WO1995012706A1 - Materiau composite et procede de production - Google Patents

Materiau composite et procede de production Download PDF

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Publication number
WO1995012706A1
WO1995012706A1 PCT/JP1993/001611 JP9301611W WO9512706A1 WO 1995012706 A1 WO1995012706 A1 WO 1995012706A1 JP 9301611 W JP9301611 W JP 9301611W WO 9512706 A1 WO9512706 A1 WO 9512706A1
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WO
WIPO (PCT)
Prior art keywords
elastic polymer
composite material
polymer substance
base material
water
Prior art date
Application number
PCT/JP1993/001611
Other languages
English (en)
Japanese (ja)
Inventor
Minoru Yoshida
Shinichi Okajima
Minoru Fukui
Original Assignee
Asahi Kasei Kogyo Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kogyo Kabushiki Kaisha filed Critical Asahi Kasei Kogyo Kabushiki Kaisha
Priority to US08/448,521 priority Critical patent/US5922445A/en
Priority to KR1019950702761A priority patent/KR0145192B1/ko
Priority to PCT/JP1993/001611 priority patent/WO1995012706A1/fr
Priority to GB9512449A priority patent/GB2288993B/en
Priority to CN93121430A priority patent/CN1057141C/zh
Publication of WO1995012706A1 publication Critical patent/WO1995012706A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other

Definitions

  • the present invention relates to a flexible and durable composite material in which an elastic polymer material is impregnated or coated on a fibrous base material such as a yarn, a knitted fabric or a nonwoven fabric, and a method for producing the same. More specifically, the present invention provides (i) excellent mechanical strength such as separation strength of a coating layer while being flexible when coated, and (i) flexible when impregnated.
  • the present invention relates to a composite material having excellent durability, such as wear resistance, which is incompatible with the composite material, and a method for producing the same.
  • the former method of kneading into yarn requires fine particles having a submicron-order particle size that is small enough to be spun. Even after this, the fine particles lose their function due to the spinning conditions (especially heat), the strength of the yarn is degraded, the spinning yield is reduced, and it is not possible to cope with small lots.
  • Adding functions in post-processing methods such as resin processing is used as a simpler method.
  • this post-processing method has a drawback that the resin restrains the fibers and significantly impairs the feel of the fibrous base material. Another drawback is that the resin itself drops off from the fibers during use and during washing, losing its function.
  • fabrics having the function (b), that is, moisture-permeable / waterproof / water-repellent functions are often used for sports applications such as windbreaking. This is generally obtained by coating urethane, which foams during solidification, onto a fabric.
  • urethane which foams during solidification
  • the penetration of the elastic polymer substance into the cloth is controlled. It is possible to improve the texture.
  • examples of such methods include a method in which the fabric is subjected to a heat calendering treatment and the surface of the fabric is pressed to smooth it, or a liquid repellent such as a fluorine compound is applied to the fabric in advance to prevent penetration. (See JP-A-58-144178).
  • the entire fabric has a paper-like hard texture. Furthermore, since the penetration of the elastic polymer material is reduced, problems such as a decrease in separation strength of the film of the elastic polymer material remain. Similarly, in the case where the cloth is subjected to the liquid repellent treatment, the penetration of the elastic polymer material is similarly reduced, so that the separation strength of the film of the elastic polymer material is reduced.
  • artificial leather which is a composite material of a nonwoven fabric and an elastic polymer substance (mainly urethane)
  • a coating layer of the elastic polymer substance is provided on the surface of the impregnated base obtained by impregnating the nonwoven fabric with the elastic polymer substance.
  • a leather or nubuck-like product made by puffing the formed artificial leather with silver or the impregnated base material described above for use in clothing or furniture such as shoes and coats. are included. For these applications, a texture closer to that of natural leather is required, and research on more flexible artificial leather is ongoing. These are intended to gain flexibility by preventing the adhesion between the fiber and urethane.
  • a nonwoven fabric is impregnated with an adhesive polymer material having a different solvent from the elastic polymer material to be impregnated and the solvent, and the surface of the constituent fibers of the nonwoven fabric is covered or a part of the space created by the constituent fibers is filled.
  • Artificial leather in which an elastic polymer material is impregnated and coagulated, and then a sizing polymer material is removed to form a gap between the fiber and the elastic polymer material (for example, Japanese Patent Publication No. 45-18745, (Refer to Japanese Patent Publication No. 49-1099697).
  • the nonwoven fabric to which the silicone resin has been applied has a reduced strength and is liable to undergo morphological changes during the processing process, and is liable to cause processing problems such as cutting.
  • sea-island fiber (b) limited to a special fiber called sea-island fiber
  • an object of the present invention is to solve the problems of the prior art in a composite material in which a fibrous base material such as a yarn, a knitted fabric, or a nonwoven fabric is impregnated or coated with an elastic polymer substance. When coated, it is flexible and has excellent peel strength of the coating layer.
  • the first object of the present invention is to provide a composite material having a coating layer of an elastic high molecular material that is flexible and has a high separation strength.
  • the elastic polymer substance is formed on a cut surface of the composite material by a coating layer of the fibrous base material and the elastic polymer substance.
  • the second object of the present invention is to provide a composite material in which a fibrous base material is impregnated with an elastic polymer substance, which is flexible and has durability such as abrasion resistance and mechanical strength.
  • a sheet-like composite material impregnated with a molecular substance (i) the total number of fibers Nt present on the cut surface of the composite material, and the elastic polymer substance on the circumference of the fiber cross section of all the fibers;
  • the ratio Nn / Nt which is the ratio to the number of fibers Nn that are not bonded at all, is 0.3 to 1, and (ii) the center of the composite material is closer to the center compared to the impregnation rate of the elastic polymer material in the surface layer. This is achieved by a sheet-like composite material having a high impregnation rate of the elastic polymer substance in the composite material.
  • the fibrous base material when the fibrous base material is coated or impregnated with an elastic polymer substance, (i) the fibrous base material contains a water-repellent silicone as a main component. (Ii) coating or impregnating the base material with a solution of the elastic polymer substance to which a hydrophilic silicone has been added, and (Hi) applying a solution of the elastic polymer substance to the base material. It can be produced by immersing in a poor solvent, or by scattering a good solvent first during drying and leaving the poor solvent to coagulate the elastic polymer substance.
  • the composite material according to the present invention on which the elastic polymer substance is coated, is suitable for coating an elastic polymer substance on a fibrous base material.
  • a fluorine-based water repellent alone or a hydrophobizing pretreatment agent combined with a water-repellent silicone is applied to the fibrous base material;
  • a hydrophilic material is added to the base material.
  • FIG. 1 is an enlarged cross-sectional view of a composite material coated on an elastic polymer substance 2 force fibrous base material 3 (woven fabric) of the present invention.
  • Reference numeral 1 denotes a fiber that exists at the interface between the fibrous base material and the hydrophilic polymer material and is surrounded by the elastic polymer material in a non-adhesive manner.
  • FIG. 2 is a schematic cross-sectional view of a composite material in which an elastic polymer substance 2 of the present invention is impregnated in a fibrous base material 3 (nonwoven fabric).
  • the straight lines AD and BC represent the position of the surface of the fibrous base material
  • the area surrounded by the straight lines EG and FH represents the central part of the fibrous base material.
  • FIG. 3 is an enlarged cross-sectional view of a composite material manufactured by a conventional technique, in which an elastic polymer substance 2 is coated on a fibrous base material 3 (woven fabric).
  • Numeral 1 indicates a fiber bonded to the elastic polymer substance among the fibers existing at the interface between the fibrous base material and the elastic polymer substance.
  • Fig. 4 (a) is an electron micrograph (2500 times) of a cross section of the composite material impregnated with the elastic polymer substance of the present invention
  • Fig. 4 (b) is a comparison of the conventional technique.
  • 13 is an electron micrograph (2500 times) of a part of the cross section of the composite material of the comparative example created in Example 10.
  • 2 is an elastic polymer Quality
  • 3 is the fiber of the fibrous base material.
  • the present inventors have developed a structure in which the elastic polymer material and the fiber are not bonded to each other as a structure that does not cause deterioration of the texture when the fibrous base material is impregnated or coated with the elastic polymer material (non-adhesive structure). Focusing on, it is possible to form a sufficient non-adhesion structure between the elastic polymer material and the fiber without using special fibers such as sea-island fiber, and to have a strong separation and strong abrasion resistance of the elastic polymer material layer.
  • the present inventors have conducted intensive studies on the structure of a composite material that simultaneously satisfies conflicting characteristics and a method for realizing the structure, and have reached the present invention.
  • FIG. 1 shows a flexible, low-noise, and peeling-off coating layer obtained by coating an elastic polymer substance 2 (urethane) of one example of the present invention on a fibrous base material 3 (woven fabric).
  • urethane elastic polymer substance 2
  • FIG. 1 is a diagram showing (a) the fibrous substrate surface, contact bonding of a urethane And (b) urethane has penetrated so as to surround the fiber 1 on the surface.
  • Fig. 3 shows the conventional window break force of the comparative example. The structure of is shown.
  • FIG. 2 is a schematic cross-sectional view of an artificial leather having excellent softness and abrasion resistance obtained by impregnating a nonwoven fabric with an example of the urethane of the present invention.
  • the coating fabric has a high peel strength despite the fact that the elastic polymer material has a soft texture without restraining the fiber.
  • the first feature of the coating fabric of the present invention is that the elastic polymer material penetrates deeper than the fibers existing at the interface between the fiber base material and the elastic polymer material layer. At least the fibers present on the surface of the fibrous substrate coated with the elastic polymer material (in other words, the fibers between the fibrous substrate and the elastic polymer layer) are coated with the elastic polymer material. Higher separation strength can be obtained if it penetrates deeper than the fiber existing at the interface). ( Deep penetration here means that the elastic polymer material has a part that penetrates to the extent that it surrounds the fiber. is there.
  • At least one elastic polymer material non-adhesively surrounds the fiber at a distance of 1000 m in electron micrographs. More than one at 500 m is better.
  • a second feature of the coating fabric of the present invention is that the elastic polymer of the fiber present at the interface between the coating layer of the elastic polymer material and the fibrous base material is used. It is characterized by high non-adhesion of the substance to the coating layer.
  • the present inventors have found that the degree of non-adhesion of the fibers present at the interface between the coating layer of the elastic polymer substance and the fibrous base material with the elastic polymer substance is determined by the flexibility of the coating cloth and the coating layer. Has been found to be extremely closely related to their separation power.
  • the total number of fibers Nt existing at the interface between the fibrous base material and the coating layer of the elastic polymer substance, and the total number of fibers existing at the interface, the elastic polymer substance on the circumference of the fiber cross section Nn / Nt, which is the ratio to the number of fibers Nn that are not bonded at all, must be 0.3 to 1, and preferably 0.5 to 1.
  • NnZNt is less than 0.3, most of the fibers become substantially adhered fibers, which is not preferable because the texture becomes hard.
  • NnZNt is calculated by the following method.
  • the thickness of the coating layer of the elastic polymer substance in the present invention is not particularly limited, it is particularly preferably 1 to 500 m for clothing. If it is less than 1 cm, the water pressure may be reduced in applications that require water pressure (for example, windscreens and car jackets). On the other hand, if it exceeds 500 zm, it is not preferable because the soft texture of the fiber does not survive and becomes a rubber-like texture.
  • impregnated cloth the composite material of the present invention in which a fibrous base material is impregnated with an elastic polymer substance (hereinafter referred to as impregnated cloth) will be described.
  • the first feature of the impregnated fabric of the present invention is that the non-adhesion between the fibers in the fibrous base material and the elastic polymer material is high. That is, the ratio of the total number of fibers Nt existing on the cut surface of the sheet-like composite material to the number of fibers Nn that are not adhered to the elastic polymer substance on the circumference of the fiber cross section NnZNt Is from 0.3 to 1.
  • the non-adhesion between the elastic polymer material and the fiber was determined by the fact that the elastic polymer material did not touch the entire circumference of the fiber cross section in an electron micrograph taken at a magnification of 350 times the cross section of the sheet-like composite material.
  • the number of non-fibers ⁇ is counted and evaluated by Nn / Nt, which is the ratio to the total number of fibers Nt present on the cut surface.
  • NnZNt is calculated by the following method.
  • a cross-sectional electron micrograph taken at a magnification of 350x at any five locations on a sheet-shaped composite material cut with a sharp blade was divided vertically into 100 micron units on the sheet surface. And get a number of split photos. From these, arbitrary 10 divided photos are extracted.
  • the outermost surface is determined by the following method for the front and back sides (corresponding to the upper and lower ends in Fig. 2) of each extracted photograph.
  • Nn / Nt in the present invention is from 0.3 to 1, preferably from 0.5 to 1 or less.
  • NnZNt is less than 0.3, most of the fibers in the fibrous base material adhere. It is not preferable because the texture becomes hard because the texture is hardened.
  • the second characteristic of the composite material impregnated with the elastic polymer substance of the present invention is that the impregnation rate of the elastic polymer substance in the central portion is higher than the impregnation rate of the elastic polymer substance in the surface layer. .
  • the surface layer and the center are defined by the following method. This will be described with reference to FIG.
  • the surface layer of the composite material is defined as E at the point on the line segment AB that is 1/3 of the distance from A to AB, and on the line segment CD at the distance of 13 the distance from D to DC on the line segment CD.
  • E When the point is G, it is the area between the line segment EC and the outermost surface AD.
  • the outermost surface AD is the surface on the front side of the sheet-like composite material.
  • the center is a point located on the line segment AB at a distance of 1 Z 3 of the distance from B to AB, and a point on the line segment DC located at a distance of 13 of the distance from C to DC on the line segment DC. Is the area between line segment FH and line segment EG.
  • the ratio of the amount of impregnation between the surface layer and the center can be obtained by the following method.
  • the area of the elastic polymer substance existing in the surface layer is Sa
  • the area of the elastic polymer substance existing in the center is Sb.
  • the ratio of the impregnation amount between the surface layer and the center is R s can be determined.
  • R s is preferably 0.7 or less.
  • the impregnation rate of the elastic polymer substance in all layers is preferably about 5 to 40% by weight, more preferably 10 to 30% by weight, based on the total weight of the sheet-like composite material. It is.
  • the sheet-like composite material according to the present invention having such a structure has an extremely soft texture, a low compressive modulus near the surface, so that a very supple touch feeling can be obtained, and high abrasion resistance and bursting.
  • the fibrous base material referred to in the present invention is a spun yarn, a multifilament, a yarn, a thread such as a braid, a synthetic paper made of paper or synthetic fiber, a woven fabric such as a plain weave, a twill weave, or a satin weave.
  • Weft knitting, rubber knitting, pearl knitting, etc. Single tilt atlas, single atlas, single code, half tricot, plain tricot, queen's code, It can be obtained by warp knitting such as sewn knitting, dry method of web forming by air lay method, card method, flash method, or sheet forming method of dispersing fibers in water etc. and forming it into a wire mesh.
  • plain weave is preferred because of its low cost, but warp and weft yarns are generally tightly converged, so there is no gap between the filaments, and it is particularly difficult for urethane to surround the fibers during coating. For this reason, it is preferable to improve the segregation of partially crimped textured yarn or ultrafine fibers (latitude 1 d or less), which increases the separation strength.
  • a nonwoven fabric made into a nonwoven fabric by applying high-speed fluid treatment to a sheet formed into a web by the papermaking method has a very supple texture, uniformity of fiber dispersion, It is preferable because of its excellent isotropy and excellent surface touch and good balance of physical properties of the process.
  • the diameter of the single yarn Short fibers with a ratio LZD of 0.8 ⁇ 10 3 to 2.0 ⁇ 10 3 are three-dimensionally entangled with each other at a length of ⁇ 25 micron, and the average distance between the fiber entanglement points
  • the distance between the fiber average entanglement points as referred to herein is defined in JP-A-58-191280. This is a value measured by the following known method, and as one measure of the entanglement density between fibers, the smaller the value, the denser the entanglement.
  • the constituent fibers are natural fibers, regenerated fibers, synthetic fibers such as polyester, polyamide, polyolefin, and acrylic, and split-type fibers obtained by composite spinning, but the materials are particularly limited. It is not done.
  • Examples of the elastic polymer substance applied to the fibrous base material include polyester-based polyurethane, polyether-based polyurethane, and polyester.Polyether-copolymer-based polyurethane, and polycarbonate-based polyurethane. It is possible to use various synthetic rubbers, polymer substances having rubber-like elasticity such as natural rubber, or a mixture mainly composed of these. From the viewpoint of flexibility, it is preferable to use a polyurethane elastic polymer material.
  • composite material refers to a fibrous elastic polymer composite in which the above-mentioned fibrous material is impregnated and coated with an elastic polymer substance or both.
  • the composite material of the present invention in which the above-mentioned fibrous base material is impregnated or coated with an elastic polymer substance is first obtained by forming a sufficient non-adhesive structure by an unconventional manufacturing method described below. Be feasible
  • the greatest feature of the production method of the present invention lies in that the fibrous base material and the elastic polymer material are improved in advance in mold release, and are wet-solidified after imparting hydrophobicity and hydrophilicity, respectively. . It is also possible to dry coagulate using a processing liquid of an elastic polymer substance dispersed in some emulsion water.
  • the water-repellent silicone used in the hydrophobizing pretreatment agent according to the present invention include dimethylpolysiloxane, alkyl-modified polysiloxane, nitrogen-modified polysiloxane, amino-modified polysiloxane, Epoxy-modified polysiloxanes and their copolymerized silicones are used.
  • methyl hydride polysiloxane and a copolymer of dimethyl polysiloxane and methyl hydride polysiloxane are preferred because of their high hydrophobicity effect on the fiber surface.
  • the hydrophobizing pretreatment agent is not limited to the water-repellent silicone described above, and may be, for example, fluorine, which is generally an acrylate or a copolymer of a methacrylate and a vinyl compound derived from a perfluoroalkyl compound. It is also possible to use a known water repellent such as a system water repellent in combination or alone.
  • the amount of the water-repellent silicone / fluorine-based water repellent attached to the fibrous base material is preferably 0.1 to 2% by weight based on the weight of the fiber. It is more preferably from 0.3 to 1% by weight. If the amount of adhesion is less than 0.1% by weight, the effect of preventing hydrophobic and hydrophilic repulsion with an elastic polymer substance to be impregnated later is small. On the other hand, if the adhered amount is more than 2% by weight, the amount becomes excessive and wasted, and if it is more than 5% by weight, there is a possibility of uneven coloring during dyeing.
  • a hydrophobizing pretreatment agent containing water-repellent silicone as a main component when a hydrophobizing pretreatment agent containing water-repellent silicone as a main component is applied to the fibrous base material, when the fibrous base material is a short-fiber entangled nonwoven fabric, May cause a decrease in power.
  • a slip inhibitor added to the hydrophobizing pretreatment agent used in the present invention Is a commonly used slip inhibitor such as, for example, colloidal silica, silicone, inorganic oxide, paraffin and ester.
  • silicone Slip inhibitors are preferred, and for example, BY22-839, a product of Toray's “Dauco Oneng” Silicone, is preferably used.
  • the hydrophilic silicone to be added to the elastic polymer substance referred to in the present invention is, for example, an alkoxy-modified polysiloxane, a carboxyl-modified polysiloxane, a copolymer thereof, or an alkyl such as dimethylpolysiloxane. Copolymers with polysiloxanes are used. Among them, alkylalkoxypolysiloxanes such as methylethoxypolysiloxane are preferable in order to impart more hydrophilicity to the elastic polymer.
  • the amount of the hydrophilic silicone added to the elastic polymer substance is preferably 0.1 to 10% by weight. If the added amount is less than 0.1% by weight, the effect of preventing the binding by the non-woven fabric constituent water and the hydrophilic repulsion is small. On the other hand, even if the amount added is more than 10% by weight, there is no difference in the anti-adhesion effect and it is just wasteful. In addition, there is a problem that the foaming property of the impregnated elastic polymer material during wet coagulation is deteriorated.
  • a commonly used hydrophilizing agent such as sorbitan yarn or polyoxyethylene yarn may be used in combination.
  • the fiber and the elastic polymer substance are still bonded at the time of wet coagulation. Even if a rubbing treatment is performed, the elastic polymer substance and the fiber are not released sufficiently from the wet solidification, as in the structure obtained by the present invention. The flexibility as in the case where the bonding is prevented cannot be obtained.
  • FIG. 4 (a) shows the composite material obtained in Example 7 of the present invention and impregnated with an elastic polymer substance. It can be seen that a space is formed between the elastic polymer material and the fibrous base material, and a good non-adhesive structure is obtained.
  • Fig. 4 (b) shows the conventional technology in which only the fibrous base material was pretreated with water-repellent silicone and the hydrophilic silicone of the elastic polymer substance was not added.
  • a cross-sectional electron micrograph of the composite material (see Comparative Example 10) is shown. As is evident from the figure, the elastic polymer substance and the fibrous base material are adhered to each other and have a hard texture.
  • the elastic polymer substance which is a feature of the composite material of the present invention, has a deep fibrous material. It is preferable because it easily penetrates the base material and easily forms a coating layer of the elastic polymer substance on the surface of the fibrous base material.
  • the viscosity at the time of impregnation with the elastic polymer substance is 50,000 cps. The following is preferred.
  • a direct coating with a roll coater or a knife coater on the woven or knitted fabric, or a release paper is used as a method of coating the solution or emulsion of the elastic polymer substance on the fibrous base material.
  • a direct coating with a roll coater or a knife coater on the woven or knitted fabric, or a release paper is used as a method of coating the solution or emulsion of the elastic polymer substance on the fibrous base material.
  • a direct coating with a roll coater or a knife coater on the woven or knitted fabric, or a release paper is used as a method of coating the solution or emulsion of the elastic polymer substance on the fibrous base material.
  • the non-adhesive structure between the elastic polymer substance and the fiber is advanced, and the impregnation rate of the elastic polymer substance at the center is shown.
  • the structure higher than the layer portion is achieved by the following manufacturing method.
  • the fibrous base material is pre-treated and dried with a sizing polymer material and a treatment liquid containing the above-described water-repellent silicone as a main component in advance, and similarly, the above-mentioned water-repellent silicone is added to the elastic material.
  • a manufacturing method characterized by extracting and removing a sizing agent and a polymer substance after impregnating and solidifying the polymer substance.
  • the sizing polymer is preferably a polymer soluble in a solvent different from the solvent of the elastic polymer to be impregnated later.
  • a solvent different from the solvent of the elastic polymer to be impregnated later.
  • polyvinyl alcohol, carboxymethylcellulose, polyvinyl acetate, or starch is used. You can also. Among them, polyvinyl alcohol and carboxymethyl cellulose are preferable because they are soluble in water and can be easily extracted.
  • the solid content of the sizing polymer substance on the fiber is preferably 0.5 to 15% by weight, more preferably 2 to 7% by weight. If the solids content is less than 0.5% by weight, even if the sizing polymer substance concentrates on the surface of the fibrous base material due to migration, it can hardly fill the interfiber space and is impregnated later.
  • the elastic polymer substance is impregnated in the surface layer and the center similarly, which is not preferable. Furthermore, a sufficient binder effect is not produced, and morphological
  • the amount of the glue polymer substance is more than 15% by weight, the gap between the fibers in the surface layer portion of the fibrous base material is almost filled by the migration of the glue polymer substance, and the elastic polymer material is removed. Impregnation becomes difficult.
  • the pre-impregnated water-repellent silicone and sizing polymer each exhibit unique behavior during the drying process.
  • the glue polymer substance selectively acts on the surface layer of the fibrous base material by migration and acts as a binder that binds at the fiber entanglement point, thereby significantly stabilizing the form stability of the fibrous base material.
  • the abundance ratio of the impregnated elastic polymer material in the surface layer portion should be lower than that in the central portion. I can do it.
  • a non-adhesive structure of the fiber and the elastic polymer material is realized in the surface layer by extracting the size polymer material.
  • the water-repellent silicone is more likely to be present at the center because migration is less likely to occur as compared to the high-molecular-weight paste. For this reason, in the center, non-adhesive production is realized by the repelling action of the water-repellent Z-hydrophilicity between the water-repellent silicone present on the fiber surface and the hydrophilic silicone present in the impregnated urethane.
  • the greatest feature of this production method is that it is pre-treated with a treatment liquid containing a sizing polymer material and a water-repellent silicone as main components and dried. If the sizing polymer material and the water-repellent silicone are treated separately on the fibrous base material (for example, after the sizing polymer material is attached and dried, the water-repellent silicone is applied), sufficient adhesion to the sizing agent surface is achieved. This is not preferred because the shape of the fibrous base material is remarkably changed or the morphological change of the fibrous base material becomes significant.
  • the elastic polymer-impregnated cloth-coated cloth obtained by the production method of the present invention becomes extremely flexible and does not reduce the volume feeling and feel of the fibrous base material.
  • the elastic high molecular substance provided in the fibrous base material exists in the continuous space created by the fibrous base material, there is no mechanical strength reduction such as abrasion resistance and burst strength.
  • the functional fine particles are pre-treated with the hydrophobizing pretreatment agent of the present invention, the functional fine particles and the elastic polymer substance are likely to have a non-adhesive structure, and the functional fine particles are added in a large amount. However, it is preferable because it does not cause deterioration in strength or flexibility. In addition, because of breathability and water absorption, It is preferable because the function of the hydrophilic fine particles (eg, antibacterial property, water retention, etc.) is easily expressed.
  • the hydrophilic fine particles eg, antibacterial property, water retention, etc.
  • Coating fabrics having the structure described above are flexible, have extremely high release strength, and have moisture permeability and water resistance, and are particularly suitable for ski wear, golf, and jogging. It is ideal for sport applications such as in-door cars.
  • Wear wheel H-22 1 kg load (The number of wears when a hole is formed in the test piece is regarded as wear resistance.
  • a windbreaker was created, and sensory evaluation of noise prevention was conducted in a wearing test (wearing all day) by 10 people. Each person was evaluated as 1 point if they were not concerned at all, and 0 points as they were concerned every time they performed the action, and 1/2 of the total score was given as a grade.
  • Single filament denier 1.5 d, a Nye B emission fibers having a fiber length of 12.5 hide, more sheets into papermaking method, and then the three-dimensional entangled basis weight only 360 g Zm 2 Thickness 1.2mm nonwoven was by high velocity fluid treatment, dimethylpolysiloxane Pretreatment liquid prepared from 0.6 parts of siloxane, 5 parts of PVA and 94.4 parts of water is immersed, and then uniformly squeezed with a nip roll so that the squeezing rate becomes 100% .Hot air at 150 ° C for 3 minutes A drier was used to adhere the dimethylpolysiloxane active ingredient to the nonwoven fabric by 0.6 to fiber weight% and the PVA active ingredient to 5 to fiber weight%.
  • a polyurethane solution comprising 11 parts of a polyurethane having a polyester ether copolymer soft segment, 1 part of methylethoxypolysiloxane and 88 parts of dimethylformamide is applied to the nonwoven fabric after the pretreatment described above. Squeezed liquid to a squeezing ratio of 250%, coagulated in water for 6 minutes, then dissolved and removed PVA in hot water at 90 ° C to 100 ° C, and dried to obtain a sheet. Since the composite material has a high NnZNt of 0.66, its bending hardness is low and it is flexible. In addition, it can be seen that Rs is as low as 0.33, and the impregnation amount in the central portion is higher than that in the surface layer portion, so that it has high wear resistance. Tables 1 and 2 show these characteristics.
  • the nonwoven fabric of Example 1 was immersed in a pretreatment liquid prepared from 0.6 part of dimethylpolysiloxane, 2 parts of PVA and 97.4 parts of water, and then uniformly squeezed with a nip roll so as to have a squeezing rate of 100%. After the mixture, the mixture was heated at 150 ° C for 3 minutes. A hot air drier was used to apply 0.6% by weight of fiber and 2% by weight of PVA to the nonwoven fabric.
  • the composite material has a high NnZNt of 0.54, it is Is low and flexible, and Rs is low at 0.37, which means that the impregnated amount in the center is higher than that in the surface layer, indicating high abrasion resistance. See Figure 2.
  • the nonwoven fabric of Example 1 was immersed in a pretreatment liquid prepared from 0.6 part of dimethylpolysiloxane and 99.4 parts of water, and then squeezed with a nip roll. After the solution was uniformly squeezed so as to have a concentration of 100%, an active ingredient of dimethylpolysiloxane was applied to the nonwoven fabric at 0.6% by weight of the fiber with a hot-air drier at 150 ° C for 3 minutes.
  • a polyurethane solution consisting of 11 parts of a polyurethane having a polyether ether copolymer-based soft segment, 1 part of methylethoxypolysiloxane and 88 parts of dimethylformamide is applied to the nonwoven fabric after the above-mentioned pretreatment. Then, the solution was squeezed to a squeezing rate of 250%, solidified in water for 6 minutes, washed with hot water at 90 ° C to 100 ° C, and dried. The resulting sheet-like composite material has a high bending strength and low flexibility due to a high NnZNt of 0.55, but has an Rs of 1.12 that is uniformly impregnated with the elastic polymer material in the thickness direction. And high abrasion resistance as in Examples 1 and 2 was not obtained (the characteristics are shown in Tables 1 and 2).
  • the nonwoven fabric of Example 1 was immersed in a pretreatment liquid prepared from 3 parts of PVA and 97 parts of water, and then uniformly squeezed with a nip roll so that the squeezing rate became 100% .Then, at 150 ° C for 3 minutes.
  • the PVA active ingredient was adhered to the nonwoven fabric at a ratio of 3% by weight of fiber by a hot air dryer.
  • the non-woven fabric after the pretreatment described above was impregnated with a polyurethane solution comprising 11 parts of polyurethane having a polyester ether copolymer soft segment and 89 parts of dimethylformamide, and squeezed.
  • the solution was squeezed to a rate of 250% and solidified in water for 6 minutes.
  • PVA was dissolved and removed in hot water at 90 ° C to 100 ° C and dried.
  • the resulting sheet-like composite material has a low NnZNt of 0.18, and thus has a high flexural hardness and a hard texture.
  • methylethoxypolysiloxane which is a copolymer silicone composed of 20 parts of a polyurethane having a polyester ether copolymer-based soft segment, about 60% of methylethoxysiloxane and about 40% of dimethylsiloxane, and 2 parts of dimethylforma 78 parts of mid, fluorine-based water repellent
  • Polyurethane solution consisting of 1.2 parts and 10 parts of cellulose fine particles (Abicell PH-MD 6, trade name: 6 ⁇ m, average particle size, manufactured by Asahi Kasei Kogyo Co., Ltd.).
  • a knife coater is applied to the fabric after pretreatment described above. At 200 g / m 2 and coagulated in water for 6 minutes, followed by washing in warm water at 60 ° C. to 70 ° C. for 20 minutes.
  • a fluorine-based water repellent is pure
  • Table 3 shows the bending elasticity and peel strength of the obtained sheet-like composite material. Since the sheet-like composite material of the present invention has a high Nn / Nt of 0.83 and a low flexural elasticity of 0.30, it does not have any treatment on both the fibrous base material and the elastic high molecular material (see Comparative Example 1). In comparison, it is very flexible. The separation strength is 1500gf / inch Yes, it was very high compared to the fluorine-based water-repellent treatment and calendered crushed product (Comparative Example 2).
  • Table 3 also shows that it has excellent water pressure resistance and moisture permeability and is an excellent windbreaker.
  • a polyurethane solution comprising 20 parts of a polyurethane having a polyester ether copolymer soft segment and 80 parts of dimethylformamide was applied to the woven fabric of Example 3 at a rate of 200 g / m 2 using a knife coater. Two coats were allowed to coagulate in water for 6 minutes, followed by washing and drying in warm water at 60 to 70 ° C for 20 minutes. Further, about 0.3 g / m 2 of a fluorine-based water repellent was adhered as a pure component by an immersion method. Table 3 shows the bending elasticity and peel strength of the obtained sheet-like composite material. The separation strength of the sheet-like composite material was as high as 1650 gfZinch. However, since Nn / Nt is as low as 0.11, the flexural elasticity is as high as 0.67, which is harder than that of the present invention shown in Example 3.
  • Example 3 The fabric of Example 3 was subjected to a water-repellent treatment using a 2% aqueous solution of a fluorine-based water-repellent. Next, a heat calendering treatment was performed under the conditions of a temperature of 160 ° C and a linear pressure of 130 kg Zcm to smooth the surface.
  • a polyurethane solution comprising 20 parts of a polyurethane having a polyester ether copolymer soft segment and 80 parts of dimethylformamide was added to the woven fabric by a knife coater using a knife coater. g / 2 coated and dried.
  • Table 3 shows the bending elasticity and separation strength of the obtained sheet-like composite material. Since the immersion of urethane is suppressed, the sheet-like composite material has a high NnZNt of 0.20 and a low flexural elasticity of 0.48 as compared to Comparative Example 1, but has a soft texture. Was 700 gf inch, which was lower than that of Example 3.
  • Table 4 shows the bending elasticity of the obtained sheet-like composite material.
  • the bending elasticity of the sheet-like composite material obtained by the present invention is as low as 0.017, and is obtained by applying a water-repellent treatment to a fibrous base material (see Comparative Example 6), a fibrous base material, and an elastic polymer material. It turns out that it is much more flexible than the untreated one (see Comparative Example 7).
  • Example 5
  • a copolymer silicone composed of 11 parts of a polyurethane having a polyester ether copolymer-based soft segment, about 60% of methyl ethoxysiloxane and about 40% of dimethyl siloxane.
  • the knitted fabric after the above-mentioned pretreatment is impregnated with a polyurethane solution composed of 88 parts of dimethylformamide, squeezed to a squeezing ratio of 150%, and solidified in water for 6 minutes. Washed and dried in warm water at 70 ° C to 70 ° C for 20 minutes.
  • Table 5 shows the bending elasticity of the obtained sheet-like composite material.
  • the flexural elasticity of the sheet-like composite material obtained by the present invention is as low as 0.020, which is obtained by subjecting a fibrous base material to a water-repellent treatment (see Comparative Example 8), a fibrous base material, and an elastic high molecular substance. It can be seen that both are much more flexible than those without treatment (see Comparative Example 9).
  • the knitted fabric obtained in Example 5 was prepared from 1 part of methylhydrogenpolysiloxane, which is a copolymer silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, 5 parts of PVA, and 94 parts of water. Immerse in the pretreatment liquid for hydrophobization, then squeeze it uniformly with a nip roll so that the squeezing rate is 60%, then dry it at 150 ° C for 3 minutes with a hot air dryer to enable methylhydrogenpolysiloxane. Ingredients 0.6% and 3% of PVA active ingredient were adhered to the knitted fabric.
  • methylhydrogenpolysiloxane which is a copolymer silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, 5 parts of PVA, and 94 parts of water. Immerse in the pretreatment liquid for hydrophobization, then squeeze it uniformly with a n
  • methylethoxypolysiloxane which is a copolymerized silicone composed of 11 parts of polyurethane having a polyester ether copolymer-based soft segment, about 60% of methylethoxysiloxane, and about 40% of dimethylsiloxane.
  • the knitted fabric after the above pretreatment is impregnated with a polyurethane solution consisting of 88 parts of dimethylformamide, squeezed to a squeezing ratio of 150%, solidified in water for 6 minutes, and then 90 ° PVA was dissolved and removed in hot water at C to 100 ° C and dried.
  • Table 5 shows the bending elasticity of the obtained sheet-like composite material.
  • the flexural elasticity of the sheet-like composite material of the present invention is as low as 0.023, which is obtained by treating the fibrous base material with a water-repellent treatment (see Comparative Example 8), the fibrous base material and the elastic polymer material. It is clear that it is much more flexible than the untreated one (see Comparative Example 9). In addition, the fibrous base material after pretreatment had extremely good morphological stability during processing due to the binder-effect of PVA.
  • the solution was dried with a hot air drier at 150 degrees for 3 minutes, and 1% of a methylhydrogenpolysiloxane active ingredient was attached to the nonwoven fabric.
  • methylethoxypolysiloxane a copolymerized silicone composed of 11 parts of a polyurethane having a polyester ether copolymer soft segment, about 60% of methylethoxysiloxane and about 40% of dimethylsiloxane.
  • a polyurethane solution consisting of 1 part of siloxane and 88 parts of dimethylformamide is impregnated into the pretreated nonwoven fabric, squeezed to a squeezing ratio of 250%, and solidified in water for 6 minutes. Washed and dried in warm water at 70 ° C to 70 ° C for 20 minutes.
  • Table 6 shows the bending elasticity of the obtained sheet-like composite material.
  • the ones obtained by the present invention were as low as 1.05 and were subjected to water repellency treatment on the fibrous base material (see Comparative Example 10), and those not treated on both the fibrous base material and the elastic polymer substance ( Compared to Comparative Example 11), it is very flexible.
  • Example 7 Prepared from the nonwoven fabric obtained in Example 7 from 1 part of methylpolysiloxane, a copolymer silicone consisting of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, 5 parts of PVA, and 94 parts of water. Immersed in the hydrophobizing pretreatment liquid, and then uniformly squeezed with a nip roll so that the squeezing rate becomes 100%, and then dried at 150 ° C for 3 minutes with a hot air drier.
  • Table 6 shows the bending elasticity of the obtained sheet-like composite material.
  • the flexural elasticity of the composite material obtained by the present invention is as low as 1.21, and the fibrous base material is subjected to a water-repellent treatment (see Comparative Example 10), and neither the fibrous base material nor the elastic polymer substance is treated at all. Very flexible compared to the ones (see Comparative Example 11) You can see this.
  • the fibrous base material after pretreatment had extremely good morphological stability during processing due to the binder effect of PVA.
  • methylhydrogenpolysiloxane which is a copolymer silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, and a slip inhibitor BY22_839 (Toray) ⁇ Dow ⁇ Koning Active ingredient 20%)
  • a pretreatment for hydrophobization prepared from 0.2 parts of water and 98.8 parts of water, and then squeeze uniformly with a nip roll so that the squeezing rate becomes 100%. Liquid.
  • a copolymer silicone composed of 11 parts of a polyester having a polyester ether copolymer soft segment, about 60% of methylethoxysiloxane and about 40% of dimethylsiloxane, and
  • the non-woven fabric after the above pretreatment is impregnated with a polyurethane solution consisting of 88 parts of dimethylformamide, squeezed to a squeezing ratio of 250%, and solidified in water for 6 minutes, and then at 60 ° C to 70 °. Washed and dried in warm water of C for 20 minutes.
  • Table 6 shows the bending elasticity of the obtained sheet-like composite material.
  • Those obtained by the present invention include those obtained by subjecting a fibrous base material to a water-repellent treatment as low as 1.33 (see Comparative Example 10) and those obtained by not treating any of the fibrous base material and the elastic polymer substance at all. This is very flexible compared to (see Comparative Example 11).
  • the fibrous base material after the pretreatment had extremely good morphological stability during processing due to the effect of the slip inhibitor.
  • Wool 48th twin yarn is converted to about 55% of methylhydrogensiloxane.
  • dimethylsiloxane and about 45% of dimethylsiloxane a copolymerized silicone consisting of 1 part of methyl hydride polysiloxane and 99 parts of water, and then squeezed by a centrifugal dehydrator at 60% squeezing rate. Then, the mixture was dried at 150 ° C. for 3 minutes with a hot-air drier, and an active ingredient of methylhydrogenpolysiloxane was attached to the twin yarn by 0.6%.
  • methylethoxypolysiloxane which is a copolymerized silicone composed of 11 parts of polyurethane having a polyester ether copolymer soft segment, about 60% of methylethoxysiloxane and about 40% of dimethylsiloxane, and 1 part of dimethyl
  • the pre-treated twin yarn is impregnated with a polyurethane solution consisting of 88 parts of formamide, squeezed to a squeezing ratio of 150%, and solidified in water for 6 minutes, followed by 60 ° C to 70 ° C. Washed in warm water for 20 minutes and dried.
  • Table 7 shows the bending elasticity and shrinkage of the composite material of the obtained impregnated yarn. Bending elasticity of impregnated yarn obtained in the present invention, 1. 32g f cm 2/100 present and rather low, the fibrous base material, the one that does not any processing on both the elastic polymeric substance (see ratio Comparative Examples 13) In comparison, it is very flexible. Also, it can be seen that the shrinkage rate is lower than that of the untreated yarn, and there is an anti-shrink effect.
  • Hydrophobizing pretreatment prepared from 1 part of methylhydrogenpolysiloxane, a copolymerized silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, and 99 parts of water was added to the woven fabric obtained in Example 4. Immersed in the liquid, then uniformly squeezed with a nip roll so as to obtain a squeezing ratio of 60%, dried with a hot air drier at 150 ° C for 3 minutes, and dried with a methylhydrogenpolysiloxane active ingredient. 0.6% was attached.
  • polyester ether copolymer soft segment Polypropylene solution consisting of 20 parts of polyurethane, 2 parts of methylethoxypolysiloxane, a copolymerized silicone composed of about 60% methylethoxysiloxane and about 40% dimethylsiloxane, and 78 parts of dimethylformamide
  • the pretreated fabric was coated with a knife coater at 500 g / m 2 , coagulated in water for 6 minutes, washed and dried in warm water at 60 ° C to 70 ° C for 20 minutes.
  • the bending elasticity and peeling strength of the obtained sheet-like composite material are shown in Table 7, and the bending elasticity of the sheet-like composite material of the present invention was as low as 0.53, which was obtained by applying water-repellent treatment to a fibrous base material ( It can be seen that it is much more flexible as compared to the case where neither the fibrous base material nor the elastic polymer material is treated at all (see Comparative Example 15).
  • the separation strength was 1500 gfZinch, which was much higher than that of the fluorine-based water-repellent treatment and calendered crushed product (Comparative Example 15).
  • the solution is uniformly squeezed with a nip roll so as to have a squeezing ratio of 60%, and then dried in a hot-air dryer at 150 ° C for 3 minutes to remove the active ingredient of the fluorine-based water repellent from the fabric. 0.30% solid content.
  • methylethoxypolysiloxane which is a copolymerized silicone composed of 20 parts of polyurethane having a polyester ether copolymer soft segment, about 60% of methylethoxysiloxane and about 40% of dimethylsiloxane, and 2 parts of dimethyl 500 g of a polyurethane solution consisting of 78 parts of formamide was added to the pretreated fabric using a knife coater. m 2 Koti Ngushi, then water coagulated 6 minutes, followed by 60. Washed in warm water of C-70 ° C for 20 minutes and dried. At the time of coating, good workability was achieved without any penetration of the urethane solution.
  • the bending elasticity and peeling strength of the obtained sheet-like composite material are shown in Table 8, and the bending elasticity of the sheet-like composite material of the present invention was low at 0.45, which was obtained by applying water-repellent treatment to a fibrous base material. It can be seen that it is much more flexible as compared to (see Comparative Example 14) and those not treated with both the fibrous base material and the elastic polymer material (see Comparative Example 15).
  • the separation strength was ZOOOgf Zincch, which was very high compared to the fluorine-based water-repellent treatment and calendered finished product (Comparative Example 16). This is thought to be because urethane penetrated non-adhesively surrounding the 0.5-d nylon 6 fiber with a small fineness, which was confirmed by an electron microscope.
  • Hydrophobic prepared from 1 part of methylhydrogenpolysiloxane, a copolymerized silicone consisting of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, and 99 parts of water on a plain cloth (tuft) of 66-inch fiber. After immersion after the pretreatment, the squeezed solution was uniformly squeezed with a nip roll to a squeezing rate of 60%, and then dried at 150 ° C for 3 minutes with a hot-air drier to remove the methylhydrogenpolysiloxane active ingredient. 0.6% was attached to the fabric.
  • methylethoxypolysiloxane 1 which is a copolymerized silicone composed of 11 parts of a polyurethane having a polyester ether copolymer soft segment, about 60% of methylethoxysiloxane and about 40% of dimethylsiloxane is used.
  • emulsion-type polyurethane dispersion consisting of 50 parts of methylethylketone, 13 parts of toluene and 15 parts of water, is impregnated into the woven fabric after the pre-hydrophobization treatment, so that the drawing ratio becomes 150%. And squeezed. It was then dried at 80 ° C for 3 minutes and then at 120 for 3 minutes.
  • the bending elasticity and separation strength of the obtained sheet-like composite material are shown in Table 8, and the bending elasticity of the sheet-like composite material of the present invention was as low as 0.47, which was obtained by applying water-repellent treatment to a fibrous base material. It can be seen that it is much more flexible as compared to (see Comparative Example 14) and those not treated with both the fibrous base material and the elastic polymer material (see Comparative Example 15). In addition, the separation strength was 1800 gf / inch, which was much higher than that of the fluorine-based water-repellent treatment and calendered product (Comparative Example 16).
  • Hydrophobizing pretreatment prepared from 1 part of methylhydrodienepolysiloxane, which is a copolymerized silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, and 99 parts of water was added to the woven fabric obtained in Example 4. Immersed in the liquid, and then uniformly squeezed with a nip roll so as to obtain a squeezing ratio of 60% .Then, the fabric was dried with a hot air drier at 150 ° C for 3 minutes, and the active ingredient of methylhydrogenpolysiloxane was added to the fabric. On the other hand, 0.6% was attached.
  • a polyurethane solution comprising 11 parts of a polyurethane having a polyester ether copolymer soft segment and 89 parts of dimethylformamide was impregnated into the woven fabric after the pretreatment, and a drawing ratio of 150 parts was obtained. %, Coagulated in water for 6 minutes, then washed in warm water at 60 ° C. to 70 ° C. for 20 minutes, and dried.
  • Table 4 shows the bending elasticity of the obtained sheet-like composite material.
  • the bending elasticity of the sheet was as high as 0.027, which was harder and more paper-like than the sheet obtained in Example 4.
  • Table 4 shows the bending elasticity of the obtained sheet-like composite material.
  • the bending elasticity of the sheet-like composite material was as high as 0.031, which was harder and more paper-like than that of the present invention shown in Example 4.
  • the knitted fabric obtained in Example 5 was subjected to a hydrophobic pretreatment prepared from 1 part of methylhydrogenenepolysiloxane, which is a copolymerized silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane, and 99 parts of water. After immersing the knitted fabric in the solution and then squeezing it uniformly with a nip roll so as to obtain a squeezing ratio of 60%, drying at 150 ° C for 3 minutes with a hot air drier, the methylhydrogenpolysiloxane active ingredient is applied to the knitted fabric. And deposited 0.6%.
  • methylhydrogenenepolysiloxane which is a copolymerized silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylsiloxane
  • the knitted fabric after the pre-treatment was impregnated with a polyurethane solution composed of 11 parts of a polyurethane having a polyester ether copolymer-based soft segment and 89 parts of dimethylformamide.
  • the solution was squeezed to 150%, coagulated in water for 6 minutes, washed in warm water at 60 ° C to 70 ° C for 20 minutes, and dried.
  • Table 5 shows the bending elasticity of the obtained sheet-like composite material.
  • the flexural elasticity of the composite material of the sheet was as high as 0.037, which was harder and more paper-like than those of the present invention obtained in Examples 5 and 6.
  • the knitted fabric obtained in Example 5 was impregnated with a polyurethane solution comprising 11 parts of a polyurethane having a polyester ether copolymer-based soft segment and 89 parts of dimethylformamide, and a drawing ratio of 150% And coagulated in water for 6 minutes, followed by warm water at 60 ° C to 70 ° C for 20 minutes While washing and drying.
  • Table 5 shows the bending elasticity of the obtained sheet-like composite material.
  • the bending elasticity of the sheet-like composite material was as high as 0.042, which was harder and more paper-like than those of the present invention shown in Examples 5 and 6.
  • Methyl hydrogenesis mouth Methyl hydridene polysiloxane a copolymer silicone consisting of about 55% of hexane and about 45% of dimethyl siloxane, is immersed in a hydrophobizing pretreatment liquid prepared from 1 part and 99 parts of water. After squeezing uniformly to a squeezing ratio of 100%, the mixture was dried with a hot air drier at 150 ° C for 3 minutes, and 1% of a methylhydrogenpolysiloxane active ingredient was adhered to the nonwoven fabric.
  • the nonwoven fabric after the pre-treatment was impregnated with a polyester solution consisting of 11 parts of polyester having a polyester ether copolymer soft segment and 89 parts of dimethylformamide, and squeezed.
  • the solution was squeezed to a rate of 250%, solidified in water for 6 minutes, and then washed and dried in warm water at 60 ° C to 70 ° C for 20 minutes.
  • Table 6 shows the bending elasticity of the obtained sheet-like composite material.
  • the bending elasticity of the sheet-like composite material was as high as 2.21, which was harder and more paper-like than those of the composite materials of the present invention shown in Examples 7, 8, and 9.
  • Example 8 The nonwoven fabric obtained in Example 8 was impregnated with a polyurethane solution composed of 11 parts of a polyurethane having a polyester ether copolymer-based soft segment and 89 parts of dimethylformamide, and the drawing ratio was reduced. The solution was squeezed to 250%, solidified in water for 6 minutes, then washed in warm water at 60 ° C to 70 ° C for 20 minutes, and dried. Table 6 shows the bending elasticity of the obtained sheet-like composite material. The bending elasticity of the sheet-like composite material was as high as 2.62, which was harder and more paper-like than those of the present invention obtained in Examples 7, 8, and 9.
  • the nonwoven fabric obtained in Example 8 was added to a surfactant A (PEG) comprising MDI, a polyethylene propylene glycol having a weight average molecular weight of 1580 (abbreviated as PPG), and a polyethylene glycol having a weight average molecular weight of 1850 (abbreviated as PEG).
  • PEG surfactant A
  • -MDI-PPG- MDI-PPG- MDI-PEG immersed in a pretreatment liquid prepared from 0.3 parts of a 60% methyl ethyl ketone solution and 99.7 parts of water, and then nip rolled to a uniform drawing ratio of 150%. After the solution was squeezed, the mixture was dried at 180 ° C for 1 minute with a hot air drier, and the surfactant A active ingredient was adhered to the nonwoven fabric by 0.23%.
  • a polyurethane solution comprising 11 parts of a polyurethane having a polyester ether copolymer-based soft segment, 9 parts of a surfactant AO, and 88.1 parts of dimethylformamide was applied to the nonwoven fabric after the pretreatment. Then, the solution was squeezed so as to have a squeezing ratio of 250%, solidified in water for 6 minutes, then washed in warm water at 60 ° C to 70 ° C for 20 minutes, and dried.
  • Table 6 shows the bending elasticity of the obtained sheet-like composite material.
  • the flexural elasticity of the composite material of the sheet was as high as 2.35, which was softer than that of the fiber substrate and the elastic polymer material which were not treated at all (see Comparative Example 11). Compared with the present invention shown in 7, 8, and 9, the hard and paper-like texture was obtained.
  • Example 10 The wool 48-count double yarn used in Example 10 was impregnated with a polyurethane solution consisting of 11 parts of a polyurethane having a polyester ether copolymer-based soft segment and 89 parts of dimethylformamide, and a drawing ratio of 150% The solution was then squeezed and solidified in water for 6 minutes, and then washed and dried in warm water at 60 ° C to 70 ° C for 20 minutes.
  • Table 8 shows the bending elasticity and shrinkage of the composite material of the obtained impregnated yarn. Shrinkage of the composite material obtained impregnated yarn is becomes 4%, but shrink effect is observed, flexural modulus as high as 2.15gfcm 2/100 present, from impregnated yarns of the present invention obtained in Example 10 Very hard.
  • methylhydrodienepolysiloxane which is a copolymer silicone composed of about 55% of methylhydrogensiloxane and about 45% of dimethylloxane, and 99 parts of water
  • the woven fabric obtained in Example 4 was added. After being immersed in the treatment liquid and then uniformly squeezed with a nip roll so as to have a squeezing ratio of 60%, the fabric was dried with a hot air drier at 150 for 3 minutes, and the active ingredient of methylhydrodienepolysiloxane was added to the fabric. On the other hand, 0.6% was attached.
  • a polyurethane solution consisting of 20 parts of a polyurethane having a polyester ether copolymer soft segment and 80 parts of dimethylformamide was added to the woven fabric after the pretreatment by a knife coater in an amount of 500 g. / m '' coated and solidified in water for 6 minutes, followed by washing in warm water at 60 ° C to 70 ° C for 20 minutes and drying.
  • the bending elasticity and separation strength of the obtained sheet-like composite material are shown in Table 8. c
  • the separation strength of the sheet-like composite material was as high as 1610 gfZinch.
  • the flexural elasticity was as high as 1.01, which was harder than that obtained in Example 11.
  • a polyurethane solution comprising 20 parts of a polyurethane having a polyester ether copolymer soft segment and 80 parts of dimethylformamide was added to the woven fabric obtained in Example 4 with a knife coater at 500 g / m. Two Coating, coagulation in water for 6 minutes, followed by washing and drying in warm water at 60-70 ° C for 20 minutes.
  • the bending elasticity and separation strength of the obtained sheet-like composite material are shown in Table 8.
  • the separation strength of the sheet-like composite material was as high as 1650 gfZinch.
  • the flexural elasticity was as high as 1.21, which was harder than that of the present invention shown in Example 8.
  • Example 4 The fabric obtained in Example 4 was subjected to a water repellent treatment with a 2% aqueous solution of a fluorine-based water repellent. Next, one heat calender treatment was performed at a temperature of 160 ° C and a linear pressure of 130 kg Zcm to smooth the surface.
  • a 500 g / m 2 coating of a polyurethane solution comprising 20 parts of a polyurethane having a polyester ether copolymer-based soft segment and 80 parts of dimethylformamide with a knife coater was applied to the woven fabric.
  • the bending elasticity and separation strength of the obtained sheet-like composite material are shown in Table 5.
  • the bending elasticity of the sheet-like composite material is as low as 0.78 and has a soft texture, but the separation strength is 750 gf Zinch. The result was lower than that of the present invention obtained in Example 11.
  • the composite material obtained according to the present invention is extremely flexible in the case of a cloth impregnated with an elastic polymer substance, and by providing an elastic polymer substance impregnated density distribution, it is possible to obtain mechanical properties such as durability such as abrasion resistance and tear strength. It can be used for clothing, furniture, shoes, power sheets, and other industrial materials as synthetic leather and artificial leather with excellent mechanical strength.
  • mechanical properties such as durability such as abrasion resistance and tear strength. It can be used for clothing, furniture, shoes, power sheets, and other industrial materials as synthetic leather and artificial leather with excellent mechanical strength.
  • various windbreakers and futon outer fabrics that are flexible, do not produce sound, have extremely high separation strength, and are excellent in moisture permeability and water pressure resistance. For maintaining the shape of knit products such as jerseys, stockings, etc., and preventing shrinkage during washing of wool, rayon, etc. It is useful for processing.

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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un matériau composite du type en feuille, qu'on obtient en revêtant ou imprégnant un substrat fibreux avec un materiau polymère élastique, qui prévient l'adhérence entre les fibres cconstituant ce substrat fibreux et le matériau polymère élastique, qui se révèle extrêmement doux et présente une résistance extrêmement élevée à l'usure ou à la séparation. On peut produire ce matériau composite en soumettant ce substrat fibreux à un traitement hydrophobe, en imprégnant ou revêtant ce substrat avec une solution d'un matériau polymère élastique à laquelle on rajoute un silicone hydrophile, puis par coagulation humide de ce substrat.
PCT/JP1993/001611 1992-05-07 1993-11-05 Materiau composite et procede de production WO1995012706A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US08/448,521 US5922445A (en) 1992-05-07 1993-11-05 Composite material and process for production of same
KR1019950702761A KR0145192B1 (ko) 1993-11-05 1993-11-05 복합 재료 및 그의 제조 방법
PCT/JP1993/001611 WO1995012706A1 (fr) 1993-11-05 1993-11-05 Materiau composite et procede de production
GB9512449A GB2288993B (en) 1993-11-05 1993-11-05 Composite material and process for production of same
CN93121430A CN1057141C (zh) 1993-11-05 1993-11-16 片状复合材料及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/JP1993/001611 WO1995012706A1 (fr) 1993-11-05 1993-11-05 Materiau composite et procede de production
CN93121430A CN1057141C (zh) 1993-11-05 1993-11-16 片状复合材料及其制造方法

Publications (1)

Publication Number Publication Date
WO1995012706A1 true WO1995012706A1 (fr) 1995-05-11

Family

ID=36933438

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1993/001611 WO1995012706A1 (fr) 1992-05-07 1993-11-05 Materiau composite et procede de production

Country Status (3)

Country Link
CN (1) CN1057141C (fr)
GB (1) GB2288993B (fr)
WO (1) WO1995012706A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009037565A1 (de) * 2009-08-14 2011-02-24 Mavig Gmbh Beschichtete Mikrofaserbahn und Verfahren zur Herstellung derselben

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05132878A (ja) * 1991-11-06 1993-05-28 Toray Ind Inc 立毛性状、柔軟性および高強力に優れた皮革様物の製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69418266T2 (de) * 1993-03-10 1999-09-09 Teijin Ltd Narbenkunstleder, verfahren zu dessen herstellung und daraus hergestellter gegenstand
KR960007596B1 (ko) * 1993-10-19 1996-06-07 김성욱 투습방수포 및 그 제조방법

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05132878A (ja) * 1991-11-06 1993-05-28 Toray Ind Inc 立毛性状、柔軟性および高強力に優れた皮革様物の製造方法

Also Published As

Publication number Publication date
CN1057141C (zh) 2000-10-04
GB9512449D0 (en) 1995-09-06
GB2288993A (en) 1995-11-08
CN1103122A (zh) 1995-05-31
GB2288993B (en) 1998-02-25

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