JPH06128392A - Light-heat conversion sheet and its production - Google Patents

Abstract

PURPOSE:To provide the title sheet which can effectively convert abundant solar radiation energy having a peak at neat 0.5mum into thermal energy and can emit the thermal energy and to provide a process for industrially massproducing such a light-heat conversion sheet. CONSTITUTION:A near-infrared absorbing substance which can emit thermal energy when bombarded by light in a wavelength region of 0.5-1.5mum is adopted as a surface light-heat converting agent to be supported on a fibrous structure or contained in a synthetic resin material. In this way, sunlight continuously and abundantly supplied to the earth can effectively be used as an energy source for clothes, buildings, agriculture (the field of house culture) or improvement of living environment (e.g. room heating or show thawing).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-heat conversion sheet-like material, and more specifically, a heat-generating light-heat conversion sheet-like material that absorbs near-infrared rays in sunlight to convert it into heat energy and emits it. The present invention relates to a method capable of industrially mass-producing such a light-heat conversion sheet material, for example, in the field of clothing such as winter clothing, and in the field of interior materials such as indoor curtains for blocking infrared rays as heat rays. Furthermore, it is possible to utilize in the field as a snow melting material by utilizing such a planar light-heat conversion effect.

[0002]

2. Description of the Related Art Sheet-like fibrous structures represented by cloth and knitted fabrics have long been used as clothing materials for wrapping the body and as heat insulating materials for blocking cold weather. Therefore, synthetic resin sheets are also widely used.

However, these conventional sheet-like materials have only the function of blocking the heat inside so that they do not escape to the outside, or blocking the outside cold to prevent them from entering the inside, and generate heat themselves. I could not expect a heating function that positively raises the temperature. In order to add a heating function to a conventional sheet-like material, either a built-in electric heater that electrically generates heat or a chemical reaction heat generating material that generates heat due to reaction heat when iron powder chemically reacts is installed. However, in each case, there was a problem in terms of durability and mobility.

However, a sheet-like far-infrared reflective material has also been proposed which utilizes the heat-retaining power of light metals such as aluminum for clothing and building materials to reflect the heat radiated from the body or the room as far-infrared rays. However, it is difficult to say that it is satisfactory in terms of appearance, durability and versatility, and it is difficult to use it on a daily basis.

By the way, the distribution of the radiant energy of the sun illuminating the earth has a peak in the vicinity of 0.5 μm and is 0.3 to
Since 95% of the total energy is concentrated in the 2.0 μm wavelength region, the amount of energy distributed in other wavelength regions is extremely small. Therefore, if a photothermal conversion sheet-like material that can efficiently use sunlight in the 0.3 to 2.0 μm region that is abundantly landed on the earth as heat energy in this way, mobility will be restricted. It should be possible to add a heating function to clothes without doing so. If such a light-to-heat conversion sheet is present, it can be industrially used not only as a material for clothing but also in other fields such as construction.

[0006]

The present invention is directed to abundant solar radiant energy having a peak near 0.5 μm, particularly 0.5 to
It is a technical object to provide a photothermal conversion sheet-like material that can efficiently convert light in the wavelength region of 1.5 μm into heat energy and emit the heat energy.

Another technical object of the present invention is to provide a new method capable of industrially mass-producing such sheet-like materials which can be efficiently converted into heat.

Further technical problems and merits of the present invention will be further clarified by the following explanation.

[0009]

Means adopted by the present inventor to solve the above technical problems will be described below.

That is, the present invention employs a means of holding a near-infrared absorbing substance, which emits heat energy when exposed to light in the wavelength region of 0.5 to 1.5 μm, as a sheet-like photothermal conversion agent on a sheet-like material. Also, 0.5 ~
An impregnating means for preparing a dispersion liquid containing a near-infrared absorbing substance that emits heat energy by being irradiated with light in a wavelength region of 1.5 μm and dyeing a sheet-like material composed of a fiber structure with the dispersion liquid is used. Or, instead of this, a resin fixing means of heat fixing or resin fixing to a sheet-like material composed of a fiber structure using the same dispersion liquid, and further, a wavelength range of 0.5 to 1.5 μm The above-mentioned technical problem was solved by adopting a means of mixing a near-infrared absorbing substance that emits heat energy when exposed to the above-mentioned light into a synthetic resin material as an additive and molding this into a sheet shape. The point is that there is a point.

However, examples of the near-infrared absorbing substance that can be adopted in the present invention include, for example, anthraquinone-based substances such as 9,10-anthracene dione; 9,10-anthraquinone; 9,10-diosoanthracene and phthalocyanine. Phthalocyanine-based substances such as complex salts, metal complex-based substances with o, o-dihydroxyazobenzene structure, X
_{-CH = (CH - CH) n} = Y polymethine material joined by such methine chain, perchlorate tri -p- tolyl aminium _{[(p-CH 3 C 6} H 4) 3 N] + Examples include an aminium-based substance such as ClO ₄ ⁻ and other diimmonium-based substances.

It is desirable that all of these near-infrared absorbing substances are finely pulverized to have an average particle size of 1.0 μm or less and used as they are, or they are dispersed in a surfactant before use. It is preferable that the amount used is as small as possible so that the whiteness of the sheet-like material is not deteriorated and the texture of the dough is not impaired, but in order to produce the temperature-increasing effect when coated, 0.1-3.0 w%, ideally
0.3 to 1.5 w% is required, and the compounding ratio should be determined appropriately according to the intended use of the product.

Next, the sheet material to which the present invention is applied is
Textile fabrics, knitted fabrics, fiber structures in the form of non-woven fabrics include polyester, polyamide, polyacrylonitrile,
Mention may be made of synthetic fibers such as polyurethane, semi-synthetic fibers such as acetate, recycled fibers such as rayon, and natural fibers such as cotton, hemp or wool.

When the present invention is applied to a synthetic resin sheet, a polyurethane resin is used as a molding material,
Conventionally known general-purpose resins such as acrylic resin, silicone resin, polyester resin, polycarbonate resin, polyacetal resin, fluorine resin, and ABS resin can be adopted.

When the sheet-like material holds the near-infrared absorptive material in this way, the flexibility of the material of the material of the sheet-like material, the texture and the aesthetics of the material are utilized, and the sun in the wavelength region of 0.5 to 1.5 μm is used. It becomes possible to convert light into heat and generate an appropriate temperature raising effect.

[0016]

EXAMPLES The present invention will now be described in more detail with reference to examples.

Example 1 A polyester processed yarn woven fabric was dyed with a treating solution having the following blending ratio at a bath ratio of 1:20 and a temperature of 135 ° C. for 15 minutes under high pressure to obtain a prototype 1. I. Anthraquinone-based near-infrared absorbing material (SIR-114 manufactured by Mitsui Toatsu Dye) 0.3 wt% b. Polyoxyethylene glycol alkyl ester 0.5 g / l c. Acetic acid 0.5 g / l d. Sodium acetate 0.5 g / l

Comparative product 1 For the purpose of comparison with Example 1 above, the same polyester processed yarn woven fabric as in Example 1 was used, and 0.5 g / l of the above polyoxyethylene glycol alkyl ester was mixed with 0.5% of the above acetic acid.
Using a treatment solution containing g / l and 0.5 g / l of the above sodium acetate, a dyeing treatment was carried out under a high pressure for 15 minutes at a bath ratio of 1:20 and a temperature of 135 ° C. to prepare Comparative Product 1.

Example 2 The polyester processed yarn woven fabric was dyed with a treating solution having the following blending ratio under a high pressure at a bath ratio of 1:20 and a temperature of 135 ° C. for 15 minutes to obtain a prototype 2. I. Metal complex type near-infrared absorbing material (SIR-132, manufactured by Mitsui Toatsu Dye) 0.3 wt% b. Polyoxyethylene glycol alkyl ester 0.5 g / l c. Acetic acid 0.5 g / l d. Sodium acetate 0.5 g / l

Comparative product 2 For the purpose of comparison with Example 2 above, the same polyester processed yarn woven fabric as in Example 2 was used, and 0.5 g / l of the above polyoxyethylene glycol alkyl ester and 0.5% of the above acetic acid of acetic acid.
Using the treatment liquid containing g / l and 0.5 g / l of the above sodium acetate, a dyeing treatment was carried out under a high pressure for 15 minutes at a bath ratio of 1:20 and a temperature of 135 ° C. to prepare Comparative product 2.

Example 3 A polyester processed yarn woven fabric was dyed with a treating solution having the following blending ratio under a high pressure at a bath ratio of 1:20 and a temperature of 135 ° C. for 15 minutes to obtain a prototype 3. I. As a near-infrared absorbing material, anthraquinone-based near-infrared absorbing material (SIR-114 manufactured by Mitsui Toatsu Dye) 0.15wt% Metal complex-based near-infrared absorbing material (SIR-132 manufactured by Mitsui Toatsu dye) 0.15wt% b. Polyoxyethylene glycol alkyl ester 0.5 g / l c. Acetic acid 0.5 g / l d. Sodium acetate 0.5 g / l

Comparative product 3 For the purpose of comparison with Example 3 above, the same polyester processed yarn woven fabric as in Example 3 was used, and 0.5 g / l of the above polyoxyethylene glycol alkyl ester and 0.5% of the above acetic acid were added.
Using a treatment solution containing g / l and 0.5 g / l of the above-mentioned sodium acetate, a dyeing treatment was carried out under a high pressure for 15 minutes at a bath ratio of 1:20 and a temperature of 135 ° C. to prepare Comparative product 3.

Example 4 The following synthetic resin compounding liquid was applied onto a release paper with a bar coater to a thickness of 200 μm in wet clearance, hot air was blown at 130 ° C. for 1 minute to perform a drying treatment, and then the release paper was removed. The film was peeled off to obtain a film (prototype 4) having a thickness of 18 μm. I. Anthraquinone-based near-infrared absorbing material (SIR-114, manufactured by Mitsui Toatsu Dye) 0.2 parts b. Polycarbonate-based urethane resin liquid (Crisbon NY333 manufactured by Dainippon Ink and Chemicals) 100 parts d. Dimethylformamide 10 parts

Comparative Product 4 For comparison with Example 4 above, a synthetic resin compounding solution containing 100 parts of the above polycarbonate-based urethane resin solution and 10 parts of the above dimethylformamide (2) was applied to a release paper with a bar coater. The wet clearance was applied to a thickness of 200 μm, and hot air at 130 ° C. was blown for 1 minute to perform a drying treatment, and then peeled from the release paper to make a film (prototype) having a thickness of 18 μm.

[0025]

[Comparative test] Prototypes 1 to 4 according to the respective examples obtained as described above were subjected to a sunlight irradiation test in comparison with each of Comparative products 1 to 4, and comparison with each prototype was made. It was found that the following temperature difference occurred between the product and the product. In addition, this comparative test was conducted in a room with a constant temperature and humidity (temperature 20 ° C: humidity
60%), a DR 125 / TL reflective sunlight lamp (manufactured by Toshiba Lighting & Technology) with a ballast (1.25 MTP-105 H: manufactured by Toshiba Lighting & Technology) at 120 mm intervals while maintaining a constant voltage with each prototype. When the temperature rises of the prototype and the comparative product were compared with each other by irradiating with the comparative product, the following results were obtained.

Comparative test 1 Sunlight lamp irradiation time Prototype 1 (Example 1) Comparative product 1 1 minute later 27.9 ° C 27.6 ° C 2 minutes later 30.6 ° C 29.9 ° C 3 minutes later 32.9 ° C 31.9 ° C 4 minutes later 34.9 ° C 33.7 ° C 5 After 3 minutes 36.6 ° C 35.3 ° C After 6 minutes 38.2 ° C 36.7 ° C After 7 minutes 39.5 ° C 37.9 ° C After 8 minutes 40.7 ° C 39.0 ° C After 9 minutes 41.8 ° C 39.8 ° C 10 minutes After 42.7 ° C 40.7 ° C 11 minutes After 43.6 ° C 41.2 ° C 12 minutes After 44.2 ° C 41.8 ° C 13 minutes later 44.7 ° C 42.3 ° C 14 minutes later 45.2 ° C 42.8 ° C 15 minutes later 45.6 ° C 43.3 ° C 16 minutes later 45.8 ° C 43.6 ° C 17 minutes later 46.2 ° C 43.8 ° C 18 minutes later 46.4 ° C 44.2 ° C 19 minutes later 46.8 ℃ 44.4 ℃ 20 minutes later 47.1 ℃ 44.6 ℃ 21 minutes later 47.2 ℃ 44.8 ℃ 22 minutes later 47.3 ℃ 44.8 ℃ 23 minutes later 47.6 ℃ 44.8 ℃ 24 minutes later 47.8 ℃ 44.8 ℃ 25 minutes later 47.8 ℃ 44.8 ℃ 26 minutes later 47.8 ℃ 44.8 ℃ According to the result of Comparative Test 1, the temperature of the comparative product 1 stopped rising at the irradiation time of 21 minutes, while the irradiation time was 2 in the prototype 1 (Example 1). The temperature continued to rise until 4 minutes, and finally prototype 1 heated up 3 ° C more than comparative product 1. It is speculated that such a temperature rise is due to the action of the near-infrared absorbing substance held in the prototype 1.

Comparative Test 2 Sunlight Lamp Irradiation Time Prototype 2 (Example 2) Comparative Product 2 1 minute later 28.1 ° C 27.6 ° C 2 minutes later 30.7 ° C 29.8 ° C 3 minutes later 32.8 ° C 31.8 ° C 4 minutes later 34.7 ° C 33.5 ° C 5 After 3 minutes 36.4 ℃ 35.0 ℃ 6 minutes after 37.9 ℃ 36.3 ℃ 7 minutes after 39.2 ℃ 37.3 ℃ 8 minutes after 40.3 ℃ 38.3 ℃ 9 minutes after 41.3 ℃ 39.2 ℃ 10 minutes after 42.2 ℃ 39.9 ℃ 11 minutes after 42.9 ℃ 40.6 ℃ 12 minutes 43.5 ℃ 41.2 ℃ 13 minutes later 44.1 ℃ 41.6 ℃ 14 minutes later 44.6 ℃ 42.1 ℃ 15 minutes later 45.1 ℃ 42.4 ℃ 16 minutes later 45.3 ℃ 42.7 ℃ 17 minutes later 45.7 ℃ 42.9 ℃ 18 minutes later 45.9 ℃ 43.2 ℃ 19 minutes later 46.2 ℃ 43.4 ℃ 20 minutes later 46.2 ℃ 43.6 ℃ 21 minutes later 46.4 ℃ 43.7 ℃ 22 minutes later 46.6 ℃ 43.8 ℃ 23 minutes later 46.7 ℃ 43.9 ℃ 24 minutes later 46.8 ℃ 43.8 ℃ 25 minutes later 46.9 ℃ 43.9 ℃ 26 minutes later 46.9 ℃ 44.1 ℃ 27 minutes later 46.9 ℃ 44.3 ℃ 28 minutes later 46.9 ℃ 44.3 ℃ According to the results of the above-mentioned comparative test 2, Comparative product 2
The temperature rise stopped at 27 minutes, and the temperature rise of the prototype 2 (Example 2) stopped at the irradiation time of 25 minutes. It was 2.6 ℃ higher. It is speculated that such a temperature rise difference is due to the action of the near-infrared absorbing substance held in the prototype 2.

Comparative Test 3 Sunlight Lamp Irradiation Time Trial Product 3 (Example 3) Comparative Product 3 1 minute later 28.4 ° C 27.6 ° C 2 minutes later 31.3 ° C 29.9 ° C 3 minutes later 33.6 ° C 31.9 ° C 4 minutes later 35.7 ° C 33.7 ° C 5 Minutes 37.8 ° C 35.3 ° C 6 minutes later 39.2 ° C 36.7 ° C 7 minutes later 40.6 ° C 37.9 ° C 8 minutes later 41.8 ° C 39.0 ° C 9 minutes 42.9 ° C 39.8 ° C 10 minutes later 43.8 ° C 40.7 ° C 11 minutes 44.7 ° C 41.2 ° C 12 minutes 45.4 ℃ 41.8 ℃ 13 minutes later 46.0 ℃ 42.3 ℃ 14 minutes later 46.5 ℃ 42.8 ℃ 15 minutes later 47.0 ℃ 43.3 ℃ 16 minutes later 47.4 ℃ 43.6 ℃ 17 minutes later 47.7 ℃ 43.8 ℃ 18 minutes later 48.1 ℃ 44.2 ℃ 19 minutes later 48.3 ° C 44.4 ° C 20 minutes later 48.6 ° C 44.6 ° C 21 minutes later 48.7 ° C 44.8 ° C 22 minutes later 48.8 ° C 44.8 ° C 23 minutes later 49.0 ° C 44.8 ° C 24 minutes later 49.1 ° C 44.8 ° C 25 minutes later 49.2 ° C 44.8 ° C 26 minutes later 49.3 ℃ 44.8 ℃ 27 minutes later 49.4 ℃ 44.8 ℃ 28 minutes later 49.5 ℃ 44.8 ℃ According to the results of the comparative test 3 above, the temperature of the comparative product 3 stopped rising after 21 minutes irradiation time. In the prototype 3 (Example 3) The increase in temperature continues until the irradiation time is 28 minutes, and finally than comparative product 3 is better prototype 3
The temperature was raised to 4.7 ° C. It is presumed that such a temperature rise is due to the action of the near-infrared absorbing substance held by the prototype 3.

Comparative Test 4 Sunlight Lamp Irradiation Time Trial Product 4 (Example 4) Comparative Product 4 1 minute later 27.8 ° C 27.6 ° C 2 minutes later 30.3 ° C 29.7 ° C 3 minutes later 32.4 ° C 31.6 ° C 4 minutes later 34.3 ° C 33.1 ° C 5 Minutes 35.9 ℃ 34.5 ℃ 6 minutes 37.5 ℃ 35.7 ℃ 7 minutes 38.8 ℃ 36.7 ℃ 8 minutes 40.0 ℃ 37.7 ℃ 9 minutes 41.0 ℃ 38.6 ℃ 10 minutes 41.8 ℃ 39.1 ℃ 11 minutes 42.4 ℃ 39.8 ℃ 12 minutes After 42.8 ° C 40.3 ° C 13 minutes later 43.3 ° C 40.8 ° C 14 minutes later 43.6 ° C 41.2 ° C 15 minutes later 44.1 ° C 41.4 ° C 16 minutes later 44.2 ° C 41.8 ° C 17 minutes later 44.4 ° C 42.1 ° C 18 minutes later 44.9 ° C 42.2 ° C 19 minutes later 45.2 ℃ 42.6 ℃ 20 minutes later 45.4 ℃ 42.6 ℃ 21 minutes later 45.5 ℃ 42.8 ℃ 22 minutes later 45.7 ℃ 42.9 ℃ 23 minutes later 45.8 ℃ 43.2 ℃ 24 minutes later 46.1 ℃ 43.2 ℃ 25 minutes later 46.2 ℃ 43.2 ℃ 26 minutes later 46.1 ℃ 43.2 ℃ 27 minutes later 46.2 ℃ 43.2 ℃ 28 minutes later 46.2 ℃ 43.2 ℃ According to the results of the above comparative test 4, the temperature of the comparative product 4 stopped rising after 23 minutes irradiation time. In the prototype 4 (Example 4) increase in temperature continues until the irradiation time is 28 minutes, and finally than comparative product 3 is better prototype 3
The temperature was raised to 3.0 ° C. It is presumed that such a temperature rise is due to the action of the near-infrared absorbing substance held by the prototype 4.

The contents of the examples illustrated in the present specification and the temperature raising effect by the photothermal conversion action of the above-mentioned Examples 1 to 4 are almost as described above, but the present invention is limited to the above-exemplified examples. It is not a matter of course, and various modifications can be made within the scope of the "claims". It goes without saying that fine powder of far-infrared emitting substances such as cordierite (cordite) or β-spodumene (lithia pyroxene), which is known to have a converting action, can be adopted as fine powder or fine powder dispersed. .

[0031]

As described above, the light-heat conversion sheet material provided by the present invention contains a near-infrared absorbing material which emits heat energy when exposed to light in the wavelength region of 0.5 to 1.5 μm. As a result, sunlight in the 0.3-2.0 μm region, which constantly falls abundantly on the earth during sunshine, can be effectively used as a heat energy source.

Therefore, when mountain climbing clothing, ski clothing, or winter clothing is sewn using the light-heat converting sheet material of the present invention as the cloth, it is 0.5 to 1.5 μm, unlike the one using a simple heat insulating material (filling pad). The solar light in the wavelength range of can be positively converted into heat energy to warm the body, and since it does not require a special heating device such as an electric heater or a chemical reaction heating material that becomes heavy and bulky, it can be used for mobility. Excellent heating functional clothing can be obtained.

Further, the light-heat converting sheet material of the present invention, when spread and laid on a snow-covered roof, efficiently converts the light of the sun into heat energy to change the temperature of the roof surface. Since it will be raised to promote snow melting, it is very useful as a snow melting material in heavy snowfall areas.

Further, when the light-heat conversion sheet material of the present invention is manufactured from a synthetic resin material and used as a tent material for an agricultural sheet house (generally called a vinyl house), the heat energy conversion of sunlight is converted. As a result, the excellent greenhouse effect can be obtained, and a favorable environment for plant growth can be prepared.

Further, the light-heat conversion sheet material of the present invention is
In the case of textile structures such as woven fabrics, knitted fabrics, and non-woven fabrics, post-processing such as dyeing, and in the case of synthetic resin sheets and films, near-infrared absorbing substances are used as pigments during molding. By kneading, it can be easily produced with high efficiency, and in any case, it can be provided at low cost.

As described above, according to the present invention, a sheet-like material which cannot be positively heated (heating) unless a special heating device such as an electric heater or a chemical reaction heating material is conventionally used. It does not require the use of heat generators depending on the field of use, and since it uses sunlight, which can be called inexhaustible as its heat source, it not only makes running costs extremely low, but also makes manufacturing simple and inexpensive. It can be provided, and its industrial utility value is extremely high.

Claims (6)

[Claims] 1. A light-to-heat conversion sheet material, characterized in that a sheet-like material holds a near-infrared absorbing substance which emits heat energy when exposed to light in the wavelength region of 0.5 to 1.5 μm. 2. The sheet material is a woven or knitted material,
Or a fibrous structure such as a non-woven fabric,
Light-heat conversion sheet. 3. The light-heat conversion sheet-like article according to claim 1, wherein the sheet-like article is a synthetic resin film. 4. A dispersion liquid containing a near-infrared absorbing substance which emits heat energy when irradiated with light in the wavelength region of 0.5 to 1.5 μm is prepared, and the dispersion liquid is used to form a sheet-like fiber structure. A method for producing a light-heat conversion sheet-like product, which comprises dyeing the product. 5. A near-infrared absorbing substance that emits heat energy when irradiated with light in the wavelength region of 0.5 to 1.5 μm is pulverized, and the pulverized near-infrared absorbing substance is composed of a fiber structure. A method for producing a light-to-heat conversion sheet, which comprises heat-fixing or resin-fixing the sheet-like material. 6. A photothermal method characterized by mixing a near-infrared absorbing substance which emits heat energy when exposed to light in the wavelength region of 0.5 to 1.5 μm into a synthetic resin material and molding this into a sheet. Method for manufacturing conversion sheet material.