KR20170105724A - A multi-functional Moisture Vapor Transmittable and water-proof film with excellent printing property and multi-functional fabric comprising the same - Google Patents

Abstract

A multi-functional waterproof fabric having an improved printing property comprises (i) a hard segment comprising polybutylene terephthalate and 30-70 wt% of a soft segment comprising polyethylene glycol and polytetraethylene glycol based on the total amount of a thermoplastic elastomer resin, wherein the polyethylene glycol is contained in the amount of 30 to 70 wt% based on the total amount of the thermoplastic elastomer resin, and the polytetramethylene glycol comprises 1 to 10 wt% of the total amount of the thermoplastic elastomer resin, and (ii) a functional filler contained in the waterproof film. The waterproof fabric of the present invention comprises (i) the multi-functional waterproof film having the improved printing property and (ii) a fabric. The multifunctional waterproof film having the improved printing property has an excellent water proof property and a printing property, and is excellent in antimicrobial activity and/or anion releasing function to be useful for sports clothing materials and casual wear materials.

Description

TECHNICAL FIELD [0001] The present invention relates to a multi-functional breathable waterproof film having improved printability and a multi-functional breathable waterproof fabric including the same,

The present invention relates to a multifunctional breathable and waterproof film having improved printability and a multifunctional breathable and waterproof fabric comprising the same. More specifically, the present invention relates to a multifunctional breathable and waterproof film having improved water repellency and waterproofing properties, printing properties and antifungal and / Functional breathable waterproof film and a multifunctional breathable waterproof fabric bonded thereto.

The breathable waterproof material is a highly functional material that combines two contradictory performances that are breathable and permeable to liquids such as raindrops to prevent penetration of liquids such as air and water vapor. Today, it is not only skiwear and rainwear, It is a popular material that has been applied to various sports wear such as mountain climbing, golf, and marine sports. Development of these breathable waterproof material has been steadily accelerating since the 1960s has been the starting point for the development of mid-to-late Gore-Tex ^® 1970 years been in a variety of development for improving the performance in progress.

The moisture permeable and waterproof material can be classified into a coating type that forms a large film depending on the processing method and a lining type that adheres a thin film to the film. The coating type can be divided into (i) forming a polyurethane coating layer having minute pores in the water phase A dry coating type in which a homogeneous polyurethane film layer is formed on a single phase by coating a resin composition containing a wet coating type and (ii) a volatile organic solvent with a constant thickness on a circular phase followed by heat treatment to volatilize the volatile organic solvent . In addition, microporous microporous type, hydrophilic hydrophilic type, nano web type, and shape memory type can be classified according to the principle of expressing the moisture permeable and waterproof function.

There are various criteria to classify moisture-permeable and waterproof materials. Basically, moisture-proof and water-proof materials can be plasticized by hard segment and soft segment in a block structure, It is common to use a thermoplastic elastomer showing recovery characteristics. When such a thermoplastic elastomer is formed into a film membrane having a thickness of several tens of micrometers, the rigid-chain continuous phase serves to prevent the penetration of water droplets or contaminants coming from the outside of the membrane, and the polymer chain is passed through the moisture to the opposite side of the membrane And as a result, the function of breathable breathable waterproof is expressed.

Various conventional techniques for breathable and waterproof materials include Japanese Patent Laid-Open Publication No. Hei 5-124144 and L-lysine disclosed in Japanese Patent Laid-Open Publication No. Hei 5-124144, which discloses a breathable and waterproof sheet made by bonding a polyethylene porous film and a heat- Japanese Patent Laid-Open Publication No. Hei 3-213581 discloses a moisture-permeable and waterproof fabric having excellent abrasion resistance, prepared by laminating a moisture permeable film made of a polyamino acid-based polyurethane containing 0.1% or more of a powder of a reaction product of an organic acid and an organic acid, A variety of dry / wet coating methods are disclosed in Japanese Patent Application Laid-Open Nos. 4-249142, 4-146275, 7-258971, 5-78984, and 8-13352.

However, the manufacturing method disclosed in the above-mentioned prior arts is very complicated, and the moisture permeable and waterproof film or membrane manufactured through the method has disadvantages in that the pores are uneven and the moisture permeability is low as a result. In addition, when an organic solvent is used in the manufacturing process, there arises a problem that the dyestuff of the fabric is escaped by the organic solvent to cause contamination.

On the other hand, in the case of polytetrafluoroethylene (PTFE) material, which is often known as Gore-Tex material, fine pores are uniformly formed in the film, and it is most preferred even though it is distributed at a high price because of excellent chemical resistance and light fastness . However, the PTEF has low mechanical fatigue strength and low durability, and releases environmentally hazardous perfluorinated and polyfluorinated compounds (PFCs), fluoroether alcohols (FTOHs), perfluorinated carboxylic acids (PFCAs), perfluorinated sulfonate (PFOS), and perfluorooctanoic acid There is a risk that it can be done.

Until recently, breathable and waterproof materials have been widely used for polyurethane, which has excellent moisture permeability and various processing methods. However, the polyurethane has poor durability against washing when it is used for clothing, There has been a problem that the mechanical strength of the material is rapidly lowered when the pore size of the membrane is increased. Furthermore, when such a polyurethane is directly coated on a single phase by a wet or dry method, there is a fear that the resin solution penetrates into the inside of the fabric and the feel of the product tends to be hard, and there is also a limit to the development of functionalities such as moisture permeability and water resistance .

On the other hand, the conventional moisture-permeable and waterproof film has a moisture-permeable and water-proofing property, but has a problem in that it is poor in printing property and does not have antibacterial and / or anion generating function.

Accordingly, the present invention provides an environmentally friendly multi-functional breathable waterproof film excellent in moisture permeability and waterproof property, excellent in touch and durability, excellent in appearance, and a breathable waterproof fabric including the breathable waterproof material based on a polyester elastomer I want to.

The present invention also provides a multifunctional moisture-permeable waterproof film having excellent moisture permeability and water repellency as well as remarkably improved printability, excellent antimicrobial activity and / or negative ion generating function, and a moisture permeable waterproof fabric comprising the multifunctional moisture barrier film.

In order to achieve the above objects, the present invention provides a thermosetting resin composition comprising a hard segment comprising polybutylene terephthalate and a soft segment comprising polyethylene glycol and polytetraethylene glycol in an amount of 30 to 70% by weight based on the total amount of the thermoplastic elastomer resin, The polyethylene glycol is contained in an amount of 30 to 70% by weight based on the total amount of the thermoplastic elastomer resin, and the polytetramethylene glycol contains a functional filler in the moisture permeable and waterproof film containing 1 to 10% by weight based on the total amount of the thermoplastic elastomer resin, A functional breathable waterproof film is produced.

An antibacterial filler and / or anion generating filler is used as the functional filler, and the content of the functional filler in the moisture permeable and waterproof film is 0.5 to 5 wt%.

The present invention also provides a multifunctional breathable and waterproof fabric by laminating the multifunctional breathable waterproof film and the base fiber with improved printing properties.

The multifunctional breathable and waterproof film of the present invention is excellent in moisture permeability and waterproof property, excellent in printing property, and excellent in antimicrobial and / or negative ion generating function, and is useful as a sports clothing material and a casual clothing material.

1 is a cross-sectional photograph of a multi-functional breathable waterproof fabric according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The multifunctional breathable waterproof film according to the present invention comprises (i) a hard segment comprising polybutylene terephthalate and a soft segment comprising polyethylene glycol and polytetraethylene glycol in an amount of 30 to 70% by weight based on the total amount of the thermoplastic elastomer resin , The polyethylene glycol is contained in an amount of 30 to 70 wt% based on the total amount of the thermoplastic elastomer resin, and the polytetramethylene glycol is contained in an amount of 1 to 10 wt% based on the total amount of the thermoplastic elastomer resin; And (ii) a functional filler contained in the moisture permeable waterproof film.

The functional filler may be an antibacterial filler, an anion generating filler, or a mixture thereof. The content of the functional filler in the moisture permeable and waterproof film may be 0.5 to 5% by weight to provide antibacterial and / or anion generating function without deteriorating moisture permeability, It is preferable to effectively improve it.

The antibacterial filler may be silver (Ag), copper (Cu), selenium (Se), zinc oxide (ZnO), copper oxide (CuO), magnesium oxide (MgO), titanium oxide (TiO ₂ )

The anion generating filler is Tourmaline natural stone, nephrite, amethyst, germanium or a mixture thereof.

The above natural stone is cesium, rubidium, cerium, nepheline, strontium or zirconium.

The tourmaline is a kind of igneous rock, which is an ore having a hexagonal crystal structure and is composed of iron, magnesium, alkali metal, borosilicate of aluminum and the like.

The mean particle size of the functional filler is preferably 0.1 to 5 탆 in order to improve the film formability and functionality at the same time.

The moisture permeable waterproof film having improved printability may further include an ultraviolet absorber, and the content of the ultraviolet absorber is preferably 0.1 to 10 wt%.

Examples of the ultraviolet absorber include 2- (2H-benzotriazloe-2-yl) -4-6-bis (1-methyl) -1-phenylethyl) phenol phenol, 2- (5-chloro) (2H) -benzotriazloe-2-yl) -4-methyl-6- (tert-butyl) phenol, 2 - (4,6-diphenyl-1,3,5-triazin-2-yl) -5- (hexyl) oxy) -phenol, Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

The soft segment constituting the moisture permeable and waterproof film may be a polyethylene glycol alone, a polytetramethylene glycol alone, or a polymer thereof, or a polymer in which dimethyl terephthalate and polyethylene glycol are bonded as shown in the following formula (1) Or may be a polymer in which dimethyl terephthalate and polytetramethylene glycol are combined.

(Formula 1)

(2)

The soft segment may be composed of two or more components and may comprise a hydrophilic polyol and a hydrophobic polyol. The hydrophilic polyol may be polyethylene glycol having a number average molecular weight of 600 to 8,000 as measured by gel permeation chromatography (GPC) to facilitate mechanical property and easy production of the elastomer, and the ratio of the hydrophilic polyol may be 30 to 70 wt% %. ≪ / RTI > When the proportion of the hydrophilic polyol is less than 30% by weight, it may be difficult to exhibit a desired moisture permeability. When the amount of the hydrophilic polyol is more than 70% by weight, the melting point may be extremely low or high, resulting in poor processability. It may swell and have appearance defects.

The hydrophobic polyol component preferably has a number average molecular weight measured by gel permeation chromatography (GPC) of 600 to 8,000 Polytetramethylene glycol, and it is preferable that 0.1 to 10% by weight of the total elastomer is included in consideration of the flexibility of the film, the modulus difference with the base fiber, and the swelling property of the film due to moisture.

In the present invention, a known method such as an inflation method or a die extrusion method can be used as a method of producing the moisture-permeable and waterproof film formed of the elastic composition containing the thermoplastic resin, and the thickness can be controlled But it is preferable to have a thickness in the range of 1 to 100 탆. At this time, when a higher level of moisture permeability is required, it is more preferable to have a thickness of 5 to 50 탆. When the thickness of the film is less than 1 탆, the thickness of the film is too thin, thereby decreasing the durability, heat resistance, water pressure and mechanical strength of the film. When the thickness exceeds 100 탆, the thickness of the whole product becomes thick, the moisture permeability decreases or the bending hardness The binding and handling becomes difficult and the range of application may be limited.

On the other hand, the moisture-permeable waterproof film is composed of a segmented copolyetherester present as a dispersed phase in soft segmen (polyether matrix), which is a soft amorphous block having a low glass transition temperature and a hydrophobic Hard segment (polyester block) The hydrophilic group and hydrophobic polymer interact with each other due to the hydrophilic / hydrophobic nature. That is, the hydrophobic region acts to push out moisture (e.g., sweat exuded from the skin), and the hydrophilic region acts to attract water or gas vapor.

Such osmotic pressure and intermolecular attraction (van der Waals force) cause the moisture emitted from the skin or the outside to be quickly absorbed into the hydrophilic amorphous block through the crystalline hydrophobic layer. Thus, the moisture permeable and waterproof film of the present invention can exhibit a water pressure resistance of JIS L 1099 (B-1) dimension of 3,000 to 100,000 (g / ㎡ * day) water vapor permeability and ISO 811 dimensions of 3,000 to 30,000 (mmH ₂ O) of .

In addition, when the moisture permeable and waterproof film is laminated on the fibers, the absorbed moisture continuously moves due to the voids and hydrophobicity of the fabric, and is quickly discharged to the atmosphere. Therefore, when the adhesive is further laminated, The osmotic action causes the moisture to move to and exit from the fabric layer more quickly. At this time, the moisture-permeable waterproof fabric of the present invention can sensitively increase the moisture-permeable amount as the temperature increases because the hydrophilic molecular chain sensitively performs micro-brown movement according to the external temperature.

Furthermore, PTFE known as Gore-Tex usually has pores and has a good moisture permeability. However, since the pores are damaged during washing, the moisture permeability is lowered and secondary contamination due to foreign matter may occur. On the other hand, So that the washing durability can be excellent.

On the other hand, the multifunctional breathable and waterproof fabric of the present invention comprises the base fiber and the multifunctional breathable waterproof film laminated on at least one side of the base fiber.

The base fiber is formed of at least one yarn selected from the group consisting of polypropylene, polyethylene, polyester, nylon, aramid, rayon, acrylic, spandex, lyocell, cotton, wool and silk Fabric, knitted fabric and nonwoven fabric.

The lamination of the base fiber and the moisture-permeable and waterproof film may be lamination by heat fusion or lamination using an adhesive.

The lamination using the adhesive may be a lamination using at least one member selected from the group consisting of a polyurethane based moisture curing type adhesive, a two-component type polyurethane type adhesive, a thermosetting hot melt polyurethane adhesive, an ethylene vinyl acetate type adhesive, a polyester type hot melt adhesive, an acrylic type adhesive, Laminating using adhesive or hot meltting.

In the case of lamination by thermal fusion, it may be a T-die direct coating method in which the film is directly bonded to the base fiber while the film is laminated. In this case, the temperature can be adjusted to 150 to 300 ° C The film is formed into a film having a uniform thickness through a die attached to the front surface of the extruder in the extruder so as to have a thickness of 5 to 100 탆. The base fiber is simultaneously injected immediately before the gel film reaches the cooling roll, And then laminated while being solidified via a cooling roll. Since the heat welding process does not require a separate bonding or laminating process, the efficiency of production is improved, and there is an advantage that the moisture permeation due to the adhesive can be prevented from deteriorating.

On the other hand, when the moisture-proof and waterproof fabric, which emphasizes touch and drape, is intended, lamination by laminating or hot-melt can be easier. At this time, a hydrophilic two-pack type polyurethane adhesive may be more preferable for laminating among the above-mentioned adhesives, and an adhesive typified by a polyurethane moisture hardening type may be suitable for hot meltting. Particularly, in the case of an adhesive suitable for hot-melting, an adhesive agent is generally used in a non-solvent form, and has a solid or viscous state at room temperature, but becomes melted and applied when it is heated. may be useful for dot coating.

More specifically, the hot-melt bonding is carried out by first feeding a hot-melt adhesive sheet formed so as to contain an adhesive component between the base fiber and the film, heat-applying the hot-melt adhesive sheet to the base fiber, And is pressed by a pressure roller. At this time, the hot-melt adhesive sheet may be an adhesive film in the form of a film, or may be in the form of an adhesive web. The lamination method using a hot-melt adhesive sheet is bonded through a heating roller of 100 to 150 ° C. When the temperature is lower than 100 ° C, the adhesive sheet is not melted smoothly and the desired adhesive strength is not exhibited. The film may be damaged due to temperature, and it may become difficult to commercialize the film.

In the present invention, additives such as a tackifier, a curing catalyst, a plasticizer, a stabilizer, a filler, a dye, a pigment, a fluorescent whitening agent, a silane coupling agent, a wax and an antiblocking agent, a thermoplastic resin, It can be appropriately selected and used within a range that does not hinder the purpose. Examples of the tackifier include, but are not limited to, rosin resin, rosin ester resin, hydrogenated rosin ester resin, terpene resin, terpene phenol resin, hydrogenated terpene resin, An aromatic resin of C9 series, a copolymer resin of C5 series and C9 series, and the like can be used.

The application of the adhesive can be carried out in the entire surface, but it is preferable that the intermittent application be performed in view of maintaining good moisture permeability and flexibility of the base fiber. Examples of the intermittent coating method include a method of coating in dot form or a method in which the coating is applied in the form of mesh. Among them, a method of coating in dot form is preferable, but not always limited thereto. For example, gravure transfer coating method, screen coating method, T-die coating method, and pie bar coating method in which a roll is sliced can be applied. At this time, the heat-melt temperature of the adhesive is preferably 80 to 130 占 폚, more preferably 80 to 120 占 폚.

The amount of the adhesive transferred onto the base fiber is preferably 5 to 50 g / m < 2 >. If the transferred amount is too large, the texture of the fabric is excessively hardened to reduce the tactile sensation. If the amount is too small, Sufficient durability can not be obtained, and as a result, the adhesion between the film and the fiber may become poor. In order to transfer the molten adhesive in a single phase, both the transfer device and the application device must be able to heat and be completely sealed so as not to be exposed to air during the process.

Next, before the adhesive transferred to the base fiber is completely cured, it is preferable to prepare the base fabric by dispersing the base fiber and the moisture-permeable and waterproof fabric in a dope roll. It is preferable to preliminarily heat with the infrared heater at the time of dipping, and after the fiber and the film are mixed, the adhesive reacts with a small amount of moisture contained in the film and air as it cools and changes into three-dimensionally crosslinked thermosetting material. So that an extremely excellent adhesive force is exhibited.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.

Example  One

37 weight% of dimethyl terephthalate, 24 weight% of 1,4-butanediol, and 39 weight% of polyethylene glycol having a number average molecular weight of 2,000 and 0.05 weight part of trimethanolpropane, which is a crosslinking agent, based on 100 weight parts of the above- 0.16 part by weight of titanium butoxide as a catalyst was added and the temperature was raised from 120 ° C to 180 ° C for 120 minutes and then maintained at 180 ° C for 60 minutes. The amount of methanol, which was a reaction effluent, was converted into a reaction rate When the reaction rate is 90% or more, the reaction is terminated to obtain an oligomer.

The oligomer was transferred to a polycondensation reactor, and 0.24 parts by weight of a phenol-based antioxidant was added thereto. Then, the temperature was raised to 245 DEG C for 120 minutes (the reaction pressure was reduced from 760 torr to 0.3 torr for 60 minutes, The reaction is terminated when the developer reaches a desired stirrer torque and the produced thermoplastic polyester elastomer is discharged out of the reactor by using nitrogen pressure and cooled It is made into a pellet.

The thermoplastic polyester elastomer pellets prepared by the melt polymerization are introduced into a rotatable reactor, the pressure in the reactor is reduced to 0.3 torr, and heated and rotated at 180-190 ° C for approximately 12-18 hours to reach the desired flow index To thereby obtain a thermoplastic polyester elastomer (elastomer A) by solid phase polymerization.

On the other hand, except for the use of 0.05 parts by weight of trimethanolpropane, which is a crosslinking agent, based on 31% by weight of dimethyl terephthalate, 24% by weight of 1,4-butanediol and 45% by weight of polytetramethylene glycol having a number average molecular weight of 1,000 And an elastomer B was prepared in the same manner as in the preparation of the elastomer A.

The elastomer A and the elastomer B thus prepared were mixed together with a UV stabilizer to prepare a thermoplastic elastomer resin. At this time, the elastomer A and the elastomer B were mixed so that the content of each of the polyethylene glycol and the polytetramethylene glycol was 37 parts by weight and 2.3 parts by weight, respectively, based on 100 parts by weight of the thermoplastic elastomer resin. The ultraviolet stabilizer contained 100 parts by weight of the thermoplastic elastomer resin By weight.

First, an elastomer A and an elastomer B were prepared in the same manner as in Example 1.

Next, 95% by weight of the thermoplastic elastomer resin prepared as described above and 5% by weight of silver (Ag) as an antibacterial filler were fed into a twin-screw extruder to prepare a master batch chip.

Next, 85% by weight of the thermoplastic elastomer resin prepared as described above and 15% by weight of the master batch chip prepared as described above were fed into a twin-screw extruder and kneaded, and a moisture permeable waterproof film having a thickness of 12 탆 was extruded through an extruder .

Various physical properties of the moisture permeable waterproof film thus prepared were measured and the results are shown in Table 1.

Example  2

First, an elastomer A and an elastomer B were prepared in the same manner as in Example 1.

Next, 95% by weight of the thermoplastic elastomer resin prepared as described above and 5% by weight of tourmaline as an anion generating filler were fed into a twin-screw extruder to prepare a master batch chip.

Next, 85% by weight of the thermoplastic elastomer resin prepared as described above and 15% by weight of the master batch chip prepared as described above were charged into a twin-screw extruder and kneaded, and then a breathable waterproof film having a thickness of 20 탆 was extruded through an extruder .

Various physical properties of the moisture permeable waterproof film thus prepared were measured and the results are shown in Table 1.

Example  3

First, an elastomer A and an elastomer B were prepared in the same manner as in Example 1.

Next, a master batch chip was prepared by charging 95% by weight of the thermoplastic elastomer resin thus prepared, 2% by weight of silver (Ag) as an antibacterial filler and 3% by weight of tourmaline as an anion generating filler into a twin screw extruder.

Next, 87% by weight of the thermoplastic elastomer resin prepared as described above and 13% by weight of the master batch chip prepared as described above were added to the twin-screw extruder and kneaded, and then a moisture permeable waterproof film having a thickness of 40 탆 was extruded through an extruder .

Various physical properties of the moisture permeable waterproof film thus prepared were measured and the results are shown in Table 1.

Comparative Example  One

First, an elastomer A and an elastomer B were prepared in the same manner as in Example 1.

The elastomer A and the elastomer B thus prepared were mixed together with a heat stabilizer and a UV stabilizer to prepare a thermoplastic elastomer resin. At this time, the elastomer A and the elastomer B were mixed such that the content of each of polyethylene glycol and polytetramethylene glycol was 10 parts by weight and 0.4 part by weight, based on 100 parts by weight of the total amount of the thermoplastic elastomer resin layer. Next, the thermoplastic elastomer resin prepared as described above was put into a twin-screw extruder and kneaded, and a breathable waterproof film having a thickness of 12 탆 was produced through an extruder.

Various physical properties of the moisture permeable waterproof film thus prepared were measured and the results are shown in Table 1.

division Water vapor permeability (potassium acetate method)
(g / m < 2 > * day) Antimicrobial activity
(%) Water pressure
(㎜H ₂ O) Anion
Number of occurrences Example 1 56,000 99.9 20,000 0 Example 2 53,000 85 20,000 560 Example 3 68,000 99.6 19,500 240 Comparative Example 1 7,300 75 20,000 0

Example  4

Polyester terephthalate multifilament as a base fiber Polyester filament Woven crimp yarn DTY 70 DEN / 48 fil (made by Kolon Fashion Material Co., Ltd.) was used as warp and weft yarns to weave plain weave fabrics and then subjected to water repellent processing (using a fluorine- (Weight 110 g / m < 2 >) was dyed black with a disperse dye (KISCO Black S-SG) by a dyeing process. Thereafter, the moisture-permeable and waterproof film prepared in Example 1 was laminated on one side of the polyester fabric using a urethane-based adhesive (adhesion amount of adhesive: 12 g / m 2) to the entire surface to prepare a multi-functional breathable and waterproof fabric .

The results of evaluating the physical properties of the fabricated multi-functional breathable waterproof fabric were as shown in Table 2.

Example  5

Polyester terephthalate multifilament as a base fiber Polyester filament Woven crimp yarn DTY 70 DEN / 48 fil (made by Kolon Fashion Material Co., Ltd.) was used as warp and weft yarns to weave plain weave fabrics and then subjected to water repellent processing (using fluorine- (Weight 110 g / m < 2 >) was dyed black with a disperse dye (KISCO Black S-SG) by a dyeing process. Thereafter, the moisture-permeable and waterproof film prepared in Example 2 was laminated on one side of the polyester fabric using a urethane-based adhesive (adhesion amount of adhesive: 12 g / m 2) on all sides to prepare a multi-functional breathable and waterproof fabric .

The results of evaluating the physical properties of the fabricated multi-functional breathable waterproof fabric were as shown in Table 2.

Example  6

Polyester terephthalate multifilament as a base fiber Polyester filament Woven crimp yarn DTY 70 DEN / 48 fil (made by Kolon Fashion Material Co., Ltd.) was used as warp and weft yarns to weave plain weave fabrics and then subjected to water repellent processing (using a fluorine- (Weight 110 g / m < 2 >) was dyed black with a disperse dye (KISCO Black S-SG) by a dyeing process. Thereafter, the moisture-permeable and waterproof film prepared in Example 3 was laminated on one side of the polyester fabric using a urethane-based adhesive (adhesion amount of adhesive: 12 g / m 2) to the entire surface to prepare a multi-functional breathable and waterproof fabric .

The results of evaluating the physical properties of the fabricated multi-functional breathable waterproof fabric were as shown in Table 2.

Comparative Example  2

Polyester terephthalate multifilament as a base fiber Polyester filament Woven crimp yarn DTY 70 DEN / 48 fil (made by Kolon Fashion Material Co., Ltd.) was used as warp and weft yarns to weave plain weave fabrics and then subjected to water repellent processing (using a fluorine- (Weight 110 g / m < 2 >) was dyed black with a disperse dye (KISCO Black S-SG) by a dyeing process. Thereafter, the moisture-permeable and waterproof film prepared in Comparative Example 1 was laminated on one side of the polyester fabric using a urethane-based adhesive (adhesion amount of adhesive: 12 g / m 2) to the entire surface to produce a multi-functional breathable and waterproof fabric Respectively.

The results of evaluating the physical properties of the fabricated multi-functional breathable waterproof fabric were as shown in Table 2.

Evaluation of physical properties of multi-functional breathable waterproof fabric division Water vapor permeability (potassium acetate method)
(g / m < 2 > * day) Water pressure
(Mm H ₂ O) Antimicrobial activity Anion
Number of occurrences Example 4 28,500 20,000 99.8 0 Example 5 26,700 20,000 84 560 Example 6 31,000 20,000 99.6 240 Comparative Example 2 3,300 20,000 75 0

Various physical properties of Tables 1 and 2 were measured by the following methods.

- Measurement of the moisture permeability (potassium acetate method, JIS L1099 measurement standard): 300 g of potassium acetate specified in JIS K 8363 was added to 100 ml of water, and the resultant was allowed to stand overnight. The moisture absorber in the state in which crystals were precipitated was placed in a moisture- Or moisture-permeable waterproof fabric, and then a test piece is prepared by attaching an auxiliary film for measurement of moisture permeability of about 10 × 10 cm to the rubber band. The mass (a3) of the test specimen is measured up to 1 mg with the film side up. After the measurement, the test specimen is inverted and mounted in a test specimen support frame in a water tank. After 15 minutes, the test specimen is taken out and measured up to 1 mg of mass (a4). The moisture permeability was calculated by the following equation (converted to 24 h) and the results of three tests were expressed as an average value.

- Water pressure measurement (KSK ISO 811-2009 measurement standard): Water permeation test was carried out using Hydrostatic Tester (FX-3300). Apply water pressure of 60cmH ₂ O / min to waterproofing film or fabric at 20 ℃ to measure water pressure at 3 places on the surface of the film or breathable waterproofing fabric opposite to the water pressure applied surface. do. In the case of measuring only the water pressure of the film, the film is swollen due to the application of water pressure due to the elasticity of the film itself, so that it is difficult to measure the water pressure appropriately. The film surface is positioned so as to come in contact with water, and the mesh fabric (PET 20Denier / 1Filament yarn , Open space of more than 75% of the fabric) is placed on top of the film surface, and then the pressure head is gripped to measure the pressure.

- Warmth, aesthetics and presence of hologram: The sensory test results were classified into two categories of "excellent" and "normal".

- Measurement of antimicrobial activity (KS K 0693: 2011 measurement standard): Inoculant-Staphylococcus aureus and pneumococcus were applied to inoculate and culture the bacteria in Example 1 and Comparative Example 1, and then cultured bacteria were shaken at a constant rate , And the number of bacteria present in the liquid is measured to calculate the bacterial reduction rate.

My washing power (durability) should not be released after 20 times of washing, and the antibacterial power should be maintained continuously.

- Measurement of the number of negative ion generation (JIS B 9929 measurement standard): The charge particle measurement device is tested by measuring the number of negative ions per unit volume using the inhalation method under the condition of 20 ° C and 36% humidity at the number of atmospheric anions 106 / cc.

Claims (15)

(I) a hard segment comprising polybutylene terephthalate, and a soft segment comprising polyethylene glycol and polytetraethylene glycol in an amount of 30 to 70% by weight based on the total amount of the thermoplastic elastomer resin, wherein the polyethylene glycol has a ratio of the total amount of the thermoplastic elastomer resin 30 to 70% by weight, and the polytetramethylene glycol is contained in an amount of 1 to 10% by weight based on the total amount of the thermoplastic elastomer resin; And
(Ii) a functional filler contained in the moisture permeable waterproof film. The multi-functional breathable waterproof film according to claim 1, wherein the functional filler is a mixture of an antibacterial filler, an anion generating filler, and an antibacterial filler and an anion generating filler. The multi-functional breathable waterproof film according to claim 1, wherein the content of the functional filler in the moisture permeable waterproof film is 0.5 to 5 wt%. The method of claim 2 wherein the antimicrobial fillers are selected from the group consisting of silver (Ag), copper (Cu), selenium (Se), zinc oxide (ZnO), copper oxide (CuO), magnesium oxide (MgO) and titanium (TiO ₂₎ oxide 1 or a mixture of two or more kinds. The multifunctional breathable waterproof film according to claim 2, wherein the anion generating filler is one kind or a mixture of two or more selected from tourmaline natural stone, nephrite, amethyst and germanium. The multi-functional breathable waterproof film according to claim 1, wherein the functional filler is a solid content having an average particle size of 0.1 to 5 占 퐉. The multi-functional breathable waterproof film according to claim 1, further comprising an ultraviolet absorber contained in the breathable waterproof film. The multi-functional breathable waterproof film according to claim 7, wherein the content of the ultraviolet absorber in the moisture permeable waterproof film is 0.1 to 10% by weight. The moisture-permeable waterproof film according to claim 1, wherein the moisture permeable waterproof film has a moisture permeability of 10,000 to 150,000 (g / m 2 * 24 hours) as measured by JIS L 1099 (B-1). The waterproof breathable waterproof film according to claim 1, wherein the breathable waterproof film has a water pressure of 5,000 to 30,000 (mmH ₂ O) based on ISO 811 measurement. The multi-functional breathable waterproof fabric according to claim 1, wherein the breathable waterproof film has a thickness of 10 to 50 μm. Base fiber; And
A multi-functional breathable waterproof fabric comprising the multi-functional breathable waterproof film of claim 1, which is laminated on at least one side of the base fiber. 13. The method of claim 12, wherein the substrate fibers are selected from the group consisting of polypropylene, polyethylene, polyester, nylon, aramid, rayon, acrylic, spandex, lyocell, cotton, wool and silk Characterized in that the fabric is one of a fabric, a knitted fabric, and a nonwoven fabric formed of at least one kind of yarn. 13. The multi-functional breathable and waterproof fabric according to claim 12, wherein the lamination is lamination by heat fusion or lamination by an adhesive. 15. The laminate according to claim 14, wherein the lamination with the adhesive comprises a polyurethane based moisture curing adhesive, a two-part polyurethane adhesive, a thermosetting hot melt polyurethane adhesive, an ethylene vinyl acetate adhesive, a polyester hot melt adhesive, an acrylic adhesive and an EVA adhesive Wherein the laminating or hot meltting is performed using at least one adhesive selected from the group consisting of polypropylene and polypropylene.

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