JPH0756111B2 - Dry touch coated fabric - Google Patents

Description

TECHNICAL FIELD The present invention relates to a coated fabric having a dry and silky touch.

(Prior Art) Conventionally, in order to impart properties such as waterproofness, water repellency, windproofness, and to impart surface changes such as color, gloss, and tactile sensation, a wide range of coating processes have been carried out on fabrics. , Polyacrylic ester, polyurethane,
A synthetic polymer such as silicone resin is used. Among these coated fabrics, these resins are used.
This is because those used for clothing tend to prefer a soft texture and require a soft synthetic polymer having a low glass transition temperature. However, many soft synthetic polymers having a low glass transition temperature are remarkably sticky, and therefore, the surface of the coated cloth has a drawback that the surface is sticky and wet.

Therefore, various methods have hitherto been tried in order to obtain a dry-touch coated cloth. One is surface treatment on the coating surface. This forms a thin film of a leveling agent such as a silicon compound or a fluorine compound or a resin having a high glass transition temperature and less stickiness on the surface of the coating film. Another method is to add fillers to the coating resin liquid, and silica, titanium oxide, pulp powder, etc. are usually used as the fillers. (For example, JP-A-61-19877,
Also, the present inventors have proposed a method of using metal soap as a filler (Japanese Patent Application No. Sho 62-53632).
62-289058).

(Problems to be Solved by the Invention) However, in many cases, a smoothing agent cannot sufficiently prevent stickiness, and a silicone compound causes a unique sliminess. On the other hand, a resin having a high glass transition temperature is sufficient to prevent stickiness, but it tends to cause the hardening of the texture.

On the other hand, in the method of adding the fillers, in order to sufficiently prevent stickiness, it is necessary to add a large amount of the fillers, and accordingly, the texture is likely to be hardened. Also, preventiveness,
It is easy to cause deterioration of physical properties such as durability and moisture permeability.

For this reason, conventionally, it has been impossible to obtain a dry-touch coated cloth which prevents stickiness of the coated surface without impairing the feeling, physical properties and the like.

The present invention solves these drawbacks, and provides a coated fabric having a silk-like dry touch by preventing stickiness of the coated surface without hardening the texture, particularly making it paper-like. The purpose is to

(Means for Solving the Problem) The present invention relates to a fabric having a flexible coating layer made of a synthetic polymer having a glass transition temperature of 0 ° C. or lower on at least one side of a fiber structure, in which fibroin particles are contained. It is a dry-touch coated cloth characterized by being scattered.

The fiber structure referred to in the present invention includes woven fabrics, knitted fabrics, non-woven fabrics, and the like, and the constituent fibers thereof include natural fibers such as cotton, hemp, wool, and silk, synthetic fiber such as nylon, polyester, acrylic, and the like. May be mixed, but 20-60
A woven fabric containing 20% by weight or more of cotton yarn of a count is preferable for maintaining the texture.

The synthetic polymer having a glass transition temperature of 0 ° C. or less as referred to in the present invention is a flexible polymer such as a polyacrylate resin,
Examples thereof include polyurethane resin, silicone resin, vinyl chloride resin and the like.

Further, the fibroin particles referred to in the present invention include fine powder silk fibroin, and examples thereof include fine powder silk fibroin alone and / or a fibroin modified product obtained by graft-polymerizing various polymers with this.

The fine powder silk fibroin has an average molecular weight of 50,000 or more and is mostly composed of water-insoluble fibroin (B structure). For example, as described in JP-B-58-38449, a scouring silk raw material is used. After being dissolved in a solvent, the silk fibroin is coagulated and precipitated by adding a coagulating salt, blowing air, stirring, or the like.

Further, the modified fibroin comprises 3 to 40% by weight of the fibroin, 50 to 95% by weight of the acrylic acid-based monomer and 0 to
Examples thereof include those containing a polymer composed of 20% by weight of an olefinic unsaturated monomer as a main component. In this case, the modified fibroin contains a carboxyl group derived from an acrylic acid-based monomer, and the carboxyl group may be a salt of an alkali metal or an alkaline earth metal, or may be an ester. Particularly preferred is ammonium salt. The modified fibroin may be produced by any production method. For example, a method in which an acrylic acid-based monomer and an olefin-based unsaturated monomer are mixed with an aqueous solution of fibroin, and radiation is applied, or a radical polymerization catalyst is added to carry out graft polymerization (Japanese Patent Publication No. 58-57974).
No.) etc. can be used.

The shape of these fibroin particles is not particularly limited as long as they are in the form of particles, and the particle size is preferably fine particles having a particle size of 50 μm or less. If the particle size exceeds 50 μm, spots and streaks may occur during coating. There is.

The coated fabric of the present invention has a synthetic polymer film in which the fibroin particles are scattered in the layer, and it is preferable that the fibroin particle weight is 2% by weight or more based on the synthetic polymer film weight. When the content of the fibroin particles is 50% by weight or more, the quality of the coated cloth may be deteriorated, which is not preferable. Also, 5% by weight
With the above, the dry touch feeling becomes remarkable, and it is 10 to 35 more.
When the content is% by weight, a coated fabric excellent in dry touch feeling and quality can be obtained. When observing the surface of the coated fabric, generally, when the content of the fibroin particles is 5% by weight or more, the fibroin particles are
Part of it is exposed, and the exposed portion is about 5 to 30 μm. FIG. 1 is a schematic diagram showing the state of the surface of the coated cloth observed with an electron microscope (1000 times), wherein (1) is fibroin particles and (2) is a synthetic polymer film.

The synthetic polymer film layer forms the above-mentioned particle exposed state,
The thickness is 5 to 20 μm to prevent the texture from hardening.
Furthermore, the coating method is preferably dry coating or wet coating, and a coating method such as a floating knife coater, a knife over roll coater, a reverse roll coater, a roll doctor coater, a gravure roll coater, or a kiss roll coater. Is available. Further, the coating film may be made porous by a known method.

The fibroin particles thus formed absorb moisture appropriately and impart lubricity to the surface of the coating film, and such lubricity suppresses slimy feeling and exerts a silk-like feel.

In addition, the fibroin particles act to improve the moisture permeability of the synthetic polymer film. In this case, if the porous particles containing SiO _{2 as a} main component are used together, the moisture permeability will be further improved. As the porous particles, those having an average particle diameter of 2 to 50 μm and a total pore volume of pores in the particles of 0.2 to 5 ml / g are usually used.
Further, those having a hydroxyl group on the particle surface are preferable. Take
Suitable porous particles containing SiO ₂ as a main component include those having a highly porous network structure in which primary particles of silica gel of the order of millimicrons are three-dimensionally connected by siloxane bonds. In addition, such a porous particle is previously mixed with a specific solvent, which is blended in the resin solution. At this time, the resin solution viscosity is 50 to 150,000 cps, and preferably 100 to 100,000 cps is preferably adjusted. The content of the porous particles is 0.5 to 150 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the resin solid content. If the blending amount is less than 0.5 parts by weight, the meaning of blending the porous particles is lost,
On the other hand, if it is more than 150 parts by weight, the physical properties of the resin film will be poor. The resin-insoluble solvent is applied to the porous particles so long as the porous particles are wetted with the resin-insoluble solvent and the pores, that is, the hollows, are filled with the solvent, and the dipping method or the spray method is used. it can. As the resin insoluble solvent,
The use of water, methyl alcohol, ethyl alcohol or isopropyl alcohol is preferable, and isopropyl alcohol is particularly preferable.

In the present invention, it goes without saying that various treatments such as water repellency and softness may be applied in addition to the coating process. However, the water-repellent treatment can be performed either before or after coating, but when it is performed before coating, it is necessary to pay sufficient attention to the adhesive strength.

(Examples) "Parts" in the examples means "parts by weight", and the water vapor transmission rate and water pressure resistance were measured according to JIS-L-1099 and JIS-L-1092 (method A).

Example 1 The modified fibroin used in this example is described in JP-B-58-57.
It was produced by the following method shown in Example 1 of 974.
That is, 1 kg of raw silk waste is used as a 1% by weight aqueous solution of Marcel soap 30
It was immersed in the solution and treated at 98 ° C. for 3 hours to substantially remove sericin and oil. 65% by weight calcium nitrate aqueous solution 2k
0.5k in 0.5g of ethyl alcohol and 0.5k of raw silk scraps after scouring
g was added, and the mixture was stirred and dissolved at 70 to 75 ° C. for 1 hour. Then 70
2 kg of hot water at ℃ was mixed and diluted, and after cooling, desalted by a hollow fiber type dialysis device. The reaction liquid was adjusted such that the ratio of fibroin and acrylic acid was 5:95 in terms of solid content, and the total amount of both solid contents was 10% by weight. Charge 100 g of the reaction solution into a reaction vessel equipped with a stir bar, nitrogen blowing tube, and thermometer, add ammonium persulfate 20 mg under a nitrogen stream, and
After raising the temperature from 80 ° C to 80 ° C over 1 hour, the reaction was allowed to continue at 80 ° C for 1 hour. The resulting viscous reaction solution was neutralized with an aqueous sodium hydroxide solution, and then dried under reduced pressure at 60 ° C. for 8 hours.
Then, by pulverization, a powder having a particle size of 5 to 30 μm was obtained.

On the other hand, a plain woven fabric in which a 40-twisted twin yarn silk yarn was used as a warp yarn, and a 90-thickness and 75th yarn twinned yarn was used as a weft yarn was dyed to obtain a fabric. Then, to 100 parts of a polyacrylic acid ester resin emulsion aqueous solution (solid content 30%), a resin solution prepared by mixing 10 parts of the above fibroin modified product and 100 parts of water,
The fabric was coated on one side with a floating knife coater and immediately dried at a temperature of 120 ° C. Next, the cloth was padded with a 5 wt% aqueous solution of a fluorine-based water repellent, dried (120 ° C.), and heat-treated (150 ° C.).

When the surface of such a coated fabric is observed under a microscope of 300 times, there is an exposed portion of the modified fibroin of 5 to 30 μm, and the coating film has a coating amount of about 6 g / m ² (solid content), Had a silky touch without stickiness and had a good texture.

Example 2 A plain fabric using 70d / 18f nylon filament yarns as warp and weft yarns was dyed and subjected to a water repellent treatment with a fluorine-based water repellent to obtain a fabric. Then, the same fibroin modification part 5 as that used in Example 1 was added to 100 parts of polyacrylic acid ester resin perchlorethylene solution (solid content 12%).
Part of the resin solution was applied to one side of the cloth using a floating knife coater, immediately dried at a temperature of 120 ° C., and then heat-treated (150 ° C.).

When the surface of such a coated fabric is observed under a microscope of 300 times, there is an exposed portion of the modified fibroin of 5 to 30 μm, and the coating film has a coating amount of about 6 g / m ² (solid content) and the surface is It had a silky touch with little stickiness and had a good texture.

Example 3 A plain fabric using 70d / 36f nylon filament yarns as warp and weft yarns was subjected to dyeing and water repellent treatment with a fluorine-based water repellent to obtain a fabric. Next, ester polyurethane resin
A resin liquid prepared by mixing 10 parts of the same fibroin modified product as used in Example 1, 15 parts of DMF and 30 parts of MEK with 100 parts of DMF / MEK solution (solid content 30%) was rolled onto a release paper. It was applied using a coater and dried at a temperature of 120 ° C. to form a film of about 7 μm. Furthermore, a two-component type in which 9 parts of an open type isocyanate, 3 parts of a crosslinking catalyst, 10 parts of DMF and 40 parts of TOL are mixed with 100 parts of an ester-based polyurethane resin DMF / MEK / TOL solution (solid content 50%, for adhesive layer). An adhesive was applied onto the film using a roll doctor coater and dried at a temperature of 120 ° C. to form an adhesive layer of about 15 μm. Then, the above-mentioned composite film is laminated on the cloth and pressure-bonded with a pressure roll, and left in a room at 50 ° C. for 2 days and nights.
After aging the adhesive, the release paper was peeled off.

When the surface of the transfer coating fabric was observed under a microscope of 300 times, it was found that there was an exposed portion of the modified fibroin of 5 to 30 μm, and the coating film was about 23 g / m 2.
The coating amount was ² (solid content), the surface had a silky touch with little stickiness, and the texture was good.

Comparative Example 1 The coated cloth obtained by removing the modified fibroin from the resin solution of Example 1 had a coating amount of about 8 g / m ² (solid content), and the surface was extremely sticky and had a wet touch. Was.

Comparative Example 2 The coated fabric obtained by removing the modified fibroin from the resin liquid of Example 2 had a coating amount of about 5 g / m ² (solid content), and the surface was extremely sticky and had a wet touch. Was.

Comparative Example 3 The coated fabric obtained by removing the modified fibroin from the resin liquid of Example 3 had a coating amount of about 22 g / m ² (solid content), and the surface was extremely sticky and had a wet touch. Was.

Examples 4 to 7 and Comparative Examples 4 to 7 A jet dyeing machine for a woven fabric obtained by refining nylon 6 taffeta having a warp density of 70 denier 18 filaments and a weft density of 70 denier 18 filaments and a warp density of 112 / inch and a weft density of 90 / inch. After being dyed and dried in, a 2% aqueous solution of a fluorine-based water repellent was padded for water repellent treatment.

Acrylic resin, the fibroin modified product used in Example 1, and silica gel primary particles having a particle diameter of 10 mμ have a three-dimensional network structure due to siloxane bonds to the woven fabric.
After coating 50 parts of porous particles having a volume of 10 μm and a pore volume of 1.5 ml / g with 50 parts of isopropyl alcohol, a porous silk liquid or the like was coated by the method shown in Table 1 and dried at a temperature of 120 ° C. Heat treatment was performed at 160 ° C. to obtain a coated fabric. The coated fabric using the modified fibroin had a silky dry touch feeling. Table 2 shows the water pressure resistance and moisture permeability of these coated fabrics.

Example 8 Fibroin particles used in this example are described in JP-B-58-38449.
It was produced by the following method according to Example 1 of No.

Using silk spinning waste as a raw material for silk fibroin,
0 part with a solution of 30 parts of Marcel soap and 3000 parts of water at 95-98 ° C
Was stirred and scoured for 3 hours, the residual glue was reduced to 0.1% or less, washed with water, and dried at 80 ° C with hot air. Anhydrous zinc chloride ZnCl
Dissolve ₂ in water to make an aqueous solution. From this, a silk fibroin solution was produced.

To the resulting fibroin solution, the same amount of ammonium sulfate as the zinc chloride used was mixed as a concentrated aqueous solution to precipitate a gel of silk fibroin, and the precipitate was directly left in a concentrated aqueous solution of ammonium sulfate at 70 ° C., Treated for 20 minutes. At this time, if the concentration of fibroin is less than 3% by weight or more than 20% by weight, a homogeneous gel is not formed and a white precipitate is formed. The precipitate is very sticky, and it is difficult to reduce the pressure in the usual manner. Further, when the product is put in a cloth bag and subjected to centrifugal dehydration, it becomes cohesive and cohesive, and it is difficult to separate by dehydration and form a huge lump, which makes it difficult to dry, so that it is not preferable to use these fibroin concentrations.

The precipitate obtained as described above is dried with a hot air dryer at 90 to 100 ° C. to obtain fibroin granules.

On the other hand, warp 70 denier 18 filament, weft 70 denier
18 filaments, warp density 112 threads / inch, weft density 90 threads
/ inch nylon 6 taffeta was woven and the scoured woven fabric was dyed with a jet dyeing machine and dried to obtain a fabric without water repellent treatment. Acrylic resin is used for the undercoat and urethane resin is used for the topcoat in order to make the fabric soft, and the acrylic resin for the undercoat is soft and has relatively good solvent resistance (see below). As the resin for the top coat, a resin having good moisture permeability (shown below) was used. A floating knife coating method was used as the coating method.

Undercoat Acrylic resin 18-20% 100 parts (Dainippon Ink's Chriscoat P-1019LV) Toluene solution Topcoat polyurethane resin 24-26% 100 parts (Dainippon Ink's Chrisbon UST-125) DMF / MEK
Solution Also, the fibroin powder used was coated in the undercoat and topcoat resins by 20% and 25% respectively.

The above coated woven fabric has a coating layer having a thickness of undercoat of about 10 μm and a topcoat of about 15 μm, and the coated surface has a silky-dry feel and has a gloss (gloss) peculiar to the coating. There is no hardening of the texture, and the texture is not paper-like.

Also, as shown in Table 3, the physical properties of this coated fabric showed almost no deterioration in both water pressure resistance and water vapor transmission rate.

Example 9 In the same manner as in Example 8, a nylon 6 taffeta was coated with a polyurethane resin as a top coat and an acrylic resin as an undercoat. In Example 9, the fibroin modified product used in Example 1 was added in the same amount instead of the fibroin particles. The coating fabric obtained has an undercoat thickness of about 10μ.
and a top coat of 15 μm, and the physical properties are as shown in Table 3.

Comparative Example 8 In the same manner as in Example 8, with respect to nylon 6 taffeta,
The top coat was coated with a polyurethane resin, and the undercoat was coated with an acrylic resin to prepare a coated fabric having the same shape without using fibroin particles. The coating layer of the coated fabric is about 10μ undercoat
m, the top coat has a thickness of about 15 μm. The physical properties are as shown in Table 3. The coated surface of this coated woven fabric has stickiness peculiar to polyurethane resin, and it cannot be said to have a favorable tactile sensation.

(Effects of the Invention) As described above, the coated fabric of the present invention is dry without stickiness and has a silky touch. Also, it is a coated fabric using a flexible resin,
Its texture is not rough and hard, and it has a high degree of moisture permeability.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a state when the surface of the coated fabric is observed with an electron microscope of 1000 times. (1) ... fibroin modified particles, (2) ... synthetic polymer film.

Claims (1)

[Claims] 1. A fabric having a flexible coating layer made of a synthetic polymer having a glass transition temperature of 0 ° C. or lower on at least one surface of a fiber structure, wherein fibroin particles are scattered in the coating layer. A dry touch coated fabric.