KR100658095B1 - A breathable and waterproof fabric with enhanced thermal properties, and a process of preparing for the same - Google Patents

Abstract

The present invention relates to a moisture-permeable waterproof fabric and a method for manufacturing the same having excellent thermal insulation function, wherein the adhesive film layer (B) of the linear water dispersible polyurethane resin and the surface film layer of the reticulated water dispersible polyurethane resin on the fabric (A) C) has a three-layer structure coated in sequence, characterized in that the phase change microcapsules are contained in the adhesive film layer (B). The moisture-permeable waterproof fabric of the present invention is excellent in waterproof performance and moisture-permeable performance and at the same time can reduce the temperature change in the garment during the manufacture of the garment, thereby expressing a comfortable fit.

Breathable waterproof fabric, thermoregulation, polyurethane, phase change, microcapsules, wet coating, fit

Description

A breathable and waterproof fabric with enhanced thermal properties, and a process of preparing for the same}

1 is a cross-sectional view of the present invention waterproof waterproof fabric.

Figure 2 is a schematic diagram of a device for measuring the temperature and temperature duration in the garment.

3 is an enlarged perspective view of a symbol 2 (square grating) in FIG. 1;

* Explanation of symbols on the main parts of the drawings

Reference Signs List 1 fabric 2 square grid 3 heater 4 heating plate

A: Fabric (layer) B: Adhesive film layer C: Surface film layer

The present invention relates to a moisture-permeable waterproof fabric and a method of manufacturing the same having excellent moisture permeability and waterproofness.

Conventional techniques for manufacturing a waterproof moisture-repellent fabric include coating a resin prepared by mixing polyurethane and dimethyl formamide, which is an organic solvent, to a predetermined thickness on a fabric and then passing fine pores on the fabric by passing it through water. There is a wet method for forming a polyurethane film layer to have, to have both moisture permeability and water resistance.

The resin prepared by dissolving polyurethane in a highly volatile organic solvent such as methyl ethyl ketone, toluene, acetone, isopropyl alcohol, etc. was coated on the fabric to a certain thickness, and then heated to volatilize the volatile organic solvent. There is a dry method for forming a homogeneous polyurethane film layer to have moisture permeability and water resistance at the same time.

Since the wet method and the dry method are applied directly to the fabric with a polyurethane resin solution, the resin solution may penetrate into the fabric and harden the product's feel.There is a limit in expressing the functions such as moisture permeability and water resistance. Have. Therefore, in recent years, a laminating method, which is a method of manufacturing a functional film separately and then using an adhesive and blending it with a fabric, has been applied to the production of a waterproof waterproof fabric.

As an example, a resin prepared by dissolving a polyurethane in a highly volatile organic solvent such as methyl ethyl ketone, toluene, acetone, and isopropyl alcohol is coated on a sheet of smooth surface (paper, film, fabric, etc.) to a certain thickness. After heat treatment to form a homogeneous polyurethane film prepared by volatilizing a volatile organic solvent, the adhesive resin prepared by mixing a polyurethane adhesive component with an organic solvent and an isocyanate curing agent is uniformly prepared by a knife. It is applied on the entire surface, or after point application using gravure, then blended with the fabric and matured to have a soft fabric feel while having moisture permeability and water resistance at the same time.

The moisture-permeable waterproof fabric manufactured by the conventional manufacturing method is designed to express two basic functionalities: moisture permeability and waterproofness. The moisture permeability improves the permeability of water molecules in the vapor state, and the waterproofness is imparted to prevent penetration of liquid water. It is functional. These all aimed at controlling the movement of moisture, which reveals limitations in controlling the movement of heat with the external environment in terms of human comfort.

As a conventional technique that secures the thermal control function of the moisture permeable waterproof fabric, a method of improving thermal insulation by adding a ceramic component having a function of receiving light energy from the sun and converting it into thermal energy is known.

This technique has the disadvantage that the weight of the coated fabric is heavy because of the addition of high specific gravity ceramics, and the feel of the fabric is hard, and the thermal insulation performance is expressed only in the presence of sunlight. At night, it can't play its role, and the thermal insulation performance is too small for the human body to detect.

U. S. Patent No. 5,366, 801 discloses a method of forming microcapsules comprising phase change material on one side of a fabric to improve the warmth of the garment. However, since the present invention does not take into account the influence of sweat vapor generated from the human body in controlling the temperature in the garment by the phase transition phenomenon of the microcapsules, the present invention presents a limit to the production of practically comfortable garments, and the coating layer containing the microcapsules is a single layer. Since the phase change material-containing microcapsules are detached by friction or the capsule membrane is broken, there is a risk that the internal phase change material is released and the temperature control function is lost. In addition, since the phase change material itself may be harmful to the human body, it is not an appropriate method for manufacturing a garment fabric. In addition, since the polymer material of the coating layer used as the binder of the phase-transfer microcapsules forms a uniform nonporous film when the film is formed, the heat loss caused by conduction through the film is large when it is actually worn, thereby maintaining and maintaining the temperature in the actual garment. There is a drawback to not doing its job.

The present invention improves the thermal insulation function of the moisture-repellent waterproof fabric, can control the exchange of heat energy with the external environment as well as the control of moisture, such as waterproof performance, moisture permeability, the fabric having the ability to keep the human body in a comfortable state at all times It relates to the manufacture of.

In the present invention, in the preparation of moisture-proof waterproof fabric, by adding a microcapsule with the ability to store and release heat in the coating resin solution, it has the functionality to reduce the temperature change in the garment by its heat exchange ability, and excellent The present invention relates to a method for manufacturing a waterproof waterproof fabric capable of simultaneously expressing waterproof performance and moisture permeability.

The present invention provides a microcapsule having heat storage and release functionality in order to improve the temperature control ability of the fabric produced by using a polyurethane resin that can form a uniform coating having fine pores. The present invention relates to a method for producing a waterproof waterproof fabric by adding a coating resin and uniformly applying the same on a fabric to express waterproof performance and moisture permeability simultaneously.                         

As the moisture-permeable waterproof fabric manufactured in this way has excellent waterproof and moisture-permeable functionality, it prevents the penetration of rain and wind, reducing body temperature loss, and appropriately discharging the sweat vapor generated from the human body during extreme exercise to the outside temperature. At the same time, when the outside temperature is very low, the heat storage in the microcapsules in the coating film is released and the release material is transferred from the liquid state to the solid state, releasing latent heat to increase the temperature in the garment. When the temperature is higher than necessary, heat storage in the microcapsules in the coating film is released and the release material transitions from the solid state to the liquid state, absorbing heat and lowering the temperature in the garment. To express the functionality to maintain.

Water-permeable waterproof fabric of the present invention for achieving such a problem is the adhesive film layer (B) of the linear water-dispersible polyurethane resin and the surface film layer (C) of the reticulated water-dispersible polyurethane resin on the fabric (A) in turn It has a coated three-layer structure, characterized in that the phase change microcapsules are contained in the adhesive film layer (B).

In addition, the method for producing a moisture-repellent waterproof fabric of the present invention by dry-coating a linear water-dispersible polyurethane resin composition on the fabric (A) to form an adhesive film layer (B), on top of which a mesh-type water-dispersible polyurethane resin composition Dry coating to form a surface film layer (C) to produce a moisture-proof waterproof fabric having a three-layer structure in which the fabric (A), the adhesive film layer (B) and the surface film layer (C) are sequentially laminated, the linear water dispersibility The phase change microcapsules are added to the polyurethane resin composition.                     

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The moisture-permeable waterproof fabric of the present invention is dry coated with a linear water-dispersible polyurethane resin composition to which microcapsules (hereinafter referred to as "phase-transfer microcapsules") having a function of storing or releasing heat on the fabric (A) are dry coated. After the film layer (B) is formed, it is prepared by dry coating a network-type water dispersible polyurethane resin composition to which phase change microcapsules are selectively added thereon to form a surface film layer (C).

At this time, the phase change microcapsules are essentially added to the linear water dispersible polyurethane resin (adhesive resin) composition, and the phase change microcapsules may or may not be added to the reticulated water dispersible polyurethane resin (surface treatment resin) composition. It may be.

Looking at one example of the method for producing a moisture-repellent waterproof fabric of the present invention, the resin composition for producing an adhesive film layer prepared as the composition 1 on a water-repellent treated fabric by a conventional method uniformly 10-200g / ㎡ by a floating coating method After coating is carried out 1-3 times in a manner of drying for 1-5 minutes at 100-150 ℃ to form an adhesive film layer (B).

-Composition 1-

Linear Water Dispersible Polyurethane Resin (Adhesive Resin): 100 parts by weight

Water: 5-20 parts by weight

Water dispersible isocyanate crosslinking agent: 2.0-10 parts by weight

Phase change microcapsules: 5-80 parts by weight

Here, the resin composition for preparing the surface film layer prepared as in Composition 2 is coated in the same manner as described above to form the surface film layer (C).

-Composition 2-

Reticulated water dispersible polyurethane resin (surface treatment resin): 100 parts by weight

Water: 5-20 parts by weight

Water Dispersible Silicone: 0.5-5 parts by weight

Phase change microcapsules: 0-50 parts by weight

The linear water-dispersible polyurethane resin (adhesive resin) has 5-50 polyethylene oxide (CH ₂ CH ₂ O) units in the molecular chain, and a carboxyl ammonium salt, an ammonium sulfate salt or a complex thereof as an ionic functional group having a total molecular weight. The linear urethane resin is used in the oligomer state which contains 1-10 weight%, and whose total molecular weight is 1000 or more and 10000 or less.

At this time, the polyethylene oxide unit serves to express the hydrophilicity of the film and the ionic functional group determines the dispersibility in water. If the number of polyethylene oxide is less than five, the hydrophilic performance of the polymer may be lowered, the moisture permeability of the final product may be lowered, and if more than 50, the mechanical properties of the film layer may be lowered. And when the ionic functional group is less than 1% by weight does not become water dispersion, when more than 10% by weight may be less hydrolysis resistance and mechanical properties may be lowered.

In order to improve the durability and hydrolysis resistance of the surface film layer, the surface treatment resin has a structure similar to the above-mentioned adhesive resin and has a molecular weight of 500-10000 or less and a total molecular weight of 5000 to 500,000 or less. A water dispersible polyurethane having a network structure is used.

The phase-transfer microcapsules used contain a phase change material that causes a phase transition from solid to liquid between 10-40 ° C., and the outer wall is composed of polyurea-based crosslinks, or polymethylmethacrylate (PMMA) Or it consists of a melamine crosslinked body, and the diameter is between 1.0-100 micrometers.

Hydrocarbons and the like are used as the phase change material having heat storage and release functionality used in the present invention. Phase change microcapsules have a change in melt enthalpy (ΔH) in the range of 30-300 J / g as measured by differential scanning calorimetry (DSC) around the phase transition temperature.

The above-mentioned linear water dispersible polyurethane resin (adhesive resin) forms a crosslinking reaction with a water dispersible isocyanate-based crosslinking agent to achieve strong adhesion with the fabric, forms a uniform non-porous film layer, expresses water resistance, and polyethylene oxide in the molecular chain. The part is hydrophilic, so make it breathable.

And since the resin for surface treatment has its own network structure, it maintains a stable dispersion state in water, and when coated, forms a strong film and has excellent hydrolysis resistance, thereby protecting the adhesive film layer (B). .

The material in the phase-transfer microcapsules functions to control the temperature in the garment by releasing or absorbing heat to the surroundings by performing phase transition from liquid to solid or from solid to liquid around a certain temperature.                     

The higher the amount of microcapsules contained in the adhesive film layer (B) and the surface film layer (C), the greater the amount of heat released and absorbed, thereby improving the temperature control ability, but possibly lowering the strength of the coating film or causing defects. Since the water resistance and moisture permeability can be reduced, the water content of the phase change microcapsules contained in the adhesive film layer (B) and the surface film layer (C) decreases. Decreases.

The content of the phase change microcapsules per yard (Yd) of the coating film is preferably 1-200 g.

Polyurethane resin used when coating the adhesive film layer (B) in the present invention is a low molecular weight linear water-dispersible polyurethane and crosslinking agent because it is mixed with the water-dispersible isocyanate crosslinking agent and the coating proceeds to a curing reaction in the drying process Crosslinking between the fabric and the polyurethane molecule results in strong adhesion, and crosslinking reaction occurs between the polyurethane molecules to form a firm film.

In addition, the hydrophilic functional groups introduced into the molecular chain quickly absorb water molecules in the vapor state and express functionalities that can be quickly discharged to the outside through a diffusion reaction. Because the phase-transfer microcapsules added in the coating resin are microencapsulated in water system, they have good compatibility and dispersibility with water-based polyurethane, so that they are uniformly distributed in the coating film when the coating process is performed, and the particle size is 1-100㎛ small. Does not impair the waterproofness of the coating film.

The phase change material in the added microcapsules is a material that causes a phase transition from solid to liquid and liquid to solid between 10-40 ° C., and its heat exchange reaction serves to keep it constant near body temperature in the garment.

In detail, if the phase transition temperature of the phase change material is 30 ° C. and the temperature in the garment is about 27 ° C., the phase change material in the microcapsules will remain solid. When the body performs vigorous exercise or the temperature of the external environment rises and the temperature in the clothing exceeds 30 ° C, the human body feels heat. At this time, the phase change material absorbs the surrounding heat while changing the phase from solid to liquid state, thereby lowering the temperature in the garment.

When the body stops exercising or the temperature outside decreases, the temperature inside the garment drops below 30 ° C, and the body feels cold. Then, the phase change material in the liquid state phase changes to a solid state and releases heat as much as the latent heat, thereby exerting the effect of raising or maintaining the temperature in the garment.

The phase change material used in the present invention uses a change in melt enthalpy (ΔH) in the range of 30-300 J / g at the time of phase change, which is added at a level of 1 g / yd to 200 g / yd in the coating film. In this case, when the ambient temperature is changed from 30 ℃ to 0 ℃, it exhibits the effect of maintaining the temperature in the garment for about 5 minutes to 1 hour at 0.5 ℃ -3.5 ℃ higher than the fabric without the phase change microcapsules. Done.

Water permeability of the present invention waterproof waterproof fabric is water-resistant 1000-10000mmH ₂ O (ISO 811 method) level, moisture permeability is 3000-10000g / ㎡ 24 hours (ASTM E 96, inverted cup method) level.

As described above, the moisture-permeable waterproof fabric manufactured by the present invention may exhibit a comfortable wearing feeling by alleviating the change in the temperature in the garment while maintaining excellent waterproof performance and moisture-permeable performance.

In the present invention, various physical properties of the waterproof fabric was evaluated by the following method.

Water pressure

Measured by the ISO 811 method.

Moisture permeability

It is measured by ASTM E 96 (CaCl ₂ method).

Adhesion

It is measured by ASTM A751 method.

· Clothing temperature

A test piece having a width of 15 cm x 15 cm is placed on the electric heater 3 that maintains 36.5 ° C. at all times as shown in FIG. 1 with the square grid 2 having a height of 3 cm interposed therebetween so that the coating surface faces downward. After leaving for 1 hour at an outside temperature of 30 ℃ and quickly put in a chamber with a temperature of 0 ℃ and left for 5 minutes and measured the temperature of the space between the fabric and the heater and evaluated it as the temperature in clothes.

Temperature duration in clothing

Each of the test piece (A) containing the phase change microcapsules and the test piece (B) not containing the phase change microcapsules was treated in the same manner as the method for measuring the temperature in the garment, and then placed in a chamber having a temperature of 0 ° C. The time required for the temperature to be equal was evaluated as the temperature duration in the garment.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

Example 1

A water-dispersible linear urethane resin having a polyethylene oxide unit number of 20 and containing 5% by weight of ammonium sulfate functional groups and a total molecular weight of about 5000 is used as the adhesive resin, and contains a phase change material (octadecane) having a phase transition temperature of 28.2 ° C. the resin composition is mixed as the microcapsules in composition 3 nylon layer fabric (a) by a floating knife with application amount 40g / m ² coating after coating two times in such a manner as to dry for 2 minutes at 150 ℃ adhesive film on the fabric (B ).

-Composition 3-

Adhesive resin: 100 parts by weight

Water: 15 parts by weight

Water dispersible isocyanate crosslinking agent: 7 parts by weight

Phase change microcapsules: 30 parts by weight

Here, using a water-dispersible network-structured polyurethane resin having a molecular weight of about 5000 and a total molecular weight of about 30000 as a surface treatment resin, the coating resin composition for surface treatment prepared as in composition 4 was applied with a floating knife. After coating 20g / m 2 and drying at 150 ° C. for 2 minutes, a surface film layer (C) is formed on the adhesive film layer (B) to prepare a moisture-permeable waterproof fabric having a three-layer structure.

-Composition 4-

Surface Treatment Resin: 100 parts by weight

Water: 10 parts by weight

Water Dispersible Silicone: 0.5 parts by weight

The results of evaluating the various physical properties of the prepared waterproof breathable fabric are shown in Table 1.

Example 2

A water-permeable waterproof fabric was prepared under the same conditions and processes as in Example 1 except that the resin composition of Composition 3 was coated once. Table 1 shows the results of evaluating various physical properties of the prepared waterproof fabric.

Example 3

Except for changing the content of the phase-transfer microcapsules in the resin composition of composition 3 to 100 parts by weight, a moisture-permeable waterproof fabric was prepared under the same conditions and processes as in Example 1. Table 1 shows the results of evaluating various physical properties of the prepared waterproof fabric.

Example 4

A moisture-permeable waterproof fabric was prepared under the same conditions and processes as in Example 1, except that a microcapsule containing a phase change material having a phase change temperature of 22 ° C. was used as the phase change microcapsules in the resin composition of Composition 3. Table 1 shows the results of evaluating various physical properties of the prepared waterproof fabric.

Example 5

Water-permeable waterproof under the same conditions and processes as in Example 1 except for adding 30 parts by weight of phase-transfer microcapsules containing a phase change material (octadecane) having a phase-transition temperature of 28.2 ° C. in the coating resin composition for surface treatment of composition 4. Fabric was prepared. Table 1 shows the results of evaluating various physical properties of the prepared waterproof fabric.

Comparative Example 1

A moisture-permeable waterproof fabric was prepared under the same conditions and processes as in Example 1 except that the phase change microcapsules were not added to the resin composition for an adhesive film layer of composition 3. Table 1 shows the results of evaluating various physical properties of the prepared waterproof fabric.

<Table 1> Result of evaluation of moisture permeable waterproof fabric

division Water pressure (mmH ₂ O) Water vapor transmission rate (g / ㎡ · 24hrs) Adhesion (g / cm) Clothing temperature (℃) Example 1 4,000 5,600 500 29 Example 2 3,000 7,000 500 28 Example 3 4,000 5,000 400 29 Example 4 4,000 5,500 500 28 Example 5 3,500 6,000 400 29 Comparative Example 1 4,000 6,000 450 26.5

The present invention is excellent in waterproofing and moisture permeability, and also excellent in thermal insulation functionality. As a result, the moisture-permeable waterproof fabric of the present invention expresses good comfort during garment manufacturing.

Claims (12)

On the fabric (A), the adhesive film layer (B) of the linear water dispersible polyurethane resin and the surface film layer (C) of the reticulated water dispersible polyurethane resin are sequentially coated, and the adhesive film layer (B). Excellent moisture retention waterproof fabric, characterized in that the phase-transition microcapsules contained in). The moisture-permeable waterproof fabric according to claim 1, wherein the adhesive film layer (B) and the surface film layer (C) contain phase change microcapsules. The thermal insulation function according to claim 1 or 2, wherein the phase change microcapsules are encapsulated with a melamine crosslinked body, a polyurea-based crosslinked body or a polymethylmethacrylate crosslinked body having a phase change temperature of 10-40 ° C. This excellent breathable waterproof fabric. The moisture-permeable waterproof fabric according to claim 1 or 2, wherein the phase-transfer microcapsules have a diameter of 1.0-100 µm. The moisture permeability excellent in thermal insulation functionality according to claim 1 or 2, wherein the content of the phase change microcapsules in the adhesive film layer (B) and the surface film layer (C) is 1-200 g per yard (Yd) of each film layer. Waterproof fabric. The moisture-permeable waterproof fabric according to claim 1 or 2, wherein the melt enthalpy change (ΔH) of the phase-transfer microcapsules measured by differential scanning calorimetry (DSC) around the phase-transition temperature is 30-300 J / g. . The method of claim 1, wherein the linear water-dispersible polyurethane has 5 to 50 ethylene oxide (CH ₂ CH ₂ O) units in the molecular chain and the ionic functional group is a carboxyl ammonium sulfate, ammonium sulfate salt or a complex thereof based on 1-10 Excellent moisture-permeable waterproof fabric, characterized in that the oligomer containing a weight% of the total molecular weight of 1,000-10,000. The moisture permeable waterproof fabric according to claim 1, wherein the mesh-type water dispersible polyurethane has a total molecular weight of 5,000-500,000 and the molecular weight between the crosslinking points is 500-10,000. The moisture-permeable waterproof fabric according to claim 1, wherein the water pressure is 1,000-10,000 mmH ₂ O and the water vapor transmission rate is 3,000-10,000 g / m 2 · 24 hours. delete Dry coating a linear water dispersible polyurethane resin composition on the fabric (A) to form an adhesive film layer (B), and dry coating the reticulated water dispersible polyurethane resin composition thereon to form a surface film layer (C) In preparing a three-layer moisture-permeable waterproof fabric in which the original fabric (A), the adhesive film layer (B), and the surface film layer (C) are sequentially stacked, the addition of phase change microcapsules to the linear water-dispersible polyurethane resin composition Method for producing a moisture-repellent waterproof fabric with excellent thermal insulation, characterized in that. The method according to claim 11, wherein the phase-transfer microcapsules are added to each of the linear water dispersible polyurethane resin composition and the reticulated water dispersible polyurethane resin composition.

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