JPH0284576A - Production of moisture-permeable sheetlike material - Google Patents

Abstract

PURPOSE:To obtain the subject sheetlike material, excellent in water resistance and moisture permeability and useful as rainwear, etc., by subjecting a fiber substrate to water and oil repelling treatment, then forming a polyurethane resin layer, dissolving and removing a water-soluble natural high polymer substance from the afore-mentioned layer. CONSTITUTION:A fiber substrate 1 is subjected to water and oil repelling treatment and a polyurethane resin containing a water-soluble natural high polymer substance 4 is then applied to at least one surface of the above-mentioned substrate to form a polyurethane resin layer 7. The high polymer substance 4 is subsequently dissolved and removed to form a cellular polyurethane resin layer and afford the objective sheetlike material.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing a moisture permeable sheet material.

[Conventional technology]

In recent years, moisture permeable sheet materials that allow water to pass through but not water have been used as materials for rainwear, sportswear, and the like.

This type of sheet-like material uses, for example, a woven fabric, non-woven fabric, knitted fabric, etc. made of nylon fiber, which is a long-fiber synthetic fiber, as a base material, and a special polyurethane resin with moisture permeability is first applied to this base material. After subtracting to seal the eyes, I applied 'Ii?' on top of this. A moisture-permeable sheet made by coating a special polyurethane resin with Wr properties that can be made microporous, making it microporous, providing a polyurethane foam layer, and then treating this sheet with water-repellent tΩ oil. It is known that

[Problem to be solved by the invention]

However, the above-mentioned moisture-permeable sheet material requires the use of a special moisture-permeable polyurethane resin as the polyurethane resin laminated to the base material, and -C polyurethane resin cannot be used, so it is expensive and - It has the disadvantage of lacking film properties, and is not suitable for using general-purpose polyurethane resin. The development of a W-based sheet material has been desired.

[Means to solve the problem]

An object of the present invention is to solve the above-mentioned drawbacks of the prior art and to provide a method for manufacturing a moisture permeable sheet material having excellent water resistance and moisture permeability.

That is, in the present invention, after a fiber base material is subjected to water and oil repellent treatment, a polyurethane resin containing a water-soluble natural polymer substance is applied to at least one side of the base material to form a polyurethane resin layer, and then the above-mentioned The gist of the present invention is a method for producing a moisture-permeable sheet material, which is characterized by forming a porous polyurethane resin layer by dissolving and removing a water-soluble natural polymer material.

〔Example〕

Hereinafter, one embodiment of the present invention will be described based on the drawings.

FIG. 1 shows an example of the method for producing a moisture-permeable sheet material of the present invention. First, a fiber base material 1 is immersed in a TA water water oil treatment tank 2.
After that, it is passed through a heating oven 3 to be dried and subjected to water and oil repellent treatment. The fiber base material 1 may include woven fabrics, knitted fabrics, non-woven fabrics using natural fibers such as cotton and linen, recycled fibers such as rayon, semi-synthetic fibers such as acetate, and synthetic fibers such as nylon and polyester, either alone or in a blend. can be mentioned. In addition, water-repellent 1B oils include fluorine-based, silicone-based, and zirconium salt-based oils, but fluorine-based oils are preferred from the viewpoint of effectiveness, and among these, ta-water and ttheta oils having perfluoroalkyl groups (e.g., Preferred is a fluorine-based tΩ water-1 oiling agent in which the chain is made of acrylic ester, methacrylic ester, polyester, polyurethane, etc. and has a perfluoroalkyl group in the side chain. The amount of these water-repellent 1θ oil agents attached to the fiber base material 1 is preferably 0.1 to 3% by weight. If the amount of water and oil repellent applied to the fiber base material 1 is too small, the adhesion between the polyurethane resin applied to the base material 1 and the base material 1 will be good;
The polyurethane resin seeps into the fiber base material 1 more often, resulting in a decrease in texture. Moreover, if the amount of adhesion is too large, the adhesiveness between the polyurethane resin and the fiber base material 1 will decrease.

Next, a solution of a polyurethane resin containing a water-soluble natural polymer substance 4 (FIG. 2) was applied to the fiber base material 1 subjected to the water-repellent 1θ oil treatment to a uniform thickness using a doctor knife 5 or the like, and then heated in a heating oven 6. The polyurethane resin layer 7 containing the water-soluble natural polymer substance 4 is formed by drying.

Examples of the water-soluble natural polymer substances 4 include starches such as sweet and bitter starch, potato starch, wheat starch, tapioca starch, and corn starch, and proteins such as glue, gelatin, casein, and collagen. It is preferable to use these water-soluble natural polymer substances 4 with a particle size of 50μ or less, particularly 30μ or less.If the particle size is too large, the polyurethane resin containing these water-soluble natural polymer substances 4 may not be uniform when applied. Therefore, it becomes difficult to apply the polyurethane resin layer 7, and streaks and the like tend to occur on the surface of the polyurethane resin layer 7.

The amount of the water-soluble natural polymer substance 4 added to the polyurethane resin is 130 to 20% by weight, especially 10% by weight based on the resin.
0 to 40% by weight is preferred. If the addition of water-soluble natural polymer substance 4 is too small) L? No improvement in properties, texture, or touch can be expected, and if the amount is too high, moisture permeability will be good, but water resistance will tend to decrease.

As the polyurethane resin to which the water-soluble natural polymer substance 4 is added, any of polyester polyurethane, polyether polyurethane, polycaprolactone polyurethane, polycarbonate polyurethane, etc. can be used. These polyurethane resins include, for example, dimethylformamide (DMF), methyl ethyl ketone (M
EK), toluene, isopropyl alcohol (IPA)
It is used as a solution by dissolving it in an organic solvent such as (these solvents can also be used as a mixture). This polyurethane resin solution is preferably applied to the fiber base material l so that the coating thickness when dried is about 5 to 50 microns.

Next, the water-soluble natural polymer substance 4 is dissolved and removed to form micropores accompanying the dissolution and removal of the water-soluble natural polymer substance, and the polyurethane resin layer 7 is made into a porous polyurethane resin layer. To dissolve and remove the molecular substance, the sheet-like material 8 on which the polyurethane resin layer 7 containing the water-soluble natural polymer substance 4 has been formed is placed in hot water at about 70 to 100'C for 0.00℃.
This can be done by soaking for about 5 to 2 hours.

Moreover, when the sheet-like material 8 is rubbed while dissolving and removing the water-soluble natural polymer substance 4, the efficiency of dissolving and removing the water-soluble natural polymer substance 4 can be improved, and the softening treatment can be performed at the same time. This rubbing treatment is preferably carried out using a jet dyeing machine because it can be carried out well. This rolling process can also be carried out in two separate steps after dissolving and removing the water-soluble natural polymer substance 4. Furthermore, the water-soluble natural polymer substance 4 is dissolved and removed.
It can also be carried out in warm water containing a degrading enzyme for the water-soluble natural polymer substance. As the degrading enzyme, amylase is used when the water-soluble natural polymer substance contained in the polyurethane resin 7 is starch, and protease is used when the water-soluble natural polymer substance 4 is a protein. . When using a degrading enzyme, it is preferable to adjust the pH of the treatment solution to a range where the activity of the degrading enzyme is high, and when the enzyme is amylase, the pH is -5 to 7, and when the enzyme is protease, the pH is 7 to Il. is preferred. The amount of these degrading enzymes added is 0.01 to 5% by weight of the water-soluble natural polymer substance 4 contained in the polyurethane resin of the sheet to be immersed.
is preferred. In addition, when enzymes are included, the processing temperature is 50 to 7
Preferably, the temperature is 0°C and the treatment time is about 0.5 to 2 hours. When an enzyme that decomposes the water-soluble natural polymer substance 4 is used, the water-soluble natural polymer substance 4 is decomposed by the enzyme and becomes easier to dissolve in water. The natural polymeric substance 4 can be dissolved and removed, and deterioration of the polyurethane resin can be prevented, and the time for dissolving and removing the water-soluble natural polymeric substance 4 can be shortened and the removal rate can be improved.

By dissolving and removing the water-soluble natural polymer substance 4 and forming a porous polyurethane resin layer in this manner, a moisture-permeable sheet-like material can be obtained. Oil treatment may also be applied.

In the present invention, for the purpose of coloring the polyurethane resin layer 7, a coloring agent such as a pigment or dye can be added to the polyurethane resin constituting the resin N7. Furthermore, other additives such as various stabilizers and fillers may be added if necessary.

Hereinafter, the present invention will be explained in more detail by giving specific examples.

Example 1 A fiber base material made of a fine denier Nye I:J plain weave fabric was added to a treatment solution in which 5 parts by weight of a fluorine-based IΩ water Iθ oil agent (manufactured by Dainippon Ink Co., Ltd.: Disokugat F-70) was added to 100 parts by weight of water. Soaked sea urchin, [・Bisokua・7pu 80%
After squeezing the liquid, dry it at 100℃ for 3 minutes, and then dry it at 140℃
C for 1 minute to give a water repellent 1B oil treatment.

Next, the water- and oil-repellent treated fiber base material was coated with an average particle size of 20
25% D of descending ester polyurethane (manufactured by Daimemoto Ink Co., Ltd.: Crisbon NB631S) containing 70% μ casein by weight and a 100% modulus of 70 kg/cnl
M F -M E K solution (contains 10 parts by weight of colorant per 100 parts by weight of resin) has a dry thickness of 20
・Apply with an if coater and heat to 100℃
and dried for 3 minutes. After that, this sheet-like material was
The casein was dissolved and removed by immersion in hot water at a temperature of 1.5 hours to form a porous polyurethane resin layer. Table 1 shows the test results of water resistance and moisture permeability of the obtained sheet material.

In addition, White J water-based is JIS 1. The water pressure resistance was tested by the -1092 method, and the moisture permeability was tested by the JIS Z-0208 method.

Example 2 A fiber base material made of a strong rayon-based plain weave fabric was immersed in a treatment solution in which 3 parts by weight of fluorine-based 1θ water (oil agent (manufactured by Dainippon Ink Co., Ltd.: Disoku Guard F-60) was added to 100 parts by weight of water). , After squeezing the liquid to 85% with Huesotopinok Asop, 1
The sample was dried at 00°C for 3 minutes, and then baked at 150°C for 1 minute to treat the IΩ water with Ω oil.

Next, a polyester polyurethane containing 50% by weight of glue with an average particle size of 15μ and a 100% modulus of 60kg/cut was added to the fiber base material treated with FA water (Ω oil).
Dainichiseika Co., Ltd.: Rezamin ME3614LP) 30% D
A MF-MEK solution (containing 15 parts by weight of colorant per 100 parts by weight of resin) was applied using a knife coater to a dry thickness of 18 microns, and dried at 100 DEG C. for 3 minutes. Thereafter, this sheet-like material was immersed in hot water at 95° C. for 1.5 hours to dissolve and remove the glue, thereby forming a porous polyurethane resin layer. The properties of the obtained sheet material are shown in Table 1.

Example 3 A fiber base material made of fine denier polyester plain weave fabric was immersed in a treatment solution in which 3 parts by weight of a fluorine-based (8 water 1 Ω oil agent (manufactured by Dairomoto Ink Co., Ltd.: Disoku Guard F-70) was added to 100 parts by weight of water). After squeezing the liquid to 80% with Wesotobinoku Asobu, drying at 100°C for 3 minutes, and then drying at 150°C.
For 1 minute, water repellent + a oil treatment was applied.

Next, on the water- and oil-repellent treated fiber base material described in -F, an average particle size of 1
2 of polyester polyurethane (manufactured by Tennichi Ink Co., Ltd.: Crispon 6116SL) with a 100% modulus of 40 kg/cni containing 60% of 7μ potato starch
A 6% DMF-ML', K solution (containing 10 parts by weight of colorant per 100 parts by weight of resin) was coated with a knife coater so that the dry thickness was 15μ, and then coated at 100°C for 30 minutes. Let dry for a minute. Thereafter, this sheet-like material was immersed in hot water at 98° C. for 1 hour to dissolve and remove the potato starch, thereby forming a porous polyurethane resin layer.

The properties of the obtained sheet material are shown in Table 1.

Example 4 After forming a casein-containing polyurethane resin layer on a fiber base material in the same manner as in Example 1, this sheet-like material was dyed with Alcalase 2. pH containing 2% OT (Novo formal attire) = 8.
The casein was dissolved and removed by immersion in warm water at 50° C. for 60 minutes and rubbing to form a porous polyurethane resin layer. The properties of the obtained sheet material are shown in Table 1.

Comparative Example 1 A sheet-like product was obtained by forming a polyurethane resin layer in the same manner as in Example 1, except that a polyurethane resin to which no casein was added was used. The properties of the obtained sheet material are shown in Table 1.

Comparative Example 2 A sheet-like product was obtained by forming a polyurethane resin layer in the same manner as in Example 2, except that a polyurethane resin containing no glue was used. The properties of the obtained sheet material are shown in Table 1.

Comparative Example 3 A sheet-like product was obtained by forming a polyurethane resin layer in the same manner as in Example 3 using a polyurethane resin not containing potato starch. The properties of the obtained solid material are shown in Table 1.

Table 1 *1 The unit of water pressure resistance is ■Water column *2 The unit of moisture permeability is g/, I・2・1 hour [Effects of the invention] As explained above, the method of the present invention repels fiber base materials. After treatment with 1Ω of water and oil, this fiber base material is coated with a polyurethane resin containing a water-soluble natural polymer substance to form a polyurethane resin layer, and then the water-soluble natural polymer substance in the polyurethane resin layer is dissolved and removed. By adopting a method of forming a porous polyurethane resin layer using polyurethane resin, it is water resistant, without the need for special moisture-permeable polyurethane resin, and without the need for undercoating, which can cause hardening of the texture. It has the effect of making it possible to obtain a moisture-permeable sheet material that has excellent moisture permeability and is also excellent in feel, texture, etc.

[Brief explanation of drawings]

The drawings show one embodiment of the present invention, and FIG. 1 is an explanatory diagram showing an example of the manufacturing method of the present invention, and FIG. 2 is a cross-sectional view taken along the vertical line 1--2 in FIG.

Claims (1)

[Claims] After water- and oil-repellent treatment is applied to the fiber base material, a polyurethane resin containing a water-soluble natural polymer substance is applied to at least one side of the base material to form a polyurethane resin layer. A method for producing a moisture-permeable sheet-like article, which comprises forming a porous polyurethane resin layer by dissolving and removing molecular substances.