JP3133131B2 - Composite sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a composite sheet. More specifically, the present invention relates to a composite sheet having excellent thermal stability that absorbs heat of fusion when the temperature rises and releases heat of solidification when the temperature falls. Further, the composite sheet of the present invention becomes a material suitable for applications such as sports clothing, casual coats, outdoor, rain gear, diaper covers, etc. by imparting moisture permeability and waterproofness thereto.

[0002]

2. Description of the Related Art As a moisture-permeable waterproof cloth, there is a cloth having not only moisture permeability and waterproofness but also various comforts. For example, there is a material in which a heat insulating material such as ceramics is added to a thermoplastic resin to impart a heat retaining effect, or a material in which metals having radiant heat reflectivity are added to a thermoplastic resin. As a cooling garment, there is a technique disclosed in Japanese Patent Application Laid-Open No. 61-89303, in which a small microfan is mounted in clothing to forcibly circulate air to cool the garment.

[0003] Japanese Patent Application Laid-Open No. 64-85374 discloses that a yarn containing a phase-change substance-encapsulated capsule utilizes energy accompanying melting and coagulation in response to a change in external temperature, and absorbs heat of fusion when the temperature rises. In addition, there is disclosed a fabric having excellent thermal stability that releases heat of solidification when the temperature drops. However, a heat insulating composite sheet to which ceramics having heat insulating properties and metals having radiant heat reflection properties are added, against the rapid decrease in the outside air temperature, is not yet sufficient by the heat insulating effect of the composite sheet alone.

Further, when kneading a phase-change substance-encapsulated capsule disclosed in Japanese Patent Application Laid-Open No. 64-85374 into yarn, the yarn has a high elongation, and the efficiency is reduced due to yarn breakage during the weaving process. There is a problem of a decrease in tear strength, and it is difficult to apply to general clothing. Further, in this case, the heat accompanying the phase change has a large heat loss due to the movement not only to the human body side but also to the outside air side, and it is difficult to control the temperature in the clothes.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to minimize the change in temperature in clothes caused by a change in environment, maintain a more comfortable state, do not reduce the strength of the fabric, and apply it to general clothing. The purpose of the present invention is to provide a composite sheet that does not cause any problem.

[0006]

Means for Solving the Problems The inventors of the present invention have made intensive studies to efficiently transfer the phase change energy to the inside of clothes, and as a result, have come to invent a composite sheet excellent in cooling, especially in heat retention. That is, according to the present invention, a thermoplastic synthetic resin layer containing ceramic and a thermoplastic synthetic resin layer containing microcapsules containing phase change material are laminated in this order on at least one surface of the fabric, and In the thermoplastic synthetic resin layer containing the capsule and / or
Alternatively, the composite sheet is present on a thermoplastic synthetic resin layer containing the phase-change-substance-encapsulated microcapsules.

Next, the present invention will be described specifically. In the present invention, the fabric may be any of synthetic fibers, semi-synthetic fibers, and natural fibers, and all fabrics that can be laminated, such as woven fabrics such as plain weave, twill weave, and satin weave, knitted fabrics such as weft and warp nets, and nonwoven fabrics. Can be used. The thermoplastic resin of the present invention includes polyurethane resin, acrylic resin, silicone resin, polyvinyl alcohol resin, nylon resin, polyester resin, polycarbonate resin, fluorine resin, polyethylene resin, polypropylene resin, and polychlorinated resin. A vinyl resin, an acrylonitrile-butadiene-styrene resin, a melamine resin, and the like can be arbitrarily used. The solid content and viscosity of the resin may be any as long as the resin film can be produced. The thickness of the thermoplastic resin layer is preferably from 5 to 50 μm from the viewpoint that when the texture and the sheet are imparted with moisture permeability and waterproofness, these properties are exhibited well.

In view of the peel strength between the cloth and the thermoplastic resin layer containing ceramic laminated thereon, it is preferable to further interpose a thermoplastic resin layer between the two, and the above-mentioned resin is optionally used. can do. Also,
In order to improve the adhesiveness, it is preferable to add a curing agent, a crosslinking agent, and the like. The thickness of this resin layer is preferably 5 to 20 μm, more preferably 5 to 10 μm. Alternatively, the above-mentioned curing agent and cross-linking agent can be added to the thermoplastic resin layer containing ceramic.

In order to obtain a moisture-permeable thermoplastic resin layer, a method of adding a foaming agent to a dissolved resin solution with a solvent that dissolves the resin and foaming at the time of coagulation, adding fine particles to the resin solution, and then coagulating the fine particles of the resin. There is a method of dissolving and extracting with a non-solvent, and a method of extracting pores by extracting a solvent of a resin solution using a solvent that freely mixes with the solvent without dissolving the resin. Also,-
_{SO 3 H, -SO 3 M,} -COOM (M: an alkali metal or ^{_{-NH 4 +) -COOH, -NH 2}} , -CN, -O
H, if introducing a hydrophilic group such as -NHCONH _2, can be obtained even moisture permeability without forming pores.

The thermoplastic resin layer of the present invention may contain various additives commonly used for resins. For example, a thickener, a curing agent, a crosslinking agent, a pigment, a glossing agent, a light stabilizer, an antioxidant, an ultraviolet absorber, a flame retardant and the like. As a laminating method for obtaining a composite sheet comprising a fabric and a thermoplastic resin layer of the present invention, a coating method of directly applying a resin solution to the fabric, and a method of forming a thermoplastic resin layer on release paper in advance and using an adhesive There is a lamination method of laminating with a fabric, but any method can be used according to the purpose. In addition, when using the coating method of applying a thermoplastic resin to the fabric, the thermoplastic resin easily permeates the inside and the back surface of the fabric,
Since it is not preferable in terms of feeling and quality, it is preferable to pre-treat the fabric in advance. As a treatment method for this purpose, there are a method of treating the cloth with a water repellent such as a fluorine-based or silicone-based substance, and a method of passing the cloth through a calender to swell the cloth and smooth the cloth. When a laminating method of forming a thermoplastic resin layer on release paper in advance and then laminating the fabric with an adhesive is used, the adhesive may be a polyurethane resin, an acrylic resin, a nylon resin, an ester resin, A vinyl acetate resin, a vinyl chloride resin, a styrene butadiene resin, an acrylonitrile butadiene resin, a polyvinyl alcohol resin, a melamine resin, a glyoxal resin can be used, and two or more kinds can be used in combination. . Further, a crosslinking agent, a coloring agent, a thickener and the like can be added as needed.

The method for producing the phase change substance-containing microphone capsule includes an interfacial polymerization method, an in-situ method, a solvent volatilization method, a coacervation / phase separation method, a porous orifice method, and a spray condensation method. In order to produce the compound effectively and economically, an interfacial polymerization method, in-situ
It is preferred to manufacture by the method. Microcapsules can be used either porous or non-porous, but the phase-change material is preferably solid or liquid, and has a problem of air diffusion and migration. The wall thickness of the capsule is preferably 0.05 to 5 μm from the viewpoint of the pressure resistance and abrasion of the microcapsule itself. The particle size is 0.5 to 50 μm, preferably 1 to 20 μm.
μm. This is because the microcapsules need to be completely covered in the thermoplastic resin layer when the thermoplastic resin layer is formed, thereby preventing the microcapsules from being damaged.

The types of resins used for the wall material of the microcapsules include melamine, methylcellulose, polyvinyl alcohol, gelatin, gum arabic, starch, polyvinylpyrrolidone, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, polyacrylic acid, ethylcellulose, polyethylene, There are polymethacrylate, polyamide, polyethylene vinyl acetate, nitrocellulose, silicone, cellulose acetate phthalate, waxes and the like, and a melamine type which can be produced stably is preferable. The amount of the microcapsules added to the thermoplastic resin layer is 0.5 wt% to 60 wt% due to the strength of the thermoplastic resin layer and the amount of the phase change substance.
Is preferred. At 0.5 wt% or less, the amount of heat of the phase change material is not sufficient, and at 60 wt% or more, the strength of the thermoplastic resin layer is significantly reduced. The higher the purity of the phase change substance added to the microcapsule, the higher the phase change energy is, and the phase change energy is preferably 50 to 100%, and more preferably 80% or more.

As the phase change substance, for example, normal paraffin (C _n H _{2n + 2} n: 10 to 30), polyethylene glycol, water, propylene glycol, etc., having a melting point of −30 ° C.
Any substance can be used as long as it is within the range of -60 ° C. The melting point of the phase change material may be arbitrarily used depending on the application. Two or more kinds of microcapsules having different phase change substances can be arbitrarily added to the thermoplastic resin layer for use.

Examples of the ceramics having thermal barrier properties include carbides of transition metals belonging to Group IV of the periodic table, such as titanium and zirconium, and carbides such as boron and silicon, silicon, titanium, chromium, manganese, and the like. Oxides such as iron, cobalt, nickel and copper zirconium, and
These composite compositions preferably have a particle size of about 25 μm from the problem of film forming properties of the thermoplastic resin layer. It is preferable that the amount of ceramic having heat insulation added to the thermoplastic resin layer is between 0.5 wt% and 60 wt%. 0.5
If the content is less than 60 wt%, the heat insulating effect is not sufficient.
%, The strength of the thermoplastic resin layer is reduced.

Metal powders such as aluminum, stainless steel, iron, nickel, magnesium, chromium and copper are used as the radiant heat reflective and heat conductive material, and aluminum having the best balance between reflection efficiency and heat conductivity is used. preferable. The method of adding the radiation heat reflective substance may be mixing with a resin, sputtering, printing, or gravure. The particle diameter of the metal powder is preferably about 25 μm or less from the viewpoint of the film forming property of the thermoplastic resin layer and the adhesion of print and gravure. The amount of metal having radiation heat reflection and heat conductivity to the thermoplastic resin layer is 0.5 wt.
% To 60 wt%. When the content is 0.5 wt% or less, the radiation heat reflection property and the thermal conductivity are not sufficient, and when the content is 60 wt% or more, the strength of the thermoplastic resin layer is reduced.

As a representative example of the composite sheet of the present invention, as shown in FIGS. 1A to 1C, a thermoplastic resin layer containing ceramic and a microcapsule containing phase change material are contained on at least one surface of a fabric. The metal powder is laminated in the order of the thermoplastic resin layer, and the metal powder is present in the thermoplastic synthetic resin layer containing the phase change substance-encapsulated microcapsules and / or on the thermoplastic synthetic resin layer containing the phase change substance-encapsulated microcapsules. The heat generated by the phase change is reduced by the thermoplastic resin layer containing ceramics, which has excellent heat insulation properties, to reduce heat dissipation to the fabric side and utilize the high thermal conductivity of metal powder. Then, heat is efficiently transferred to the inside of the clothes. In addition, the heat insulating effect of the ceramic is also effective against changes in the outside air temperature, and is excellent in temperature constancy in clothes.

In the present invention, as the post-processing of the composite sheet, a water-repellent processing, a water-absorbing processing, a flexible processing, a flame-retardant processing, and the like may be optionally performed as required.

[0018]

EXAMPLES Hereinafter, the composite sheet of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the measuring method of the characteristic shown in the Example is as follows. Moisture permeability JIS L-1099 A-1 method Waterproof JIS L-1092 Water resistance test Absorption and heat dissipation Using a device shown in Fig. 2 in a place where the temperature and humidity at an outside temperature of 20 ° C and a humidity of 65% can be adjusted over a day and night. Using the conditioned sample, the apparatus was placed on a hot plate heated to a constant temperature of 40 ° C., and the temperature after 15 seconds was measured. Thereafter, after the temperature of the fabric reached equilibrium, the apparatus was set on a plate which was constantly cooled to 10 ° C., and the temperature after 15 seconds was measured in the same manner. A fabric having a smaller temperature change in both temperature rise and cooling, that is, a fabric having a lower temperature when ascending and a higher temperature as it is cooled, is more excellent in uniformity of the temperature inside the garment.

[0019]

Example 1 70 denier nylon 66 (density 13
6 / inch, weft density 104 / inch) fabric was coated with a fluorinated water repellent (Asahigard LS31 manufactured by Meisei Chemical Co., Ltd.).
7) After immersion in 0.8% and squeezing at a squeezing ratio of 80%, 150 ° C
For 2 minutes. Next, 100 parts of an acrylic resin (Chris Coat P-1220 manufactured by Dai Nippon Ink Co., Ltd.) and an isocyanate crosslinking agent (Chris Bon N manufactured by Dai Nippon Ink Co., Ltd.)
X) A solution prepared by mixing 2 parts of EtAC and 10 parts of EtAC was used as a resin solution, and the prepared resin solution was laminated on one surface of the fabric with a knife coater to form three coating layers. The first layer is ceramic (TISMO manufactured by Otsuka Chemical Co., Ltd.), the second layer is microcapsules containing phase change material (paraffin wax having a melting point of 36 ° C., the average particle diameter is 5 μm), and the third layer is aluminum (Asahi Kasei Kogyo). (STAPAPV-10) was added to the resin film in an amount of 15 wt%. Each resin layer is 8
Heat treatment was performed at 0 ° C. for 2 minutes to produce a composite sheet by dry coagulation. The coating amount was 30 g / m ² in total.

The resulting composite sheet was measured for moisture permeability, waterproofness, and moisture absorption / release properties, and the results are shown in Table 1.

[0021]

Example 2 70 denier nylon 66 (density 13
6 / inch, weft density 104 / inch) fabric was coated with a fluorinated water repellent (Asahigard LS31 manufactured by Meisei Chemical Co., Ltd.).
7) After immersion in 0.8% and squeezing at a squeezing ratio of 80%, 150 ° C
For 2 minutes. Next, 100 parts of a polyurethane resin (Heimlen X-3038 manufactured by Dainichi Seika Co., Ltd.), 2 parts of an isocyanate crosslinking agent (Resamine X manufactured by Dainichi Seika Co., Ltd.) and a water repellent (Asahigard manufactured by Meisei Chemical Co., Ltd.) AG650) 2 parts and toluene / MEK, 18/13 parts and water / MEK, 50
/ 5 parts of the prepared solution was used as a resin solution, and the prepared resin solution was laminated on one surface of a fabric with a knife coater to form three coating layers. The first layer is ceramic (TISMO manufactured by Otsuka Chemical Co., Ltd.), the second layer is microcapsules containing phase change material (paraffin wax having a melting point of 36 ° C., the average particle diameter is 5 μm), and the third layer is aluminum (Asahi Kasei Kogyo). (STAPAPV-10) was added to the resin film in an amount of 15 wt%. Each resin layer was heat-treated at 80 ° C. for 2 minutes and then heat-treated at 120 ° C. for 2 minutes to produce a composite sheet by dry coagulation. The applied amount was 50 g / m ² in total.

The resulting composite sheet was measured for moisture permeability, waterproofness, and moisture absorption / release properties, and the results are shown in Table 1.

[0023]

Comparative Example 1 In the same resin solution and processing method as in Example 2, a composite sheet in which 15% by weight of phase change substance-encapsulated microcapsules was added to the second layer, and the applied amount was 50 g / m ^{2 in} total. Was.

[0024]

Comparative Example 2 The same resin solution and processing method as in Example 2 except that ceramic, a capsule containing phase change material, and aluminum were not added. Coating amount is 50g / m in total
^{Was 2} .

[0025]

Comparative Example 3 The same resin solution and processing method as in Example 2 except that ceramic was added to the first layer and aluminum was added to the third layer in an amount of 15 wt% to the resin film. The applied amount was 50 g / m ² in total. The moisture permeability, waterproofness, and heat dissipation of the composite sheets of Comparative Example 1, Comparative Example 2, and Comparative Example 3 were measured, and the results are shown in Table 1.

From the results shown in Table 1, it was found that the present invention is a composite sheet having moisture permeability and waterproofness, and further having excellent temperature constancy.

[0027]

[Table 1]

[0028]

The present invention relates to a composite sheet comprising a fabric and a thermoplastic resin, which contains microcapsules encapsulating a phase-change substance in the resin, and has excellent heat insulating ceramic and radiant heat reflectivity and heat conductivity. By adding an excellent metal powder to the thermoplastic resin layer, it is possible to manufacture composite sheets that have excellent heat transfer efficiency and do not impair fabric strength, and that have excellent thermostatic properties against sudden changes in temperature. ,
When used for outdoor applications, rain gear, diaper covers, etc., it is a comfortable garment that exhibits excellent temperature constancy against temperature changes in the external environment and is excellent in cooling, especially in heat retention.

[Brief description of the drawings]

1 (A) to 1 (C) are cross-sectional views of a composite sheet of the present invention.

FIG. 2 shows an apparatus for measuring the heat absorbing and releasing properties of the composite sheet of the present invention.

[Explanation of symbols]

 1: Fabric 2: Ceramic 3: Thermoplastic resin 4: Microcapsule containing phase change material 5: Metal powder 6: Nylon taffeta 7: Metal container 8: Thermocouple 9: Measurement sample

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁷ , DB name) D06M 11/00-11/84

Claims (1)

(57) [Claims] 1. A thermoplastic synthetic resin layer containing ceramic and a thermoplastic synthetic resin layer containing microcapsules containing phase change material are laminated on at least one surface of the fabric in this order, and a metal powder is contained in the microparticles containing phase change material. A composite sheet, wherein the composite sheet is present in a thermoplastic synthetic resin layer containing capsules and / or on a thermoplastic synthetic resin layer containing microcapsules containing the phase change substance.