JPH03220371A - Coated cloth having dry touch - Google Patents

Abstract

PURPOSE:To obtain a coated cloth having dry and silky touch by covering a surface of a textile structure with a flexible film layer containing fibroin particles dispersed in a polymer having a glass transition temperature lower than a specific level. CONSTITUTION:At least one surface of a textile structure composed of a synthetic fiber such as nylon or polyester is coated with a resin liquid containing fibroin particles (preferably fine particles having particle diameter of <=50mum) dispersed in a synthetic polymer having a glass transition temperature of <=0 deg.C (e.g. polyacrylate resin or polyurethane resin) and the coated textile is heat- treated to obtain the objective coated fabric containing the fibroin particles sporadically exposed on the surface. The fabric is tack-free and flexible and has high moisture-permeability. The amount of the fibroin particle is preferably >=2wt.% based on the polymer film. When the content exceeds 5wt.%, the dry touch becomes remarkable and a fabric having excellent dry touch and quality can be produced at a fibroin content of 10-35wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a coated fabric having a dry and silk-like touch.

(Conventional technology) Conventionally, a wide range of coating processes have been carried out on fabrics in order to impart properties such as waterproofness, water repellency, and windproof properties, as well as surface changes such as color, gloss, and texture. is polyacrylic ester, polyurethane,
Synthetic polymers such as silicone resins are used. ξThese resins are used in coating fabrics,
This is because there is a tendency for soft textures to be preferred for items used in clothing, and soft synthetic polymers with low glass transition temperatures are required. However, many of the soft synthetic polymers with a low glass transition temperature are extremely sticky, and therefore the surface of the coated fabric also has the drawback of becoming sticky and wet-touch.

Therefore, various methods have been tried in the past in order to obtain coated fabrics with a dry touch.

One is surface treatment on the coating surface. this is,
A thin film of a smoothing agent such as a silicon compound or a fluorine compound, or a low-stickiness resin having a high glass transition temperature is formed on the surface of the coating film. Another method is to add liquefied fillers to the coating resin, and silica, titanium oxide, valve powder, etc. are usually used as the fillers. (For example, JP-A-61-
(Japanese Patent Application No. 191177, Japanese Patent Publication No. 1911-177, Japanese Patent Publication No. Sho A2-RTASA No. 2) The present inventors have also proposed a method of using metal soap as a filler (Japanese Patent Application No. Sho 62-2811058).

(Problems to be Solved by the Invention) However, in many cases, smoothing agents cannot sufficiently prevent stickiness, and silicon compounds cause a unique sliminess. On the other hand, resins with a high glass transition temperature are sufficient to prevent stickiness, but tend to harden the texture.

On the other hand, in the method of adding fillers, in order to sufficiently prevent stickiness, it is necessary to add a large amount of fillers, which tends to harden the texture. Also, waterproof′
It also tends to cause a decrease in physical properties such as strength, durability, and moisture permeability.

For this reason, conventionally, it has not been possible to prevent the coated surface from becoming sticky without impairing the feel, physical properties, etc., and to obtain a coated fabric that is dry to the touch.

The present invention solves these drawbacks, and provides a coated fabric that prevents stickiness on the coated surface and has a silk-like dry touch without hardening the texture, especially without making it paper-like. The purpose is to

(Means for Solving the Problems) The present invention provides a fabric having a flexible coating 1 made of a synthetic polymer having a glass transition point temperature of 0°C or less on at least one side of a fibrous structure, in which the coating 1 contains: A dry-touch coated fabric characterized by scattered fibroin particles.

Go with this invention! #I structures include woven fabrics, knitted fabrics, nonwoven fabrics, etc., and their constituent fibers include cotton, linen, wool,
Natural fibers such as silk, composite fibers such as nylon, polyester, acrylic, or mixtures thereof may be used, but 20
Fabrics containing 20 weight or more of cotton threads of about 60 to 60 count are preferred in order to maintain texture.

In the present invention, the synthetic polymer having a glass transition temperature of 0° C. or lower in a greenhouse is a flexible material, such as a polyacrylic acid ester resin,
Examples include polyurethane resin, silicone resin, and vinyl chloride resin.

In the present invention, the fibroin particles are made of finely powdered silk fibroin, and include finely powdered silk fibroin alone and/or fibroin modified products in which each II polymer is grafted thereto. It will be done.

Silk fibroin powder has an average molecular weight of 50,000 or more and is mostly composed of water-insoluble fibroin (B structure). As described in No. 18-311449, after dissolving the refined silk raw material in a melt,
Silk fibroin is coagulated and precipitated by adding a coagulating salt, blowing air, stirring, etc.

The modified fibroin product is mainly composed of a polymer consisting of 5 to 401 parts of the fibroin, 60 to 95 parts by weight of an acrylic acid monomer, and 0 to 20 parts by weight of an olefinic unsaturated monomer. Examples include things to do. in this case,
The modified fibroin product contains a carboxyl group derived from an acrylic acid monomer, and the carboxyl group may be a salt of an alkali metal or an alkaline earth metal, or may be nigethyl, especially an ammonium salt. The salt is wild. Do not purchase modified fibroin products manufactured by any method. For example, a method in which an acrylic acid monomer and an olefinic unsaturated monomer are mixed into an aqueous fibroin solution and the mixture is irradiated with radiation or the like, or a radical polymerization catalyst is added to combine the graft 1 (Japanese Patent Publication No. 5
g-57974) etc. can be used.

The shape of these fibroin particles is not particularly limited as long as they are particulate, and fine particles with a particle size of 5G, gm or less are preferable, and if the particle size exceeds 50 μm, spots or surfaces will occur during coating processing. There is a risk that

In the coated fabric of the present invention, the fibroin particles have a synthetic polymer film scattered therein, and the fibroin particles contain at least 2 times the weight of the synthetic polymer film based on the weight of the synthetic polymer film. preferable. If the content of the buproin particles exceeds 50 wt. weight, the quality of the coated fabric may deteriorate, which is not preferable. Also, 5
If the amount is more than -, the dry touch feeling will be noticeable, and if the weight of the yarn is 10 to s5, a coated fabric with excellent dry touch feeling and quality will be obtained. When observing the surface of this coated fabric, generally speaking, when the content of fibroin particles is 5 weight or more, a part of the fibroin particles is exposed from the surface of the synthetic polymer film, and this exposed part is about 5 to 30 μm. be. FIG. 1 is a schematic diagram showing the state of the surface of such a coated fabric as inspected with an electron microscope W111E (1000 m), in which (1) is the fibroin particle and (2) is the synthetic polymer film.

The synthetic polymer film 'l has a thickness of 5 to 20 mm in order to form the above-mentioned particle exposed state and to prevent hardening of the texture.
μm is preferable, and the coating method may be either dry coating or wet coating, and coating methods such as floating knife coater, knife over roll coater, reverse roll coater, roll doctor coater, gravure roll coater, kiss roll coater, etc. is available. Further, the coating film may be made porous by a known method.

The fibroin particles thus formed absorb moisture to an appropriate degree and impart lubricity to the surface of the coating film, and this lubricity acts to suppress sliminess and create a silk-like feel.

In addition, the fibroin particles serve to improve the moisture permeability of the synthetic polymer film. In this case, 8i0z
Moisture permeability is further improved when porous particles containing as a main component are used in combination. The porous particles usually have an average particle diameter of 2 to 50
Particles having a pore volume of 0.2 to 6 rnl/g are used. Further, particles having hydroxyl groups on the surface of the particles are preferable. Suitable porous particles containing 5iO1 as a main component include those having a highly porous network structure in which millimicron-order silica gel particles are three-dimensionally connected through siloxane bonds.

In addition, such porous particles are made to contain a specific solvent in advance and blended into the resin solution, and in this case, the resin solution viscosity is 50 to 150,000 cps.

Preferably, it is adjusted to 100 to 100,000 cps, and the amount of porous particles blended is 100 cps of resin solids!
0.5 to 150 parts by weight, preferably 1 to 10 parts by weight
0 parts by weight is preferable. If the amount is less than 0.5 parts by weight,
The inclusion of porous particles becomes meaningless; on the other hand, if the amount exceeds 150 parts by weight, the physical qx of the bulky skin becomes poor. Application of the resin-insoluble solvent to the porous particles is as follows: 1! Any method may be used as long as the pores, ie, cavities, are wetted with an insoluble solvent and the pores, that is, cavities are filled with the solvent, and a dipping method or a spray method can be used. As the resin-insoluble solvent, water, methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferably used, and isopropyl alcohol is particularly preferred.

In the present invention, it goes without saying that in addition to coating, various treatments such as water repellency and flexibility may be applied.

However, water repellent finishing can be done either before or after coating, but if it is done before coating, it is necessary to pay sufficient attention to the adhesive strength.

(Example) In the examples, "part" means "rIji part", and the moisture permeability and water pressure resistance are JIS-L-109!1, JI8-L-101.
12 (Method A).

Example 1 The fibroin modified material used in this example was
It was produced by the following method shown in Actual Blood Example 1 of No. 57974. That is, 1 kg of raw silk waste was immersed in 50 g of Full Cell soap aqueous solution weighing about 1 weight, and treated at 98° C. for 3:1 to remove sericin and oil suddenly. 0.5 kjJ of the refined raw silk waste was added to 2 kg of 855 parts by weight aqueous calcium nitrate solution and 0.5 kg of ethyl alcohol, and 70 to 7
The mixture was stirred and melted at 5°C for 1 hour. Then 7G'C hot water 2
K (J) was mixed and diluted, and after cooling, it was desalted using a hollow fiber type dialysis device.The ratio of this fibroin and acrylic acid was 5=85 in terms of solid content, and the ratio of both solid content was 100 parts by weight. A reaction solution was prepared.

100 g of the reaction solution was placed in a reaction vessel equipped with a stirring rod, a nitrogen blowing tube, and a thermometer, and 20 mg of ammonium persulfate was added under a nitrogen stream. The reaction was allowed to continue for a period of time. After neutralizing the resulting viscous reaction solution with an aqueous sodium hydroxide solution, it was incubated at 60°C for 8 hours. ! E-pressure drying was carried out, followed by pulverization to obtain a powder having grain size of 5 to 50 μm.

On the other hand, a fabric was obtained by dyeing a plain woven fabric using a 40 count double yarn cotton yarn as the warp and a 90 count and 15 count double yarn cotton yarn as the weft. Next, a resin solution prepared by mixing 100 parts of a polyacrylic acid ester sugar emulsion aqueous solution (solid content: 01), 10 parts of the above fibroin modified material, and 100 parts of water was applied to one side of the fabric using a floating knife coater. The coating was applied using a vacuum cleaner and immediately dried at a temperature of 120°C. Next, the fabric was padded with a 5N aqueous solution of a fluorine-based water repellent, dried (120°C), and heat-treated (
150'C).

When the surface of the coated fabric was observed under a microscope with a magnification of 500 times, it was found that there was an exposed area of 5 to 30 μm of fibroin modified material, and the coating film weighed approximately 8 g.
/m'' (solid content), the surface had a silk-like touch without stickiness, and the texture was also good.

Example 2 A plain woven fabric using 70d/18f nylon filament yarns for the warp and weft was dyed and water-repellent treated with a fluorine-based water repellent to obtain a fabric. Subsequently, acrylic acid ester resin perchlorethylene solution [(solid content 12-Ji)
100 parts and 5 parts of the same fibroin modified portion as used in Example 1 were mixed together to coat one side of the fabric using a floating knife coater, and immediately heated to 120°C. , followed by heat treatment (
150"C) was carried out.

When the surface of such a coated fabric was observed under a 500x microscope, it was found that there was one part of the modified fibroin material with a size of 5 to 30 μm, and the coating film was about 6 g/m!
(solid content), the surface had a silk-like touch with little stickiness, and the texture was also good.

Example 5 A plain woven fabric using 7Qd156f nylon filament yarn for the warp and weft yarns was dyed and treated with a fan-based water repellent to create a fabric. ! 11! A solution (solid content: 316) in ester-based polyurethane DMF/ME was added to
For 0 parts, IF fat liquid prepared by mixing 3 parts with Fibroin modified J: PJ (10 parts, DMF 15 parts) and Mfl, which were the same as those used in Example 1, was added to A! It was coated on U1m using a roll doctor coater and dried at a temperature of 12 (1'C) to form a film of about 7μm.Furthermore, ester polyurethane resin DMF/MEK/TOL solution (solid content 50%, for 100 parts of contact W1), 9 parts of open type isocyanate, 3 parts of medium for frame i11''!
A two-component skin adhesive containing 10 parts of DMF and 40 parts of TOL was applied onto the skin using a ζ coal doctor coater and dried at a temperature of 12 G'C to form a 1R layer of approximately 15 μm.
II was formed. Next, the above-mentioned composite film was rolled onto the fabric and pressed with a pressure roll, and left to stand in a SO'C room for 2 days and nights to age the adhesive (the release paper was peeled off).

The surface of such a transfer coated fabric is 500 times more powerful than a! As a result, it was found that there was an exposed part of the modified fibroin material with a diameter of 5 to 50 μm, and the coating film was approximately 2 μm thick.
3g/m! (solid content), the surface had a silk-like touch with little stickiness, and the texture was also good.

Comparative Example 1 A coated fabric obtained by removing the fibroin modified material from the resin solution of Example 1 had a weight of about 8 g/m! (solid content), and the surface had a very sticky and wet touch.

Comparative Example 2 The coated fabric obtained by removing the fibroin modified material from the a1m liquid of Example 2 had a weight of about 5 g/m! (solid content), and the surface had a very sticky and wet touch.

Comparative Example 3 A coated fabric obtained by removing the modified fibroin from the resin solution of Example 5 had a weight of about 22 g/m! (solid content), and the surface had a very sticky and wet touch.

Examples 4-7. Drawing ratio examples 4 to 7 A fabric made by freezing nylon 6 taffeta with a warp of 10 denier and 18 filaments, a weft of 70 denier and 18 filaments, a warp density of 112 threads/1 nch, and an embroidery thread number of 90 threads/1 nch using a jet dyeing machine. After dyeing and drying, water repellency treatment was performed by padding with a 2% aqueous solution of a fluorine-based water repellent.

In this relic, acrylate resin, the fibroin modified material used in Example 1, silica gel particles with a particle size of 10 mμ had a three-dimensional network structure due to siloxane bonding, an average particle size of 10 μm, and a pore volume of 1.5 m. A porous silica solution containing 50 parts of porous particles of 1/g and 50 parts of isopropyl alcohol was coated with the treatment shown in Table 1, dried at 120°C, and then heated at 160°C for 4 steps. The coated fabric is heated to t%. The coated fabric made with fibroin had the dry-touch feel of silk. Furthermore, Table 2 shows the water pressure resistance and moisture permeability of these coated fabrics.

(Below - Margin Example 8 The fibroin particles used in this example were
It was produced in the following manner according to Example 1 of 443'i+.

Using silk-spun skin as a fibroin-based material, one of these
00 parts was mixed with a solution of 30 parts of Marcel soap and 5 aoo parts of water at 95 to 88°C with stirring for 3:1 to remove the remaining glue.
．． It was reduced to less than 1 drop, washed with water, and then dried with hot air at 80'C. Anhydrous zinc chloride ZnC#! Dissolve in water to make an aqueous solution. From this, a fibroin solution was prepared.

The same amount of ammonium sulfate as the zinc chloride used was mixed with the aged fibroin solution as a concentrated aqueous solution to precipitate a gel-like substance of silk fibroin. 20
It was processed separately. At this time, if the fibroin concentration is less than 3% by weight or more than 20% by weight, a homogeneous gel is not produced, but a white precipitate is produced. The precipitate is very sticky and is difficult to apply under normal vacuum. Furthermore, when the fibroin is placed in a cloth bag and subjected to centrifugal dehydration, it becomes agglomerated and sticky, making it difficult to separate by dehydration and forming a huge lump, making dry photography difficult, so it is not preferable to use these fibroin concentrations.

The precipitate obtained as described above is dried with hot air drying*a at 90 to 100'C to obtain fibroin particles.

On the other hand, warp 70 denier 18 filament, weft 707
'Niel 18 filament, warp density 112/1n
Nylon 8 taffeta having a yarn density of 59 G threads/1 nch was produced, and the shoulder-lined fabric was dyed in a jet dyeing process and dried to obtain a fabric without water repellent treatment. In order to soften the texture of the fabric, an acrylic resin is used for the undercoat, and a urethane resin is used for the top coat.The acrylic resin for the undercoat is soft and relatively solvent resistant. (shown in Figure 1), and *The fat for the top coat (shown below 1 L) with good moisture permeability was used. Moreover, the floating knife coating method was used for the coating method.

Undercoat acrylic resin 18-20% 100 parts (Dainippon Ink Co., Ltd., Criscoat P-1019LV) Toluene, solution Top coat polyurethane resin 24-28% 100 parts (Dainippon Ink Co., Ltd. Crisbon UST-125) DMF
/MEK solution Also, the fibrous and insulating powders used were coated with 20% and 25% I in the undercoat and topcoat resins, respectively.

In the above coated fabric, the thickness of coating 1 is approximately 10 μms for the undercoat and approximately 15 μms for the top coat.
The surface of the coating is silk-like and dry, without the luster (gloss) that is characteristic of coatings, and does not harden and has a paper-like texture. do not have.

Furthermore, as shown in Table 3, there was almost no decrease in the physical properties of this coated fabric in both water pressure resistance and moisture permeability.

Example 9 In the same manner as in Example 8, nylon 6 taffeta was coated with a polyurethane resin top coat and an acrylic II Ml undercoat. In Example 9, the same amount of the fibroin modified material used in Example 1 was added instead of the fibroin particles. The resulting coated fabric had a coating thickness of about 10 μm for the undercoat and 15 μm for the top coat, and its physical properties were as shown in Table 3.

Comparative Example 8 In the same manner as in Example 8, for nylon 6 taffeta,
A coated fabric of the same shape was produced by coating the top coat with a polyurethane resin and the undercoat with an acrylic resin without using fibroin particles. The coating fabric has an undercoat of about 10
μms) The film thickness of the tube coat is approximately 15 μm. The physical properties were as shown in Table 3. The coated surface of this coated fabric has stickiness characteristic of polyurethane ALFL#, and it cannot be said to have a pleasant feel.

(Hereinafter referred to as blank spaces) (Effects of the Invention) As described above, the coated fabric of the present invention is dry and has a silk-like touch without stickiness. In addition, it is a coated fabric using a flexible resin, does not have a rough or hard feel, and has a high degree of moisture permeability, so its usefulness is obvious.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing the state of the surface of the coated fabric as observed under an electron microscope with a magnification of 1000 times. (1)...Fibroin modified particle, (2)...Synthetic polymer film. Appearance: Kanebo Co., Ltd. Procedural Amendment March 14, 1990 Figure 1: 1990 Patent Application No. 6016 2 Name of the invention: Dry tuffy coated fabric 3: Person making the amendment Relationship to the case Patent Applicant Address: Tokyo 5-17-4 Sumida, Sumida-ku, Tokyo 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka 534 Kanebo Co., Ltd. Patent Department Telephone (06) 921-1251 4. Date of amendment order Voluntary 5. Increase due to amendment. Number of claims: None 6, "Detailed Description of the Invention" column 7 of the specification to be amended, Contents of the amendment il+ Table 2 described on page 17 of the specification is amended as shown in the attached sheet. 8. List of attached documents (1) At least 1 attached sheet

Claims (1)

[Claims] (1) A fabric having a flexible film layer made of a synthetic polymer having a glass transition point temperature of 0° C. or less on at least one side of a fibrous structure, characterized in that fibroin particles are scattered in the film layer. Dry touch coated fabric.