JPH038874A - Production of coated fabric - Google Patents

Abstract

PURPOSE:To obtain a coated fabric having excellent water-proofing property and moisture-permeability by applying a fluorinecontaining polyurethane resin solution and a water-miscible organic solvent solution containing a specific fluororesin copolymer to a surface of a textile substrate and immersing the substrate in water to extract the solvent. CONSTITUTION:At least one surface of a textile substrate is coated with a liquid mixture produced by homogeneously mixing (A) a solution of a fluorine- containing polyurethane resin produced e.g. by copolymerizing a fluorine- containing compound having two active hydrogen atoms in a urethane- constituent component and (B) a fluororesin solution produced by dissolving a fluororesin copolymer containing a fluororubber as a stem polymer in a water- miscible organic solvent. The coated substrate is immersed in water to extract the solvent and dried. The mixing ratios of the above resin solutions are preferably 50-90% of the fluorine-containing polyurethane resin and 10-50% of the fluororesin. The coated fabric produced under the optimum conditions has a moisture-permeability of 10,000-12,000g/m<2>.24hrs and water-resistance of >=1,500mm.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for manufacturing a coated fabric, and more specifically, to a method for producing a coated fabric that is waterproof, moisture permeable, has a flexible texture, and has excellent durability. This relates to a manufacturing 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
150 in water pressure measurement according to L-1079 (the same applies below)
For coated fabrics with a thickness of 0 mm or more, the moisture permeability is JI.
5 in moisture permeability measurement according to SZ-0208 (the same applies hereafter)
At present, only about 000-8000g/m"・24hrs can be obtained.

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, by using a polyurethane resin solution/fluororesin solution or a polyurethane resin solution/fluororesin solution/polyamino acid urethane resin solution dissolved in a water-miscible organic solvent, the base material can be mixed uniformly. After coating, it is immersed in water and extracted with a water-miscible organic solvent.
A method for manufacturing a coated fabric with excellent waterproofness and moisture permeability, which is characterized by drying afterwards, has also been proposed, but there is a problem that long-term stability is lacking because the uniformity of mixing is still insufficient.

In addition, the coated fabric wet-coagulated using polyamino acid urethane resin/urethane resin solution has a water pressure resistance of 1500III m or more and a moisture permeability of 7000 g/m.
・Known to have a performance of 24 hours or more (
JP-A-60-162872).

However, the present invention has a water pressure resistance of 1500mm or more and a moisture permeability of 7000g/
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 is a method for improving moisture permeability in a wet coagulation method of a polyurethane resin solution by mixing a fluorine-containing polyurethane resin solution and a fluororesin copolymer having fluororubber as a backbone polymer with water. A fluororesin solution dissolved in a water-miscible organic solvent (hereinafter simply referred to as fluororesin solution) is mixed and homogenized to coat at least one side of the fiber base material, and then immersed in water to form a water-miscible organic solvent. The present invention provides a method for producing a coated fabric with excellent waterproofness and moisture permeability, which comprises extracting and drying the coated fabric.

For use> The present invention will be explained in detail below.

When a homogenized mixture of a fluorine-containing polyurethane resin and a fluororesin solution is immersed in water, the solidification rate of the fluororesin is faster than that of the fluorine-containing polyurethane resin. Spaces are created and micropores are formed.

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. , and the composition of the fluorine-containing polyurethane resin. Furthermore, since the polyurethane resin used contains fluorine, it has excellent compatibility with the fluororesin, and can continue to maintain a uniformly mixed state over time.

The urethane component of the fluorine-containing polyurethane resin in this invention is generally referred to as polyurethane, polyurethane urea resin, or polyurea resin, and has a molecular weight of 40.
0 to 4000 polyalkylene ether glycol or polyester polyol having a hydroxyl group at the end, polyε
- Caprolactone polyol or polycarbonate diol alone or as a mixture is reacted with an organic diisocyanate, but preferably one obtained by chain-extending with a compound having two active hydrogens if necessary. Examples of the polyalkylene ether glycol include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, glycerin propylene oxide adduct, chip polyether polyol with ethylene oxide added to the terminal, and vinyl monomer grafted polyether polyol. Polyester polyols include alkylene glycols such as ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, succinic acid, geltar acid, adipic acid,
Those obtained by reacting carboxylic acids such as sepatic acid, maleic acid, fumaric acid, phthalic acid, and trimellitic acid so that the terminal becomes a hydroxyl group are preferable.

Next, as organic isocyanates, 2,4- and 2.6-
-)-Aromatic isocyanates such as lylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, 1. There are aliphatic isocyanates such as tohexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 3-isocyanatemethyl-3,5,5'-trimethylcyclohexyl isocyanate 2.6-diisocyanate methyl caproate, and these may be used alone or in combination.

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

The fluorine-containing polyurethane resin in the present invention is one in which fluorine is copolymerized into the urethane constituents described above, and the following methods can be cited as means for this.

The first method is to copolymerize an acrylic resin that contains a fluoroalkyl group and a hydroxyl group in its molecule and can be copolymerized with a polyurethane resin into the urethane component.

Here, acrylic resin includes acrylic acid (or methacrylic acid) having a fluoroalkyl group and acrylic acid (or methacrylic acid) having a hydroxyl group as comonomer components, and as comonomer components other than the above. , acrylic acid, methacrylic acid, or their derivatives, i.e., acrylic acid (or methacrylic acid) and methanol, ethanol, propatool, butanol, octyl alcohol, decyl alcohol, dodecyl alcohol, cetyl alcohol, stearyl alcohol, cyclohexanol, etc. esters, acryl (or methacryl) amide, acrylonitrile, styrene, and other monomers with α,β-unsaturated ethylenic bonds are polymerized using peroxides or azo radical polymerization initiators. This means that a fluorine-containing polyurethane resin can be obtained by copolymerizing this acrylic polymer during the reaction of the aforementioned urethane constituents.

The second method is to copolymerize a fluorine-containing compound having two active hydrogen atoms into the urethane component.

Here, the fluorine-containing compound having two active hydrogens means 3
-(2-perfluorohexyl)ethoxy-1,2-dihydroxypropane, N-n-propyl-N-2,3-
Dihydroxypropyl, perfluorooctylsulfonamide, 2.2-bis(4-hydroxyphenyl)hexafluoropropane, 2.2-bis(4-(4-aminophenoxy)phenyl) hexafluoropropane, 1.3-
It refers to bis(2-hydroxyhexafluoroisopropyl)benzene or the like alone or as a mixture, and a fluorine-containing polyurethane resin can be obtained by copolymerizing this fluorine-containing compound during the reaction of the aforementioned urethane constituents.

A third method is to copolymerize a fluorine-containing compound having a fluoroalkyl group and at least one active hydrogen at the terminal end of the urethane component.

Here, the fluorine-containing compound having a fluoroalkyl group and at least one active hydrogen is generally referred to as a fluorinated alcohol, such as trifluoroethanol, N-
n-propyl-N-perfluoro-octanesulfonic acid amide ethanol, hexafluoroinpropertool,
〇-or P-trifluoromethylbenzyl alcohol,
It refers to a fluorinated alcohol ethylene oxide adduct, etc. alone or as a mixture, and a fluorine-containing polyurethane resin can be obtained by copolymerizing this fluorine-containing compound at the molecular terminal during the reaction of the urethane constituents.

In addition, the fluorine-containing polyurethane resins obtained by the above-mentioned method can be used not only individually by mixing with a fluororesin solution, but also by mixing or copolymerizing these fluorine-containing polyurethane resins. .

In addition, the fluorine-containing polyurethane resin used in this invention is preferably blended and reacted so that no incyanate group remains at the end, and has an average molecular weight in the range of 30,000 to 120,000, and furthermore, the fluorine content in the molecule is 0.
．． The content is preferably 1 to 5.0% by weight. When the fluorine content in the molecule is 5.0% by weight or more, problems arise in liquid stability, liquid viscosity, and solubility in solvents, making it difficult to obtain a uniform resin solution.

Dimethylformamide (hereinafter referred to as DMF) is typically used as a water-miscible organic solvent, but dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, dioxane, etc. may be used alone or in mixtures thereof. When a mixture of a fluorine-containing polyurethane resin solution and a fluororesin solution mixed and homogenized with these solvents is immersed in water, only the solvent dissolves in the water, and the resin solidifies in the water.

As the fluororesin solution, a fluororesin copolymer having fluororubber as a backbone polymer, for example, a vinylidene fluoride copolymer, a graft copolymer of fluororubber and polyvinylidene fluoride resin, and a water-miscible organic material such as DMF are used. A solution dissolved in a solvent is used.

In addition, it is effective to add polyfunctional polyisocyanates (eg, Coronate EH, Coronate H, manufactured by Nippon Polyurethane Industries, Ltd.) as additives 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, various physical properties differ depending on the mixing ratio of the fluorine-containing polyurethane resin solution and the fluorine-containing polyurethane resin solution, but the moisture permeability of the fluorine-containing polyurethane resin solution alone is 4000 to 5000.
g/m"-24 hrs, and good wet coagulation film forming properties cannot be obtained unless the formulation and reaction conditions are taken into consideration. In addition to such a fluorine-containing polyurethane solution, a fluororesin solution as in the present invention is used. Moisture permeability can be improved by mixing fluorine-containing polyurethane resin with a resin ratio of 10% or more.
This results in a moisture permeability of .

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 polyurethane resin solution/fluororesin solution or polyurethane resin solution/fluororesin solution/polyamino acid urethane resin solution, liquid separation will gradually occur after uniform mixing even if the resin formulation and mixing ratio are selected. Regarding the uniformity of mixing and uniform application of the mixed solution, it took about 48 hours at most, but the fluorine-containing polyurethane resin solution/fluororesin solution of this invention had excellent mixing uniformity and could be left standing for two weeks after uniform mixing. Liquid separation does not occur in liquids either.

The mixing ratio of the fluorine-containing polyurethane resin solution/fluororesin solution can be set arbitrarily, but in order to obtain good values for liquid stability, adhesion to the base material, moisture permeability, and water pressure resistance, the resin content ratio must be adjusted. , fluorine-containing polyurethane resin 50
~90%, fluororesin 10~50% is desirable, and the coated fabric obtained under optimal conditions has a moisture permeability of 10,000~
12000g/m"24hrs, water pressure 1500mm
As a result, the above performance can be obtained uniformly over the entire coated surface without causing any uneven coating.

The fluorine-containing polyurethane resin solution and the fluororesin solution can be mixed by stirring at room temperature until they become homogeneous.
The mixture may be heated and stirred at ~60°C.

The mixed solution can be applied to the fiber base material by a normal coating method, and the coating thickness is 10 to 300 μm.
m is appropriate.

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. Further, the dipping time must be 30 seconds or more. This is because if the immersion time is 30 seconds or less, the resin will not solidify sufficiently. In addition, in order to completely remove the remaining organic solvent, hot water washing at 30 to 80° C. for 3 to 10 minutes may be performed.

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 conventional batting method, coating method, spraying method, or the like.

According to the method of this invention described above, the water pressure resistance is 1500 mm.
Despite the above, moisture permeability is 7000g/m"-24hr
It is possible to obtain a coated fabric with excellent waterproofness and moisture permeability of s or more.

(The resulting coated fabric 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 by examples, but the present invention is not limited to these examples. still,
All parts in the examples are parts by weight.

Example 1 300 parts of butylene adipate having an average molecular weight of 3000 and having hydroxyl groups at both ends, 25 parts of ethylene glycol
24 parts of an acrylic resin having a hydroxyl group and a fluoroalkyl group in the molecule were uniformly mixed under a nitrogen stream, 125 parts of diphenylmethane diisocyanate (hereinafter referred to as MDI) was added, and the mixture was heated and reacted in DMF to obtain a 30%
A fluorine-containing polyurethane resin solution of 50,000 cps/30° C. was obtained using a DMF solution.

The above acrylic resin having a hydroxyl group and a fluoroalkyl group in the molecule contains 236 parts of methyl methacrylate,
LH,11(,21(,2H-hebutadecafluorodecyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., part name: Viscoat 17FM) 60 parts, 2-hydroxypropyl methacrylate 4.5 parts, azobisisobutyronitrile 0 ．．
It was obtained by suspension polymerization of 3 parts.

100 parts of this fluorine-containing polyurethane resin solution and fluororesin (manufactured by Central Glass Co., Ltd., trade name: Cepural Soft G)
38 parts of a 20% DMF solution of -180) was mixed and homogenized,
Furthermore, 1 part of polyfunctional polyisocyanate (manufactured by Nippon Polyurethane Kogyo Co., Ltd., trade name: Coronate EH), 2 parts of DMF
0 parts were added and mixed to prepare a coating liquid.

On the other hand, a wool fabric (taffeta) made of 6 nylon fibers as a base material was batted 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 D) IIP.

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

Example 2 400 parts of ethylene butylene adipate having an average molecular weight of 4000 and having hydroxyl groups at both ends, 34 parts of ethylene glycol, and 10 mole ethylene oxide adduct of 3-(2-perfluorohexyl)ethoxy-1,2-dihydroxypropane 46 uniformly mixed under a nitrogen stream,
Add 175 parts of MDI and react by heating in DMF to give 3
A fluorine-containing polyurethane resin solution of 50,000 cps/30° C. was obtained using a 0% DMF solution. 100 parts of this fluorine-containing polyurethane resin solution and the fluorine resin solution 3 of Example 1
Mix and homogenize 8 parts, and further add 11 parts of Coronate E) and DM.
20 parts of F was 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.

Example 3 600 parts of ethylene-diethylene adipate having an average molecular weight of 3000 and having hydroxyl groups at both ends, and 60 parts of polytetramethylene ether glycol having an average molecular weight of 3000.
0 parts of ethylene glycol, 6 parts of dicyclohexylmethane-4,4-diisocyanate and 262 parts of dicyclohexylmethane-4,4-diisocyanate were mixed uniformly under a nitrogen stream, and after heating reaction, 77 parts of inphorondiamine,
Add 49 parts of 10 mole ethylene oxide adduct of N-n-propyl-N-perfluorooctane sulfonic acid amide-ethanol and react in DMF to obtain 30% DM
A fluorine-containing polyurethane resin solution of 50,000 cps/30° C. was obtained using the F solution.

100 parts of this fluorine-containing polyurethane resin solution and 38 parts of the fluororesin solution of Example 1 were 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.

Example 4 50 parts each of the fluorine-containing polyurethane solutions obtained in Examples 1 and 3 and 38 parts of the fluororesin solution of Example 1 were mixed and homogenized, and further 1 part of Coronate EH and 20 parts of DMF were added.
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.

Comparative Example 1 Using only the fluorine-containing polyurethane resin solution obtained in Example 3, 11 parts of Coronate E) and DMF were added to 100 parts of the solution.
20 parts were added and mixed to prepare a coating liquid.

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

Comparative Example 2 30 parts of butylene adipate having an average molecular weight of 3000 and having hydroxyl groups at both ends, 25 parts of ethylene glycol
125 parts of MDI were added thereto and reacted by heating in DMF.
A polyurethane resin solution of 0 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 and mixed to prepare a coating liquid. This was then subjected to the same steps as in Example 1 to produce a coated fabric.

Comparative Example 3 100 parts of the polyurethane resin solution obtained in Comparative Example 2 and 38 parts of the fluororesin solution of Example 1 were mixed and homogenized, and further 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.

The coated fabrics obtained in Examples 1 to 4 and Comparative Examples 1 to 3 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 In Example 3, 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 extremely high washing resistance. It is suitable for use in ski anoraks, sportswear, raincoats, etc.

Claims (1)

[Claims] A fluorine-containing polyurethane resin solution and a fluororesin solution in which a fluororesin copolymer having fluororubber as a backbone polymer is dissolved in a water-miscible organic solvent are mixed and homogenized, and a mixed solution is coated on at least one side of a fiber base material, A method for producing a coated fabric with excellent waterproofness and moisture permeability, which comprises immersing the fabric in water to extract a water-miscible organic solvent, and then drying the fabric.