproof fabric, comprising the steps of: