JPH08291473A - Composite material, its production and moisture-permeable waterproofing cloth made thereof - Google Patents

Abstract

PURPOSE: To provide a composite material composed of a fibrous substrate and an elastic polymer substance, having high moisture permeability in spite of soft texture, exhibiting high peeling strength, tearing strength and abrasion resistance of the elastic polymer and free from the bleeding of the elastic polymer substance and to provide its production process and moisture-permeable waterproofing cloth made of the composite material. CONSTITUTION: This composite material is a sheet having a layer of an elastic polymer substance formed on one surface of a fibrous substrate made of bulky textured yarn. The elastic polymer substance is intruded into the gap between single fibers of the fibrous substrate in the cross section of the sheet and the composite material satisfies the formula 0.3<=Nn/Nt<=0.95 wherein Nt is the total number of fiber cross sections existing on the surface of the fibrous substrate having the elastic polymer substance layer and Nn is the number of fiber cross sections free from adhesion to the elastic polymer substance on the circumference of the fiber cross section. This invention also relates to its production process and a moisture-permeable water-proofing cloth for clothes composed of the composite material having the elastic polymer substance layer of 1-200μm thickness.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite material in which a layer of an elastic polymer substance is formed on one surface of a fibrous base material such as a knitted fabric.

[0002]

2. Description of the Related Art In recent years, with increasing interest in comfort and health, especially in the use of clothing and daily life materials, it has moisture-permeable, waterproof, and water-repellent functions, and has a soft texture when worn. Fabrics with less noise have been demanded. Conventionally, as a method of fulfilling such a demand, for example, a method of laminating a polymer film on a cloth made of bulky yarn obtained from nylon 66 multifilament (JP-A-4-17).
No. 3011) and the like are generally used, and the obtained cloth having moisture-permeable, waterproof, and water-repellent functions is often used for sports applications such as windbreakers. Such fabrics are generally obtained by coating the fabric with urethane that foams upon solidification. However, according to such a conventional method, the resin penetrates into the inside of the fiber structure, and this restrains the fiber and significantly reduces the degree of freedom of the fiber, so that the texture of the obtained fabric is hardened and its tear strength is increased. There is a problem of decrease. It is extremely difficult to avoid the problems of hardening the texture and lowering the tear strength even if a soft resin such as urethane is used.

Proposals for such problems have already been made. For example, in JP-A-4-114431, a fibrous base material is subjected to a water-repellent silicone treatment, and a solution of an elastic polymer substance to which a hydrophilic silicone is added is coated and then wet coagulated. This proposal realizes a structure (abbreviated as a non-adhesive structure) in which the adhesion between the elastic polymer substance and the fiber is obstructed, and is an extremely flexible and highly peelable cohesive coating that could not be achieved by the prior art. A composite material having a coating layer is said to be obtained.

However, in the method proposed above,
During coating, the elastic polymer substance penetrates deeply into the fibrous base material and reaches the back surface, so that the back roll of the processing machine is soiled, and further, for example, the wind breaker using the coating surface as the back side. In such a case, the elastic polymer substance may exude to the front side, which may cause color defects or white blur of the obtained composite material. In addition, in a fibrous base material such as a woven fabric, it is difficult to sufficiently permeate the elastic polymer substance into the single fibers due to the narrow single fiber gap of the fibrous base material, and thus the peel strength and abrasion strength are reduced. There was a problem of doing.

[0005]

The problem to be solved by the present invention is to solve the drawbacks of the prior art by using a fibrous base material and an elastic polymer material, which is flexible and has a high moisture permeability, and is elastic. (EN) Provided are a composite material having high peel strength, tear strength, and abrasion strength of a polymeric substance and having no exudation of an elastic polymeric substance, a method for producing the same, and a moisture-permeable waterproof cloth comprising the same.

[0006]

As a result of intensive studies to solve the above problems, the present inventors have succeeded in finding a composite material and a method for producing the same that can achieve the objects of the present invention. Has been completed. That is, the present invention is a sheet-shaped composite material in which a layer of an elastic polymer substance is formed on one side of a fibrous base material using a bulky processed yarn, and the elastic polymer substance is Of the total number Nt of fiber cross-sections existing on the surface of the fibrous base material on the side where the layer is formed, with respect to Nt of the number Nn of fiber cross-sections not bonded to the elastic polymer substance on the circumference of the fiber cross section. The ratio Nn / Nt is 0.
It is a sheet-shaped composite material characterized by being 3 to 1.

Further, the present invention is a moisture-permeable waterproof cloth for clothing, comprising the composite material, wherein a layer of an elastic polymer material is formed on one side of a fiber base material using a bulky processed yarn with a thickness of 1 to 200 μm, Further, the present invention is a method for producing a composite material in which an elastic polymer material layer is formed on one surface of a fibrous base material, wherein (1) the fibrous base material is formed by using a bulky processed yarn, and ( 2) A hydrophobizing pretreatment agent containing a fluorine-based water repellent as a main component is attached to the fibrous base material, and (3) the base material is
Coating with a solution or emulsion of an elastic polymer substance to which hydrophilic silicone is added, and (4) dipping the substrate in a poor solvent for the elastic polymer substance to solidify it, or by scattering the solvent by drying. A method for producing a composite material, which comprises solidifying.

The present invention will be described in more detail below. In order to facilitate understanding of the present invention, an outline of the present invention will be first described with reference to the drawings. FIG. 1 is a diagram showing an enlarged cross-sectional structure of a composite material as an example of the present invention. In FIG. 1, 1 is a fiber, 2 is an elastic polymer substance (polyurethane) 3 is a fibrous base material.

Fibers 1 in FIG. 1 are fibers existing at the interface between the fibrous base material 3 and the elastic polymer substance 2 and surrounded by the elastic polymer substance 2 in a non-adhesive manner. FIG.
(A) a suitable gap is provided between the monofilaments on the surface of the fibrous base material using the bulky processed yarn, and the monofilaments are covered with polyurethane, and most of them have no adhesion to the polyurethane. It is shown that, while (b) polyurethane is permeated so as to surround the single fibers 1 on the surface, exudation to the back side is suppressed. By forming the structures of (a) and (b) in this way, the composite material according to the present invention has excellent flexibility and high moisture permeability, and at the same time, peeling of the polyurethane layer having an antinomic relation with these characteristics. At the same time, the properties such as strength, tear strength, and wear strength are satisfied, and in addition, defects such as bleeding of polyurethane can be suppressed. On the other hand, FIG. 2 is an enlarged cross-sectional structure of a composite material which is a comparative example lacking a part of the constitution of the present invention. That is, in FIG. 2, the single fibers 1 on the surface of a general fiber substrate 3 do not have an appropriate gap, and a polyurethane non-adhesive structure is formed, but there is little polyurethane covering the single fibers. I understand things. In this case, although flexibility is obtained, it is unavoidable that the peel strength, tear strength, and abrasion strength of the polyurethane layer deteriorate. FIG. 3 shows an enlarged cross-sectional structure of a composite material which is a comparative example of the present invention. In FIG. 3, polyurethane 2
Indicates that the monofilament 1 on the surface of the fibrous base material 3 is bonded. In the composite material having such a structure, flexibility, peeling strength, tear strength, and abrasion strength are greatly influenced by the degree of adhesion area between the single fiber and polyurethane, and it is almost impossible to satisfy all of them at the same time.

FIG. 4 is also a diagram showing an enlarged sectional structure of a composite material which is a comparative example of the present invention. Although the non-adhesive structure is formed in this figure, it is shown that the elastic polymer substance oozes out to the back side (4 in the figure is that portion). In this case, when viewed from the back side (it becomes the front side when worn), it becomes a color defect of the fibrous base material and cannot be put to practical use as it is.

Next, the elastic polymer substance in the present invention means
Polyester type, lactone ester type, polyether type, polyester / polyether copolymer type, polycarbonate type polyurethane or polyvinyl chloride type or polyacrylic acid ester type synthetic resin, and butadiene type
It is a polymer material having rubber-like elasticity such as styrene-based, nitrile-based or chloroprene-based synthetic rubber or natural rubber, or a mixture mainly containing these. Of these, polyurethane-based elastic polymer substances are preferable because of their excellent flexibility.

Further, the inventors of the present invention have surprisingly been able to obtain a high moisture permeability by forming a non-adhesive structure on a fibrous base material using a bulky processed yarn, and have an extremely excellent dew condensation preventing effect. I found that. For example, as shown in FIG. 1, when observing a cross-sectional structure of a composite material obtained by coating a fibrous base material using a bulky processed yarn with a urethane resin, it is possible to obtain a large number of fibers in the urethane layer by debonding the fibers and urethane. Independent monofilaments can be recognized. With such a structure, the gap portion of the urethane layer becomes large and the moisture permeability can be improved. However, as shown in FIG. 3, when urethane is coated on a fibrous base material using a bulky processed yarn as is conventionally done, the gap between the urethane layer where the fiber and the urethane are bonded is small and the moisture permeability is reduced. To do. Also, when urethane is coated on a fibrous base material that does not use a bulky processed yarn as shown in FIG. 2, the resulting composite material has few independent single fibers present in the urethane layer,
As a result, it is not possible to expect much improvement in moisture permeability.

The bulky yarn used in the present invention is a synthetic fiber,
Fluid disturbance treatment of yarns consisting of semi-synthetic fibers and natural fibers, fluid disturbance treatment with no difference in the yarn feed amount between the core yarn and the sheath yarn, and the overfeed rate of the sheath yarn is made larger than that of the core yarn. A bulky processed yarn obtained by any method such as fluid disturbance treatment or false twisting may be used.

The term "fluid disturbance treatment" as used herein means injection crimping such as Taslan or interlace. Desirable yarn fineness for performing the fluid disturbance treatment is preferably 0.1 to 5 d from the viewpoint of processing stability and bulkiness. Also,
The sheath yarn has a single yarn fineness of 0.1 to 3d, and the core yarn has 0.5
It is preferable that the sheath yarn has a fineness equal to or smaller than that of the core yarn in order to obtain a flexible bulky yarn.

With respect to the bulky textured yarn obtained by false twisting, the crimp shape factor (CE / N) described later is set to 0.3 to 5 in order not to make the appearance paper-like and to prevent the fastener phenomenon from occurring. It is preferable. Further, false twisting may be performed by mixing yarns having different finenesses. The fibrous base material using the bulky processed yarn in the present invention,
Woven fabrics such as plain weave, twill weave, satin weave, etc. using the above-mentioned bulk textured yarn as weft yarns and / or warp yarns, and weft such as plain knitting, rubber knitting, and pallet knitting using bulky textured yarn at least in part Knitting, single tricot knitting, single atlas knitting, single code knitting, half tricot knitting, plane tricot knitting, queen's code knitting, spelling and other warp knitting.

The composite material referred to in the present invention means that a layer of an elastic polymer substance is formed on one side of the fibrous base material using the above-mentioned bulky processed yarn (including naturally partially impregnated ones). Fiber / elastic polymer composite. The degree of penetration of the elastic polymer substance into the fibrous base material in the present invention is preferably within 1/2 of the thickness of the fibrous base material. If this penetration exceeds 1/2, unevenness in color due to the bleeding of the elastic polymer material to the back side of the coating surface or a so-called white blur, which is a dull white color, occurs, and the coating process This is because the back roll and the like are sometimes contaminated and processing troubles such as long processing cannot be performed.

Further, in the present invention, it is preferable to increase the portion where the elastic polymer substance permeates so as to surround the fibers of the outermost layer of the fibrous base material.
The peeling strength of the coating layer can be extremely increased. In the composite material of the present invention, the appearance frequency of the fibers surrounded by the elastic polymer substance is preferably one or more per 1000 μm in the direction parallel to the sheet surface on the electron micrograph. It is more preferable if one or more is present in 500 μm or more.

In the present invention, of the total number Nt of fiber cross sections existing on the surface of the fibrous base material, the ratio Nn of the number Nn of fiber cross sections not bonded to the elastic polymer substance on the circumference of the fiber cross section to Nt. / Nt is measured as follows. That is, a cross section of a sheet-shaped composite material cut at an arbitrary 5 positions with a sharp blade was photographed at a magnification of 350 times, and the obtained electron microscopic cross-sectional photograph was perpendicular to the sheet surface of the composite material. It is divided into 500 μm units to obtain a large number of divided photographs. An arbitrary 10 divided photographs are extracted and observed from this, and the total number Nt of fiber cross-sections present on the surface of the fibrous base material is obtained on the side coated with the elastic polymer material. Then, the number Nn of fibers observed so that the elastic polymer substance is not in contact with the circumference of the fiber cross section is determined. Then, the ratio Nn / Nt is calculated.
In the present invention, this ratio Nn / Nt needs to be 0.3 or more and 1 or less, and more preferably 0.5 to 1.

The inventors of the present invention have found that the degree of non-adhesion between the elastic polymer substance and the fibers existing at the interface between the layer of the elastic polymer substance and the fibrous base material depends on the flexibility of the composite material and the elastic polymer substance. The fact that the peel strength, tear strength, and wear strength of the layer of is very closely related was found out, and based on this fact, the present invention has been completed, and a structure in which this Nn / Nt falls within the above range was constructed. By forming the composite material, it is possible to obtain the composite material of the present invention capable of simultaneously providing excellent flexibility and excellent peeling strength and tear strength of the coating layer, which are properties contradictory to this flexibility.

When Nn / Nt is less than 0.3, the structure is such that substantially most of the fibers are bonded to the elastic polymer substance, so that the texture is hard and the tear strength is remarkably lowered.
The thickness of the coating layer of the elastic polymer material in the present invention is preferably 1 to 200 μm for clothing. If the thickness is less than 1 μm, the water pressure resistance may decrease in applications such as windbreakers and jackets that require water pressure resistance. If it exceeds 200 μm,
It is not preferable because the soft texture of the fibers does not live and gives a rubber-like texture.

Next, a method of manufacturing the composite material according to the present invention will be described. As the fluorine-based water repellent used as the main component of the hydrophobizing pretreatment agent for the fibrous base material in the present invention, for example, some or all of the hydrogen atoms of the alkyl compound having 3 to 20 carbon atoms are replaced with fluorine. Examples thereof include a fluorine-based water repellent agent comprising a fluoroalkyl compound or a copolymer of an acrylate or methacrylate derived from a perfluoroalkyl compound and a vinyl compound. The critical surface tension of the surface of the fibrous base material treated with the fluorine-based water repellent is preferably 30 dynes / cm or less.

Further, as a secondary additive for improving flexibility, it is used in combination with the above-mentioned fluorine-based water repellent, and is in a range of less than the amount of the fluorine-based water repellent containing water-repellent silicone as a main component. It can be used in. This water repellent silicone used in combination
As the resin, for example, dimethylpolysiloxane, alkyl-modified polysiloxane, hydrogen-modified polysiloxane, amino-modified polysiloxane, epoxy-modified polysiloxane, or a copolymerized silicone thereof may be used. Among them, methylhydrogenpolysiloxane and a copolymer of dimethylpolysiloxane and methylhydrogenpolysiloxane are particularly preferably used in the present invention because they have a high hydrophobic effect on the fiber surface.

The amount of the fluorine-based water repellent in the present invention attached to the fibrous base material is 0.1 to 2% by weight based on the weight of the fiber.
It is preferred that More preferably, it is 0.3 to 1% by weight. When the adhesion amount is less than 0.1% by weight, the effect of preventing the binding between the elastic polymer substance and the fiber due to the repulsive action of hydrophobicity and hydrophilicity is small. On the other hand, if the adhered amount is more than 2% by weight,
If the amount is 5% by weight or more, dyeing unevenness may occur during dyeing.

Further, in the present invention, before applying the elastic polymer to the fibrous base material which has been subjected to the hydrophobizing pretreatment, it is smoothed by thermal calendering or the like to the extent that voids on the surface of the fibrous base material are not damaged. May be. Examples of the hydrophilic silicone added to the elastic polymer substance in the present invention include, for example, alkoxy-modified polysiloxane, carboxyl-modified polysiloxane and copolymers thereof, or alkyl polysiloxane such as dimethyl polysiloxane. Copolymers are used. Of these, alkylalkoxypolysiloxanes such as methylethoxypolysiloxane and polyoxyethylenealkylpolysiloxane are preferable because they can further enhance the degree of hydrophilicity imparted to the elastic polymer substance.

The addition amount of the hydrophilic silicone in the present invention to the elastic polymer substance is preferably 0.1 to 10% by weight. If the amount added is less than 0.1% by weight, the effect of preventing adhesion between the elastic polymer substance and the fiber is small due to the hydrophobic and hydrophilic repulsion of the fiber. On the other hand, if the addition amount is more than 10% by weight, the anti-adhesion effect is not further improved, but the increased amount is merely wasted. In addition, the water resistance of the elastic polymer material layer is lowered, and the water pressure resistance of the resulting composite material is lowered. Further, a sorbitan-based or polyoxyethylene-based hydrophilizing agent which is usually used may be used in combination as an auxiliary component.

The hydrophilic silicone may be added to the elastic polymer substance by adding it to a wet coagulation type solution in which the elastic polymer substance is dissolved in a good solvent in advance, or by adding a poor solvent and it. The method of adding to an emulsion dispersed in a mixed solvent with a good solvent having a low boiling point is preferably used in the present invention because it can be added uniformly. When polyurethane is used as the elastic polymer substance, examples of the good solvent for the polyurethane solution include dimethylformamide, dimethylacetamide, methylethylketone, and alcohol / aromatic solvents.

The elastic polymer substance emulsion is, for example, an organic solvent solution or slurry of the elastic polymer substance.
It means the type of emulsion in which water is dispersed,
Examples of the good solvent for the solution in this case include methyl ethyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate and the like, which have a higher vapor pressure than water at low temperature. Examples of the poor solvent include water and toluene, xylene, mineral spirit, or a mixed solvent thereof having a vapor pressure lower than that of water.

As a method for applying the elastic polymer substance to the fibrous base material in the present invention, a solution or emulsion of the elastic polymer substance is applied to a floating knife coater or a knife over roll coater. , Liver roll coater,
Direct coating on woven and knitted fabrics by a conventional method such as a roll coater, a gravure roll coater, a kiss roll coater, a nipple roll coater, and a pipe doctor (comma) coater. May be applied.

The solution viscosity of the elastic polymer material solution coated on the fibrous base material is 500 to 50,000 c.
It is preferably ps. This is based on the fact that the elastic polymer substance, which is a feature of the composite material of the present invention, can be coated so as not to strike through, and that the layer of the elastic polymer substance can be more easily formed on the surface of the fibrous base material. As a method for coagulating the elastic polymer substance in the present invention, the elastic polymer substance dissolved in a good solvent is dipped in a poor solvent for wet coagulation. Alternatively, the elastic polymer substance dissolved in a mixed solvent of a good solvent and a poor solvent is volatilized first by a method such as heating to evaporate the good solvent having a higher vapor pressure at a low temperature, and the ratio of the poor solvent in the elastic polymer substance is reduced. Is increased to cause gelation, and then dried at a temperature higher than the heating temperature at which the poor solvent evaporates to dry-coagulate. In the present invention, the low temperature heating is preferably 50 ° C to 120 ° C, and the high temperature heating is preferably 100 ° C to 190 ° C.

In the present invention, as described above, in both the wet and dry methods, the poor solvent of the elastic polymer substance is allowed to intervene in the coagulation process of the elastic polymer substance solution to repel the fluorine-based water repellent agent on the fiber. The mutual repulsion between the water group and the hydrophilic group of the hydrophilic silicon in the elastic polymer material forms a good non-adhesive structure between the fiber and urethane. The composite material according to the present invention has an extremely high effect of preventing adhesion between the fiber and the elastic polymer substance, and does not exude the elastic polymer substance.
This is probably because the following two mechanisms act synergistically. When the fiber (I) is treated with a fluorine-based water repellent, the fiber is imparted with water repellency and oil repellency, which prevents the exudation of the elastic polymer substance and improves the releasability. (II) Since the fiber surface is hydrophobized and the elastic polymer substance is made hydrophilic, a repulsion action works through the poor solvent during coagulation, and a non-adhesive structure is formed between the fiber and the elastic polymer substance. To be done.

By simply improving the releasability of the fiber or the elastic polymer substance as in the known method, the fiber and the elastic polymer substance are released from each other when the elastic polymer substance is solidified. Instead, it must be followed by physical demolding work such as rubbing. However, even if it is subjected to rubbing treatment or the like, it is not sufficiently released from the mold, and is obtained when the elastic polymer substance and the fiber are prevented from adhering from the solidification stage of the elastic polymer substance as in the structure obtained by the present invention. There is no such flexibility.

The coating cloth made of the elastic polymer material obtained by the production method of the present invention becomes extremely flexible and impairs the feeling of volume and texture originally possessed by the fibrous base material using the bulky processed yarn. There is nothing. In addition, the elastic polymer substance penetrates into the fibrous base material without penetrating the fibrous base material and surrounds the fiber, and is present in the continuous space created by the fibrous base material, so that the high moisture permeability is high. High peeling strength, tear strength and abrasion strength of elastic polymer material layer.

Further, the composite material obtained in the present invention can satisfy the contradictory performances of waterproofness and moisture permeability at the same time, even though the layer of the elastic polymer substance is formed, and in particular, the moisture permeable waterproofness for clothes. It is useful as a cloth. In the present invention, in the elastic polymer material, for example, antibacterial agents and deodorants such as copper and silver compounds, heat storage agents such as zirconium carbide, cellulose, wool, collagen, hygroscopic agents such as chitosan fine particles,
Addition of high-performance fine particles such as, for example, not only for wear and washing durability but also as a flexible, highly-functional processed fabric for a wide range of applications such as shoe materials, furniture, medical applications, etc. Since the application can be expected, it is also preferable in the present invention to add the highly functional fine particles to the elastic polymer substance.

Of course, if the functional fine particles to be used are previously treated with the hydrophobizing pretreatment agent of the present invention, it is easy to form a non-adhesive structure between the applied functional fine particles and the elastic polymer substance,
Even if functional fine particles are added, there is almost no deterioration in strength or flexibility due to the addition. Therefore, the above treatment is preferably used in the present invention. Further, since the elastic polymer substance and the functional fine particles have a non-adhesive structure as described above, the function of the functional fine particles such as antibacterial property and water retention is easily exhibited, and the present invention is preferably used also from this aspect. Of.

The elastic polymer substance in the present invention may contain various additives which are usually used. For example,
It is an additive such as a thickener, a curing agent, a cross-linking agent, a pigment, a gloss imparting agent, a light stabilizer, an antioxidant, an ultraviolet absorber and a flame retardant.

[0036]

EXAMPLES Examples of the present invention will be shown below. In the examples below, all amounts are by weight unless otherwise noted. In addition, the measurement items shown in the examples are measured by the following. (A) Crimp shape factor (CE / N) The crimp shape coefficient (CE / N) is a value that contributes to the elongation per crimp and is measured by the following method.

Crimp shape factor = crimp elongation ratio / crimp number Crimp elongation ratio ... value according to JIS L1090-1977 crimp number ... value according to JIS L1015 (b) Bending elasticity KES manufactured by Kato Tech Co., Ltd. (Kawabata E
volume system) Pure bending test.
The smaller the value, the more flexible it is. (C) Peeling strength According to JIS L-1086 (peeling strength). (D) Tear strength According to JIS L-1096 (Pendulum method). (E) Abrasion Strength Using the friction test type II described in JIS L-8023, the degree of wear of the elastic polymer layer when the elastic polymer layer of the composite material and the white cotton cloth for friction are abraded 500 times at a load of 200 g is ○, Evaluation was made in three levels of Δ and X. (F) Water pressure resistance According to JIS L-1092 (water resistance test). (G) Moisture permeability According to JIS L-1099 (A-1 method). (H) Sounding Evaluation A cloth is sewn on a rubber tube having an outer diameter of 31 mm, a thickness of 3 mm and a length of 150 mm without wrinkles. At this time, the lengthwise direction of the rubber tube and the warp direction of the cloth fabric are sewn in parallel, and the lengthwise direction of the rubber tube and the warp direction of the cloth fabric are sewn at right angles. Both ends should be fixed so that the sewn fabric does not come off the rubber tube.

Next, a pressing load of 100 g / cm ² , 120 times / combined with the former combination of the rubber tubes covered with the cloth and the combination of the former and the latter rubber tubes covered with the cloth.
Reciprocate in minutes. Rion Co., Ltd.
Using a sound level meter manufactured by the same company, trade name NA-29, with the frequency correction circuit set to A and the operability set to SLOW, the noise level (L
p) is measured, and the noise level during silence (24 at 4 KHz)
And compared. (I) Washing resistance According to JIS L-0217 washing resistance method. Washing at a water temperature of 40 ° C. for 5 minutes and rinsing for 4 minutes was set as one cycle, and after performing 10 cycles, predetermined physical property evaluation was performed. (J) Judgment of strike-through prevention property Evaluation was made by visual judgment. (K) Comprehensive evaluation A comprehensive evaluation is made based on the above-mentioned measurement results, and evaluation is made in three grades of ◯, Δ, and ×.

[0039]

Example 1 Nylon 66 having a fineness of 3d is used as a weft thread as a core thread.
Multifilament (50d / 100) of nylon 66 microfiber with a fineness of 0.5d for the fiber (30d / 10f) and sheath yarn
A bulky processed yarn was obtained under the following fluid agitation treatment conditions using f). Processing speed 300 m / min Fluid disturbing pressure 7.5 kg / cm ² Nozzle manufactured by Heberline Co., Ltd. Hema jet TE-312K Overfeed rate 10% core yarn, 25% sheath yarn Feeding method Core yarn, 2 sheath yarns Warp yarn As a core thread, nylon 66 fiber (30d
/ 10f) and a multifilament (50d / 100f) of nylon 66 ultrafine fibers having a fineness of 0.5d for the sheath yarn, to obtain a bulky processed yarn under the following fluid disturbance treatment conditions.

Processing speed 300 m / min Fluid disturbance pressure 2.0 kg / cm ² Nozzle Awa Spindle Co., Ltd. Awa Nozzle MK-2 (23 type) Overfeed rate 2% Yarn feeding method Two simultaneous yarn feeding Next A plain woven fabric having a warp density of 130 yarns / inch and a weft yarn density of 70 yarns / inch was woven using a bulky processed yarn, and the following dyeing finishing process was performed.

Relax Refining 60 ° C. × 30 minutes Dye, manufactured by Meisei Kagaku Co., Ltd. Alizarin Light Blue 4GL,
3% owf Dyeing condition 100 ° C. × 40 min. The dyed taffeta was treated with a perfluoroalkyl-based fluorine-based water repellent (AG-710, manufactured by Meisei Chemical Co., Ltd.) 5
1 part by weight of a copolymerized polysiloxane composed of about 55% by weight of methyl hydrogen siloxane and about 45% of dityl siloxane and a melamine resin (M- manufactured by Sumitomo Chemical Co., Ltd.).
3) Immerse in 0.5 parts by weight and 93.5 parts by weight of water in a pre-hydrophobizing treatment solution, and then squeeze 60 with a nip roll.
After squeezing evenly to give a
It was dried in a hot-air dryer to prepare a hydrophobized pretreatment fabric in which the active ingredient of the fluorine-based water repellent was adhered to the woven fabric at a solid content of 0.50%.

Next, 20 parts by weight of polyurethane having a polyester soft segment, 1.6 parts by weight of methyl ethoxy polysiloxane which is a copolymerized silicone comprising about 60% of methyl ethoxy siloxane and about 40% of dimethyl siloxane, and a solvent system. A polyurethane solution consisting of 1.5 parts by weight of a fluorine water repellent (LS-520 manufactured by Meisei Chemical Co., Ltd.) and 77.9 parts by weight of dimethylformamide was added to the pretreated fabric with a knife coater at 100 g / m 2. ² coats, solidify in water for 6 minutes, then 60-70
It was washed in warm water at 0 ° C. for 20 minutes and dried. Then, a solvent-based silicone water repellent was further attached by a dipping method in a pure amount of about 0.3 g / m ² to obtain a composite material of Example 1.

[0043]

[Example 2] Nylon 66 fiber (30
d / 10f) and a nylon 66 ultrafine fiber multifilament (50d / 100f) with a fineness of 0.5d for the sheath yarn, and false twisting was performed under the following conditions to obtain a bulky yarn. The crimp shape factor of this yarn was 2.5. Pin false twisting condition Spindle speed 30,000 rpm Twisting number Z 3800 T / m Set temperature 200 ℃ Overfeed rate 0% Winding feed rate + 3.0% 130 warp yarns / inch, weft yarn using the above bulky processed yarn Was processed in the same manner as in Example 1 except that a plain weave of 70 fibers / inch was woven to obtain a composite material of Example 2.

[0044]

Example 3 The procedure of Example 3 was repeated except that the polyurethane solution obtained in Example 1 was added with about 10% of zirconium carbide (average particle size: 2 μm) based on the polyurethane solid content. A composite material was obtained.

[0045]

[Comparative Example 1] Weft yarn, a yarn in which nylon 66 fibers (30d / 10f) with a fineness of 3d and multifilaments (50d / 100f) of nylon 66 ultrafine fibers with a fineness of 0.5d are aligned and used, and the warp density is 130 yarns. / Inch, weave plain weave having a weft density of 70 yarns / inch was woven, and
The composite material of Comparative Example 1 was obtained by performing the same processing as described above.

[0046]

Comparative Example 2 A composite material of Comparative Example 2 was prepared by processing in the same manner as in Example 1 except that the pretreatment for hydrophobization of Example 1 was not performed.

[0047]

Comparative Example 3 A composite material of Comparative Example 3 was prepared by processing in the same manner as in Example 1 except that the polyurethane solution of Example 1 did not contain hydrophilic silicone.

[0048]

Comparative Example 4 The composite of Comparative Example 4 was processed in the same manner as Comparative Example 3 except that about 10% of zirconium carbide (average particle size 2 μm) was added to the polyurethane solution obtained in Comparative Example 3. Got the material. Examples 1 to 3 and Comparative Example 1
Table 1 shows the structures and physical properties of the composite materials of Nos. 4 to 4.

From Table 1, in the case of Examples 1 to 3, Nn /
Nt is 0.85, resin loss, flexibility, peeling strength,
The composite material was excellent in tear strength and abrasion strength, was flexible, and had little noise, but in Comparative Example 1, a composite material in which peeling strength was low, and in Comparative Example 2 resin loss occurred, and in Comparative Examples 3 and 4, Nn was obtained. Since / Nt was 0.1, which was out of the specified range of the present invention, the texture was hard and the noise was loud. Furthermore,
The moisture permeability of Examples 1 to 3 was higher and better than that of Comparative Examples 1 to 4.

Further, comparing Example 3 with Comparative Example 4, in the composite material according to the present invention, since fibers and polyurethane form a non-adhesive structure, a large number of fine particles of polyurethane are aggregated. It seems that it is difficult to form a structure that causes mechanical defects even if zirconium carbide is present. The zirconium carbide generated heat when exposed to white light, but when the temperature sensor was wrapped with the composite material of Example 3 and white light was applied, the temperature increased by 5 ° C. in about 1 minute. This performance is JIS L-0217 wash resistance test 1
About 90% was retained after 0 times, but 40% in Comparative Example 4.
It was only retained.

[0051]

Example 4 Methyl ethyl ketone (52 parts by weight), toluene (16 parts by weight), water (20 parts by weight), fine particles of hydrophobic polyether polyurethane having a diameter of about 1 μm (8 parts by weight) and hydrophilic polyurethane surfactant (2 parts by weight) were used. A dispersed / emulsified W / O type emulsion (I) was prepared. Next, about 60 parts of methylethoxysiloxane was added to this emulsion (I).
%, And 1 part by weight of methylethoxypolysiloxane, which is a copolymerized silicone of about 40% dimethylsiloxane, was added to prepare a dry polyurethane emulsion (II) for coating.

Emulsion (II) was applied to the pretreated fabric used in Example 1 using a knife coater at 100 g / m ² coat.
1 minute at 60 ° C, 2 minutes at 80 ° C, then 1
The composite material of Example 4 was prepared by drying at 20 ° C. for 2 minutes.

[0053]

Comparative Example 5 The woven fabric used in Example 2 was processed in the same manner as in Example 4 to obtain a composite material of Comparative Example 5.

[0054]

Comparative Example 6 A composite material of Comparative Example 6 was obtained by processing in the same manner as in Example 4 except that the dyed fabric used in Example 4 was provided with a fluorine-based water repellent.

[0055]

Comparative Example 7 Comparative Example 7 was processed in the same manner as in Example 4 except that the emulsion (I) described in Example 4 was coated.
A composite material of Table 1 shows the structures and physical properties of the composite materials of Example 4 and Comparative Examples 5 to 7. In Example 4, Nn / N
Since t was 0.85, a composite material which was excellent in resin loss, flexibility, peeling strength, tear strength, abrasion strength, and was soft and had less noise was obtained, but in Comparative Example 5, the peeling strength was low, and Comparative Example 6
In Comparative Example 7, Nn / Nt was 0.1, which was outside the specified range, and the texture was hard and the noise was loud. Furthermore, the moisture permeability of Example 4 was higher than that of Comparative Examples 5 to 7 and was good.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

INDUSTRIAL APPLICABILITY As described above, the composite material obtained by the present invention is a composite material of the base material using the bulky processed yarn, in which the layer of the elastic polymer material formed on the fibrous base material does not show through. It does not kill the texture that it has, and has peeling strength and tear strength of the elastic polymer layer,
It is a composite material with high abrasion strength, flexibility and low noise, and excellent moisture permeability and water pressure resistance. It can be used for various windbreakers such as ski wear, golf and jogging. When the fibrous base material is a knitted fabric, it has excellent stretch-back properties and fits on the body such as sportswear or jerseys with less slack in joints such as knees and elbows, and pantyhose for support. It can be used for good pantyhose and spats. Further, when it is applied to acrylic spun yarn, bulky yarn such as wool and rayon, it is possible to improve stretch back property and shape retention property, which is useful, and it can be expected to be applied to a wide range of applications.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view of a composite material of the present invention in which an elastic polymer material is coated on a fibrous base material using a bulky textured yarn.

FIG. 2 is an enlarged cross-sectional view of a composite material that is a comparative example of the present invention.

FIG. 3 is an enlarged cross-sectional view of a composite material that is a comparative example of the present invention.

FIG. 4 is an enlarged cross-sectional view of a composite material that is a comparative example of the present invention.

[Explanation of symbols]

 1 fiber 2 elastic polymer substance 3 fibrous base material 4 part where elastic polymer substance oozes out on the back surface

Claims (3)

[Claims] 1. A sheet-like composite material comprising a layer of an elastic polymer substance formed on one side of a fibrous base material using a bulky textured yarn, the elastic polymer substance being present at the cut surface. Of the total number Nt of fiber cross sections existing on the surface of the fibrous base material on the side on which the layer of the elastic polymer material is formed, the circumference of the fiber cross section. A sheet-like composite material, characterized in that the ratio Nn / Nt of the cross-section number Nn of fibers not bonded to the elastic polymer substance to Nt is 0.3 or more and 1 or less. 2. A transparent material for clothing made of the composite material according to claim 1, wherein a layer of an elastic polymer material is formed on one surface of a fiber base material using a bulky processed yarn with a thickness of 1 to 200 μm. A damp waterproof cloth. 3. A method for producing a composite material comprising an elastic polymer material layer formed on one surface of a fibrous base material, wherein (1) the fibrous base material is formed by using bulky processed yarn, and (2) A hydrophobizing pretreatment agent containing a fluorine-based water repellent as a main component is attached to the fibrous base material, and (3) the base material is coated with a solution or emulsion of an elastic polymer substance containing hydrophilic silicone. And (4) immersing the base material in a poor solvent for the elastic polymer material to coagulate it, or to scatter the solvent by drying to coagulate it.