JPH04163373A - Production of coated fabric - Google Patents

Abstract

PURPOSE:To obtain the subject soft fabric having waterproofness and moisture permeability excellent in durability by dissolving a reaction product of a polyurethane-based resin with a polyvinylidene fluoride-based resin in a water- miscible organic solvent, applying the resultant resin solution to a textile material and wet coagulating the applied solution. CONSTITUTION:A reaction product composed of a polyurethane-based resin and a polyvinylidene fluoride-based resin is dissolved in a water-miscible organic solvent (e.g. dimethylformamide) and the resultant resin solution is then applied to one surface of a textile substrate such as nylon fiber and wet coagulated to afford a waterproof coated fabric excellent in moisture permeability. If the aforementioned coated fabric is further subjected to treatment with a water repellent, water ' pressure resistance can be improved. Since resistance to washing is also excellent, the resultant fabric is suitable as uses such as anoraks for skiing and raincoats.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for producing a coated fabric, and more specifically, a method for producing a coated fabric that is waterproof, moisture permeable, has a soft texture, and has excellent durability. It is about the method.

<Conventional technology and its problems> Various types of waterproof and moisture permeable coated fabrics have been known so far, and the representative one is a fabric coated with a microporous film made of polyurethane resin, and its manufacturing method is currently unknown. An example of this is the so-called wet coagulation method, in which a water-miscible solvent solution of polyurethane resin is applied to a fiber base material, and then immersed in a water bath to form a microporous film made of polyurethane resin (Japanese Patent Publication No. 60-47955). issue).

However, although this production method produces a coated fabric with a fine porous film that is waterproof and breathable, from a performance standpoint, it is not possible to create a coated fabric based on the balance between waterproof performance and breathable performance. Because of this, the water pressure resistance is JIS
15 in water pressure measurement according to L-1079 (the same applies below)
Currently, for coated fabrics with a thickness of 00 mm or more, the moisture permeability is only about 5000 to 7000 g/m2.241 (rs) by moisture permeability measurement according to JIS Z-0208 (the same applies hereinafter).

Also, a method for manufacturing a moisture-permeable waterproof fabric by using polyvinylidene fluoride/polyurethane that does not have uniformity in mixing, and applying shear to the resin during coating to form particularly long cells in a direction parallel to the fabric surface. is also known (Japanese Patent Publication No. 63-60156), but there is a problem in putting it into practical use because the liquid separation of the liquid mixture is severe.

Furthermore, the mixing uniformity of polyurethane resin solution/fluororesin solution, polyurethane resin solution/fluororesin solution/polyamino acid urethane resin solution, fluorine-containing polyurethane resin solution/fluororesin solution, etc. dissolved in a water-miscible organic solvent is generally improved. A method for producing a coated fabric with excellent waterproofness and moisture permeability, which is characterized by coating a substrate with a fabric, immersing it in water to extract a water-miscible organic solvent, and then drying it. JP-A No. 2-99671 and JP-A No. 2-104771) have also been proposed, but they have the problem of lacking long-term stability because the mixing uniformity is still insufficient.

In addition, the coated fabric wet-coagulated using polyamino acid urethane resin/urethane resin solution has a water pressure resistance of 1500 mm or more and a moisture permeability of 7000 g/m2.2.
It is known to have a performance of 4 hours or more (Japanese Patent Application Laid-open No. 162872/1983).

However, the present invention has a water pressure resistance of 1500 mm or more and a moisture permeability of 7000 g/
This was obtained as a result of studies aimed at obtaining a coated fabric that has a performance of m2.24 hrs or more and has excellent mixing uniformity of the mixed liquid.

<Means for Solving the Problems> That is, the present invention provides a water-miscible solution containing a reactant mainly composed of a polyurethane resin and a polyvinylidene fluoride resin as a means for improving moisture permeability in a wet coagulation method of a polyurethane resin solution. Waterproof and moisture permeable material characterized by coating at least one side of a fiber base material with a resin solution dissolved in an organic solvent, then immersing it in water to extract the water-miscible organic solvent, and then drying it. The present invention provides a method for producing an excellent coated fabric.

<Effect> The present invention will be explained in detail below.

When polyvinylidene fluoride resin is reacted with polyurethane resin and the resin solution dissolved in a water-miscible organic solvent is immersed in water, the solidification rate of the polyvinylidene fluoride resin segment is faster than that of the polyurethane resin segment in the resin. This results in distortion between the segments, creating spaces and forming micropores.

Regarding the pore size of these micropores, if the pore size is small, the moisture permeability will decrease, and if the pore size is large, the water pressure resistance will be poor. It is determined by the ratio of the system resins and their respective compositions.

In addition, in this invention, since a reactant of polyurethane resin and polyvinylidene fluoride resin is used, there is no problem with long-term liquid storage stability, and furthermore, there is no need for water repellent treatment using conventionally known fluorine water repellents. In terms of durability of water pressure resistance, the drop in water resistance pressure after washing can be significantly improved compared to the conventional method of adding a small amount of water repellent.

The urethane component of the polyurethane resin in this invention is generally referred to as polyurethane, polyurethane urea resin, or polyurea resin, and has a molecular weight of 400 to 40.
00 polyalkylene ether glycol or a polyester polyol having a hydroxyl group at the end, a polyε-caprolactone polyol, or a polycarbonate diol alone or in a mixture is reacted with an organic diisocyanate, but if necessary, a compound having two active hydrogens may be used. Those obtained by chain extension are preferable, and it is necessary to have an unsaturated bond in the molecule.

Examples of the polyalkylene ether glycol include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, glycerin propylene oxide adduct, chipped polyether polyol with ethylene oxide added to the end, and vinyl monomer grafted polyether polyol. Polyester polyols include ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol,
Alkylene glycols such as dipropylene glycol and neopendel glycol and carboxylic acids such as succinic acid, geltaric acid, adipic acid, sebadic acid, maleic acid, fumaric acid, phthalic acid, and trimellitic acid are combined so that the terminal end is a hydroxyl group. It is better to give something in response to.

Next, as organic isocyanates, 2.4- and 2.6-
-) Aromatic isocyanates such as lye diisocyanate, 4.4' diphenylmethane diisocyanate, 1.5-naphthalene diisocyanate, xylylene diisocyanate, 1.6-hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3- Incyanate methyl-3,5,5'-1-
There are aliphatic isocyanates such as lymethylcyclohexyl isocyanate and 2,6-dicyanatomethylcabroate, which can be used alone or in combination.

Furthermore, as chain extenders, hydrazine, ethylenediamine, tetramethylenediamine, water, piperazine, isophoronediamine, ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, etc. may be used alone or used in combination.

Furthermore, as a means for having unsaturated bonds in the urethane resin component, diols that support unsaturated bonds such as unsaturated polyester polyols, or acrylic resins and monomers having hydroxyl groups containing unsaturated bonds can be used. These may be used alone or in combination.

In this invention, the polyurethane resin refers to a polyurethane resin made from the above-mentioned urethane constituents, as well as monomers such as amino acids, acrylic, acrylic rubber, silicone, vinyl chloride, epoxy components, and monomolecular units such as diols. Polymer units such as oligomers and polymers can be used alone or in combination and reacted.

Furthermore, fluorine compounds having active hydrogen, such as 3-(2
Diols such as -perfluorohexyl)ethoxy-1,2-dihydroxypropane, diamic acids, or fluorinated alcohols such as trifluoroethanol can be used alone or in combination.

As the polyvinylidene fluoride resin, a polyvinylidene fluoride resin or a Graph 1 to copolymer of a vinylidene fluoride copolymer fluororubber and a polyvinylidene fluoride resin can be used.

Next, the reaction product of polyurethane resin and polyvinylidene fluoride resin is prepared by adding the above-mentioned polyurethane resin, polyvinylidene fluoride resin, and peroxide in the coexistence of oxygen to 80%
Obtained by heating at ~120°C for 5 to IO hours.

Dimethylformamide (hereinafter referred to as DMF) is typically used as a water-miscible organic solvent, but dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dioxane, etc. may also be used alone or in combination with these solvents. A mixture of polyurethane resin and polyvinylidene fluoride resin can be used as the main component, and when the compound is dissolved in these solvents and immersed in water, the power of the solvent dissolves in the water and the resin is dissolved. It solidifies in water.

In addition, if necessary, monomers such as amino acids, acrylic, acrylic rubber, silicone, vinyl chloride, epoxy components,
Oligomers made by reacting monomolecular units such as diols,
Polymers and other polymer units can be used singly or in combination,
Reacted products, as well as fluorine compounds with active hydrogen,
For example, 3-(2-perfluorohexyl)ethoxy-1
, diols such as 2-dihydroxypropane, diamines, or fluorinated alcohols such as trifluoroethanol, alone or in combination, are reacted to reactants consisting of polyurethane resin and polyvinylidene fluoride resin. It is possible to arbitrarily mix them within a range of 50% or less in terms of ratio.

When 50% or more is mixed, satisfactory physical properties such as water repellency and moisture permeability cannot be obtained.

In addition, as additives, it is effective to add polyfunctional polyisocyanates (for example, brand names Coronate EH and Coronate HL, manufactured by Nippon Polyurethane Industries, Ltd.) in order to improve the adhesion to the coating substrate. Additionally, it is effective to add a nonionic surfactant as a speed regulator for solvent removal during wet coagulation.

Naturally, physical properties vary depending on the ratio of polyurethane resin and polyvinylidene fluoride resin, but polyurethane resin alone has a moisture permeability of 4000 to 5000 g/m2/24 hr.
s, and good wet coagulation film forming properties cannot be obtained unless the formulation and reaction conditions are taken into account. By reacting such a polyurethane resin solution with a polyvinylidene fluoride resin as in the present invention, moisture permeability can be improved. That is, when polyvinylidene fluoride resin is reacted with polyurethane resin in a resin ratio of 2% or more, a moisture permeability of 7,000 to 13,000 g/m244 hrs can be obtained.

In addition, the wet film forming properties are greatly improved, and no destruction of the formed porous cells is observed even when heated at 160°C.

In addition, in the case of polyurethane resin solution/fluororesin solution or polyurethane resin solution/fluororesin solution/polyamino acid urethane resin solution, even if the resin composition and mixing ratio are selected, liquid separation will gradually occur after uniform mixing, and mixing will occur. Regarding the uniformity of mixing and uniform application of the solution, although it takes about 48 hours at most, liquid separation does not occur in the product whose main components are the reactants of the polyurethane resin and polyvinylidene fluoride resin of this invention.

Furthermore, there is no need for water repellent treatment using conventionally known fluorine-based water repellents, and in terms of water pressure durability, the drop in water pressure after washing is reduced compared to the conventional method of adding a small amount of water repellent. This can be significantly improved.

The blending ratio of these polyurethane resin/polyvinylidene fluoride resin solutions can be set arbitrarily, but the
In order to achieve good adhesion with the base material, moisture permeability, and water pressure resistance, the resin content ratio should be 50 to 9.
8%, polyvinylidene fluoride resin 2 to 50% is desirable, and the coated fabric obtained under optimal conditions has a moisture permeability of 1.
0,000 to 12,000 g/m2-24 hrs, water pressure resistance of 1,500 mm or more, and as a result, the above-mentioned performance can be obtained uniformly over the entire coated surface without causing uneven coating.

The obtained resin solution can be applied to the fiber base material by a normal coating method, and the coating thickness is 10 to 10.
300 IIm is suitable.

The water temperature when this coated fabric is immersed in water is 0.
The appropriate temperature is ~30°C, and if the temperature exceeds 30°C, the pores of the resin film will become larger and the water pressure resistance will decrease. Also, the soaking time is 3
0 seconds or more is required. This is because if the time is 30 seconds or less, the solidification of the resin will be insufficient. In addition, in order to completely remove the remaining organic solvent, soak it in warm water at 30 to 80°C for 30 minutes.
You may perform hot water washing for ~10 minutes.

After washing with hot water and drying, the resulting coated fabric can be further coated with a water repellent to improve water pressure resistance.

There are various types of water repellent such as paraffin type, silicone type, fluorine thread, etc., and it may be selected as appropriate depending on the purpose. The water repellent may be applied by a commonly used patting method, coating method, spraying method, or the like.

According to the method of this invention described above, the water pressure resistance is 1500 m.
24 with moisture permeability of 7000g/m”
It is possible to obtain a coated fabric with excellent waterproofness and moisture permeability exceeding hrs.

The coated fabric thus obtained can be used for golf wear,
It can be used for a very wide range of purposes, including sportswear such as ski wear, winter clothing, rain clothing, and work clothing.

<Examples> Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples. still,
All parts in the examples are parts by weight.

Example 1 350 parts of ethylene butylene adipate with an average molecular weight of 4,000 having hydroxyl groups at both ends, 34 parts of ethylene glycol, ethylene glycol with an average molecular weight of 4,000 having hydroxyl groups at both ends, itaconic acid, fumaric acid, and adipic acid. 50 parts of a saturated polyester polyol and 46 parts of a 10 mole adduct of ethylene oxide of 3-(2-perfluorohexyl)ethoxy-1,2-dihydroxypropane were uniformly mixed under a nitrogen stream,
4.4'-diphenylmethane diisocyanate (MDI
) was added and reacted with heating in DMF to give 30% D.
An unsaturated bond and fluorine-containing polyurethane resin solution of 5000 cps/30°C was obtained using the MF solution.

Next, a graft copolymer of vinylidene fluoride-based copolymer fluororubber and polyvinylidene fluoride resin (manufactured by Central Glass Co., Ltd., trade name: Cefral Soft) was added to 100 parts of this unsaturated bond and fluorine-containing polyurethane resin solution as a fluororesin solution. 40 parts of a 20% DMF solution of G-180),
Mix 04 parts of benzoyl peroxide uniformly and add 10ml of air while stirring! /min, held at 100°C for 8 hours, and 3500 cps/30°C as a 27% DMF solution.
A reactant solution was obtained.

100 parts of this reactant solution and a polyfunctional polyisocyanate (manufactured by Nippon Polyurethane Industries Co., Ltd., trade name Coronate EH)
) and 20 parts of DMF were added and mixed to prepare a coating liquid.

On the other hand, a woolen fabric (taffeta) made of 6 nylon fibers as a base material was padded with a 1% aqueous solution of a fluorine water repellent emulsion, and heat treated at 160° C. for 1 minute.

The coating liquid obtained above was applied onto the water-repellent substrate using a floating knife coater at a rate of 200 g/m'' (
After coating (wet), the resin was immersed in a 20°C water bath for 1 minute to solidify the resin. Thereafter, it was immersed in warm water at 50°C for 10 minutes to fully extract DMF.

After drying, padding was performed with a 5% aqueous solution of fluorine-based water repellent emulsion at 160°C.
A coated fabric of the present invention was obtained by heat treatment for 3 minutes.

Example 2 600 parts of ethylene diethylene adipate having an average molecular weight of 3000 and having hydroxyl groups at both ends, polytetramethylene ether glycol 6 having an average molecular weight of 3000
00 parts, 6 parts of ethylene glycol, and 262 parts of dicyclohexylmethane-4,4'-diisocyanate were mixed uniformly under a nitrogen stream, and after heating reaction, 77 parts of isophorone diamine was obtained.
1 part, 6.5 parts of 2-hydroxyethyl meccrylate was added, reacted in DMF, and diluted with 50,000 parts of 3% DMF solution.
An unsaturated bond-containing polyurethane resin solution of cps/30''C was obtained.

Next, this unsaturated bond-containing polyurethane resin solution 10
0 parts, 30 parts of a 2% DMF solution of polyvinylidene fluoride resin (manufactured by Pennwalt, trade name Kynar 460) and 0.35 parts of benzoyl peroxide were uniformly mixed, and while stirring, air was added at 10 nt/mjn. 100°C58
Hold for 30,000 cps/3 in 26% DMF solution.
A reactant solution at 0°C was obtained.

To 100 parts of this reactant solution, 1 part of Coronae) EH, DM
A coating liquid was prepared by adding and mixing 20 parts of F. This was then subjected to the same steps as in Example 1 to obtain a coated fabric.

Comparative Example 1 300 parts of butylene adipate with an average molecular weight of 3000 having hydroxyl groups at both ends, 25 parts of ethylene glycol
were uniformly mixed under a nitrogen stream, and 1125 parts of MD was added to D.
50,000 in 30% DMF solution by heating reaction in MF.
A polyurethane resin solution of cps/30°C was obtained.

Using only this polyurethane resin solution, this solution
1 part of Coronate EH and 20 parts of DMF were added to
The mixture was mixed to prepare a coating solution. This is described in Example 1 below.
A coated fabric was obtained through the same process.

Example 3 50 parts of the reactant solution obtained in Example 2 and 40 parts of the polyurethane resin solution obtained in Comparative Example 1 were uniformly mixed, and further 1 part of Coronate E H and 20 parts of DMF were added and mixed to form a coating liquid. was prepared. This was then subjected to the same steps as in Example 1 to obtain a coated fabric.

Example 4 50 parts of the reactant solution obtained in Example 1, 15 parts of a 20% DMF solution of vinyl chloride-polyurethane resin copolymer (manufactured by Nippon Polyurethane Industries Co., Ltd., trade name Dominus K-6501), and 15 parts of a 20% DMF solution obtained in Comparative Example 1. 20 parts of the polyurethane resin solution prepared above was mixed and homogenized, and 1 part of Coronate EH and 20 parts of DMF were added and mixed to prepare a coating liquid. This was then subjected to the same steps as in Example 1 to obtain a coated fabric.

Comparative Example 2 100 parts of the polyurethane resin solution obtained in Comparative Example 1 and 38 parts of the fluororesin solution of Example 1 were mixed and homogenized, and further 1.3 parts of Coronate EH and 20 parts of DMF were added and mixed,
A coating solution was prepared.

This was then subjected to the same steps as in Example 1 to obtain a coated fabric.

The coating fabrics obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured for performance such as water pressure resistance and moisture permeability, and the results shown in Table 1 were obtained.

In addition, each measurement was performed according to the following method.

Water pressure resistance JIS L-1079 Moisture permeability JIS Z-0208 Table 1 As is clear from Table 1, the coated fabric obtained by the method of the present invention has a water pressure resistance of 1500 mm or more and a water vapor permeability of 8000 mm or more. ~11000g/m
``It recorded a high value of 24 hours, and was recognized to have both outstanding moisture permeability and waterproof performance.

On the other hand, in Comparative Example 1, the wet coagulation film formation (creation of micropores) was not complete (and the moisture permeability was low), and in Comparative Example 2, liquid separation occurred over time.

<Effects of the Invention> As described above, in addition to the above-mentioned good performance, the coated fabric obtained by the present invention has a flexible texture, good surface smoothness, and good washing resistance. It was found to be suitable for use in ski anoraks, sportswear, raincoats, etc.

Applicant's agent: Patent attorney Kazu 1) Showa procedure neho sho (self-motivated) November 21, 1990 Coated fabric manufacturing method 3, relationship with the case of the person making the amendment Patent applicant's address Iyo, Nishi-ku, Kobe City Junwa Tanimachi 1109 Ariku Name Seiko Kasei Co., Ltd. 4, "Detailed explanation of the invention" column 6 of the agent's specification, contents of the amendment (1) Specification box page 3, line 8 "-For boat fishing " is corrected to "-temporarily."

(2) Page 15, line 9 r　5000cps/30℃'' r　50000cps/30°C''.

(3) Page 15, line 19 r　3500cps/30°C" r　35000cps/30℃''.

(b) Page 19, line 2 r　K　-6501'' I will correct it to r　K　-650FJ.

Claims (1)

[Claims] A resin solution obtained by dissolving a reactant consisting of polyurethane resin and polyvinylidene fluoride resin in a water-miscible organic solvent as main components is coated on at least one side of the fiber base material, and then immersed in water to mix it with water. A method for producing a coated fabric with excellent waterproofness and moisture permeability, which comprises drying after extracting a synthetic organic solvent.