JP2003238815A - Far-infrared ray-emitting plastic sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a far-infrared ray-emitting plastic sheet which is useful in heat storage, storage, quality improvement and the like by exhibiting a high spectral emissivity in a broad range of the far-infrared wavelength region at normal temperatures. <P>SOLUTION: The plastic sheet which exhibits a spectral emissivity as high as ≥80% in a broad wavelength region of 5 μm to 20 μm at normal temperatures is obtained by incorporating diamide lime, which is inexpensive, does not require high temperature firing on production, and is easy to disperse in a resin, into an olefin resin (a polypropylene resin and the like), and sheeting the resulting mixture. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a far-infrared ray-generating substrate which can exert the excellent effect of infrared rays by being generated and which can be easily manufactured. The present invention relates to a far-infrared ray-generating plastic sheet which is useful for storage, quality improvement, etc., has good moldability, and exhibits an excellent far-infrared ray effect.

[0002]

2. Description of the Related Art Generally, the definitions of infrared rays and far infrared rays are not so clear, but in the present specification, the wavelength from red light (wavelength 0.83 μm), which is the long wavelength end of visible light, to wavelength 100.
An electromagnetic wave corresponding to a region up to 0 μm is an infrared ray, and an infrared ray having a wavelength of 3 μm or more is a far infrared ray.

All objects that have a temperature emit electromagnetic waves,
Although absorbed, it emits electromagnetic waves to the long wavelength side at low temperatures and to the low wavelength side at high temperatures, depending on the temperature of the substance. In general, almost all substances radiate far infrared rays in any material, and ordinary substances such as wood, natural fiber, and paper are
It has a spectral emissivity in the entire wavelength range of far infrared rays.

The spectral emissivity as used herein means the ratio of thermal radiation when the emissivity of an ideal black body at that temperature is 100%, and is used as an index of far infrared radiation generation at each wavelength. You can

Far-infrared radiation largely changes depending on the type of substance, density, purity, particle size, surface state, etc., and the structure and shape of the material as well as the type of substance have a great influence on its generation. Further, when the period of the molecular vibration of the molecules constituting the object is matched, the wavelength range of far infrared rays is absorbed.

In the heating device, a far infrared heat treatment device which uses far infrared rays as a heat source has been widely put into practical use, and is used for drying the baking finish of a car, heat reduction treatment of waste styrene material, and cooking utensils (rice cooker, fish). It is used for baking machines, etc.).

On the other hand, in recent years, far-infrared rays generated from substances that do not have a heat source at room temperature have effects such as heat storage and heat retention effect, growth promotion effect, food quality improvement effect, deodorant antibacterial effect, and air cleaning effect. , Practical far-infrared [separate volume] published by Human and History Co., Ltd. It has been announced in far-infrared related patent information by field.

[0008] Ceramics such as alumina and black bodies made of carbon and ash have been known as materials that generate far infrared rays at room temperature. Among these materials, ceramics, etc. have a far-infrared spectral radiation pattern determined by their molecular structure, and in all wavelength ranges,
Few materials exhibit high emissivity.

Black bodies are fired products obtained by firing organic substances at a high temperature and are capable of generating far infrared rays in a wide wavelength range. Examples of black bodies include plant materials such as wood powder and lignin, mineral materials such as tar and pitch mixed with a binder resin, and heated and dehydrated under an inert gas atmosphere such as nitrogen and argon. Activated charcoal obtained by heating and firing at 500 ℃ ~ 950 ℃ bamboo charcoal, charcoal black body such as Bincho charcoal, fly ash and clinker ash and resin under inert gas atmosphere High-temperature polymer obtained by baking in a furnace or a reducing flame furnace and then baking at 800 ° C to 850 ° C to obtain a ceramic blackbody or resin such as phenol resin at 700 ° C to 800 ° C in an inert gas. Examples include black bodies.

These conventional far-infrared ray-generating materials are a mixture of carbon and ash, and in order to obtain a far-infrared ray-generating substrate having a uniform and good performance, the raw material is controlled at high temperature. It is necessary to dry and bake under the conditions, 500 ℃
The above high temperature firing furnace was necessary.

The fired material may be in a block shape depending on the conditions, and if it is to be uniformly dispersed in a resin so that it can be formed into a sheet, a fine pulverization / classification process is required, and a far infrared ray generating material is blended. The plastic sheets made were expensive.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to efficiently generate far infrared rays in all wavelength regions by using a far infrared ray generating material which can be supplied in large quantities and at low cost without firing at high temperature. It is to provide a far infrared ray generating plastic sheet capable of

[0013]

The present invention has been made to solve the above problems, and provides a far-infrared ray-generating plastic sheet containing diamide lime.

Preferably, diamide lime is used as the base resin 10
The far-infrared ray-generating plastic sheet according to claim 1, which is contained in an amount of 5 to 50 parts by weight with respect to 0 parts by weight.

Preferably, the far-infrared ray-generating plastic sheet whose base resin is a polyolefin resin is provided.

It is preferable to provide a far-infrared ray-generating plastic sheet in which the base resin is a polypropylene-based thermoplastic elastomer resin.

The sheet thickness is preferably 30 μm to 500 μm
And the generation of far infrared rays is 80 in the wavelength range of 5 μm to 20 μm.
% Far-infrared ray-generating plastic sheet.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The far-infrared ray-generating plastic sheet of the present invention contains diamide lime which is a water-insoluble component when lime nitrogen is dispersed in water and carbon dioxide gas is blown therein. Lime nitrogen is a mixture of calcium cyanamide, calcium oxide, carbon particles and the like, and by dispersing lime nitrogen in water and blowing carbon dioxide gas, diamide lime mainly composed of water-insoluble carbon particles and calcium carbonate particles is obtained. To generate.

For example, commercially available lime nitrogen is dispersed in water so as to have a cyanamide concentration of 3% to 15%, a gas having a carbon dioxide concentration of 30 to 50% is blown, and the temperature of the aqueous solution is 30 to 30%.
An aqueous dispersion of diamide lime can be produced by stirring and mixing at 60 ° C. and pH of 6 to 8.

The water-insoluble matter is separated from the dispersed aqueous solution by a method such as centrifugation, filtration or sedimentation, and then dried by an appropriate method.

The drying method is not particularly limited, but considering the shape of the particles after drying, a drying method that does not have a physical share such that the particles have a structure in which carbon particles are uniformly attached and dispersed on the surface of the particles is used. It is preferable to take them, and static box type drying, band drying and the like are particularly preferable.

The drying temperature is from 80 ° C to 300 ° C, preferably from 100 ° C to 200 ° C, particularly preferably from 100 ° C to 15 ° C.
It is 0 ° C. If the drying temperature is 80 ° C or higher, it will not take a long time to dry, and if it is 150 ° C or lower,
It does not affect the quality or structure of the component compounds.

The diamide lime particles thus obtained are inorganic particles containing calcium carbonate, calcium hydroxide and carbon, and are a mixture of calcium carbonate / calcium hydroxide particles and carbon fine particles, and have an average particle diameter. Is 30-5
It is a particle having a secondary structure in which carbon fine particles having an average particle size of 0.5 to 10 μm are dispersed almost uniformly and adhered on the surface of 0 μm of calcium carbonate / calcium hydroxide particles.

The above-mentioned calcium carbonate / calcium hydroxide particles are in a state in which the two components are uniformly dispersed, or a part of the particles are calcium hydroxide-modified calcium carbonate particles, and particularly a part of the surface is water. Calcium oxide-modified calcium carbonate particles are preferred.

The diamide lime may contain other inorganic compounds in addition to calcium carbonate and calcium hydroxide. As used herein, the other inorganic compounds include oxides of carbon, calcium oxide, magnesium oxide, aluminum oxide, iron oxide, etc., inorganic carbonates such as potassium carbonate, sodium carbonate, barium carbonate, chlorides such as calcium chloride, magnesium chloride, etc. And hydroxides such as aluminum hydroxide and silicic acid compounds such as calcium silicate.

The particle diameter of calcium carbonate / calcium hydroxide particles of diamide lime is 20 to 70 μm, the carbon particles are amorphous fine particulate carbon powder, and the average particle diameter of carbon particles is 0.5 to 10 μm. Is.

In the diamide lime particles, it is considered that calcium carbonate / calcium hydroxide particles play a role of a dispersion carrier for carbon particles, and an appropriate calcium hydroxide portion adheres, fuses, and holds carbon particles on the surface. , Which has a dispersibility different from that of a simple mixture, and when mixed with a resin,
It is presumed that it has an excellent far-infrared ray generation effect.

The far-infrared ray generating sheet of the present invention is prepared by mixing the above-mentioned diamide lime with a base resin to form a sheet. For example, as the base resin, the diamide lime particles can be dispersed and formed into a sheet. The resin is not particularly limited as long as it can be used, but in view of easiness of forming into a sheet, treatment of the sheet after disposal, and the like, a polyolefin resin that does not generate a harmful substance during incineration is preferable.

The polyolefin resin of the present invention includes a polyolefin resin and a modified olefin resin.

A polyolefin resin in a narrow sense has 2 to 2 carbon atoms.
A low crystalline or highly crystalline resin obtained by polymerizing or copolymerizing olefin of 8 as a main component, which is ultra low density polyethylene (hereinafter sometimes abbreviated as VLDPE), low density polyethylene (LDPE), straight chain Low density polyethylene (LLDPE), high density polyethylene (HD
PE), polypropylene (PP), atactic polypropylene, polybutene-1 (PB-1) and the like.

The modified olefin resin referred to herein means a resin obtained by copolymerizing an olefin and a monomer other than the olefin within a range that does not inhibit the generation of negative ions. Examples of the olefinic monomer include ethylene, propylene, butene, butadiene, isoprene, hexene, heptene, octene, and the like, and examples of the monomer to be copolymerized include EPDM, styrene, alkylstyrene, vinyl ether, and the like.

Examples of the styrene-olefin copolymer resin include styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene / butylene-polymer.
Styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SE
PS), styrene-ethylene / propylene block copolymer (SEP), styrene-ethylene-ethylene / propylene-styrene block copolymer (SEEPS), and the like. In addition, other random copolymers such as styrene / butadiene random copolymer (SBR) and hydrogenated styrene / butadiene random copolymer (HSBR) can also be used.

Considering the sheet formability among the above polyolefin resins, ultra low density polyethylene, linear low density polyethylene, low density polyethylene, high density polyethylene, polypropylene, polybutene-1, styrene-
At least one selected from olefin-based copolymer resins
A resin composition of at least one kind is preferable, and among them, a polypropylene resin containing polypropylene as a main constituent is preferably used because of good moldability and negative ion generation effect.

Particularly, in consideration of the formability of a sheet and the physical properties of the sheet, a polypropylene-based thermoplastic elastomer (T
PO) is most preferred. Depending on the manufacturing form, TPO
Simple blend type TPO (thermoplastic polyolefin resin and elastomer-imparting component such as EPDM are physically blended by a dispersing machine such as Banbury or Plastomill, and a rubber component is dispersed in an olefin matrix),
Implant type TPO (in which a hard segment portion and a soft segment portion are sequentially formed in a reactor by polymerizing an olefin in two steps to impart elastomeric properties), and a dynamic cross-linking type TPO (dispersing machine such as Banbury or plastomill) Which is obtained by subjecting the rubber component to a cross-linking reaction while being physically mixed with the above, and the cross-linked rubber component is finely dispersed in the thermoplastic polyolefin matrix).

The resin of the present invention may contain, in addition to the above-mentioned polyolefin resin, a resin in a range not hindering sheet moldability and generation of negative ions. Examples of the resins that can be mixed include (meth) acrylic acid ester-based resins, styrene-based resins, urethane-based resins, polyester-based resins, polyoxyethylene-based resins, and polyamide-based resins.

The resin composition of the present invention may contain a lubricant in the polyolefin resin. The blending amount of the lubricant varies depending on the kind of the lubricant, but is 0.1 part by weight to 1.0 part by weight, preferably 0.2 parts by weight with respect to 100 parts by weight of the resin.
Parts by weight to 0.8 parts by weight, particularly preferably 0.3 parts by weight
Contains 0.7 parts by weight. The amount may be selected so that the releasability from a metal surface such as a calendar roll, an extruder screw, a cylinder, or a mold is sufficient.

The lubricant is not particularly limited as long as it has sufficient releasability from the metal surface, but a fatty acid metal salt lubricant, a fatty acid ester lubricant, and a low molecular weight polyethylene lubricant can be used. Examples of the fatty acid metal salt-based lubricant include a calcium salt, a magnesium salt, a zinc salt, and a barium salt of a fatty acid having 0 to 3 double bonds in 8 to 30 carbon atoms or 0 to 1 hydroxyl group. As a fatty acid ester-based lubricant, a double bond in 0 to 30 carbon atoms
Examples include fatty acid having 3 groups or having 0 to 1 hydroxyl group and glycol, glycerin, pentaerythritol alone or complex monoester, diester, triester, tetraester, and low molecular weight polyethylene lubricant manufactured by Allied Chemical Co., Ltd. AC6A, AC629A,
AC7A, AC316A, Mitsui Petrochemical's high wax 410P, 420P, 210MP, 220MP, 40
51E, 4052E, 4202E, Eporene N-10, N-11, N-12, N manufactured by Eastman Chemical Company.
-14, Sanyo Kaseisha Sun Wax 131P, 151
P, 161P, 171P, 310P, 330P, 250
The fatty acid metal salt is preferred from the viewpoint of releasability from the metal surface, and the oleic acid metal salt is most preferred in consideration of the non-bleeding property of the molded sheet.

Particularly when polypropylene-based thermoplastic elastomer is used as the base resin, 0.3 to 1.0 part of an aliphatic metal salt lubricant such as calcium oleate, magnesium oleate or zinc oleate is used. Most preferably.

The resin may contain various additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, a colorant and the like, as long as the sheet moldability and the appearance are not impaired.

As the ultraviolet absorber, organic ultraviolet absorbers such as benzophenone type, benzotriazole type, cyanoacrylate type and benzoate type, and inorganic type ultraviolet absorbers such as ultrafine particle titanium oxide and cerium oxide can be used. In addition, it is also possible to use an inorganic pigment such as titanium oxide having an ultraviolet shielding property.

Examples of the light stabilizer include Tinuvin 123, Tinuvin 144, Tinuvin 119, Tinuvin 622, Tinuvin 765, Tinuvin 7 manufactured by Ciba Specialty Chemicals.
70, Tinuvin 944, and Tinuvin 2020 can be preferably used.

As the antioxidant, hindered phenol-based, phosphite-based, lactone-based, α-tocopherol-based, and hydroxylamine-based compounds can be used.

The filler or pigment is not particularly limited, and wet silica, dry silica, alumina, titanium oxide, zinc oxide, zinc sulfide, glass beads, glass balloons, acrylic beads, styrene beads, silicone beads, zeolite, sulfuric acid. Barium, magnesium hydroxide,
Aluminum hydroxide, hydrotalcite, hydrocalumite and the like can be mentioned, and they can be appropriately used depending on the purpose.

In order to produce the resin composition of the present invention, a known method may be used to knead calcium carbonate / calcium hydroxide particles, carbon particle mixed particles and a lubricant into a polyolefin resin. , A Banbury mixer, an extrusion pelletizer, a cokneader, etc., and a Banbury mixer or an extrusion pelletizer is particularly preferable.

The amount of diamide lime mixed with the above resin is 5 to 50 parts by weight, preferably 10 to 20 parts by weight, based on 100 parts by weight of the resin, in consideration of the formability, appearance, strength and the like of the sheet. Is good. A good far-infrared ray generating effect can be realized by mixing 5 parts by weight or more, and a mixing amount of less than 50 parts by weight does not significantly change the strength and appearance of the sheet, which is preferable.

The method of forming the resin composition containing the diamide lime thus obtained into a sheet is not particularly limited as long as the intended sheet thickness can be obtained, but calender molding, T-die extrusion Although molding and inflation die extrusion molding methods are possible, calender molding and T-die extrusion molding are particularly preferable in view of economic efficiency.

The sheet thickness depends on the method of use,
30 in consideration of sheet strength, flexibility, and far-infrared ray generation effect
μm to 500 μm, particularly preferably 50 μm to 300 μm
Is. If the thickness is 30 μm or more, a sheet having diamide lime dispersed therein can have sufficient strength, which is preferable.
If it is less than μm, it is advantageous in terms of cost.

The sheet containing diamide lime produced as described above exhibits an emissivity of 80% or more in the wavelength range of far infrared rays of from 5 μm to 20 μm, and uses the far infrared ray generation effect to provide a heat retention heat storage sheet or a heat retention sheet. It is effectively used for building materials for cold regions, container materials, etc.

The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

[0050]

Reference Example 15 L of water was charged into a 50 L stirrer, a cooling jacket and a stainless steel reaction layer equipped with a reflux condenser, and commercially available carbon dioxide under stirring was introduced from a cylinder.
6.3 kg of commercially available lime nitrogen (manufactured by Nippon Carbide Industry Co., Ltd.) was added little by little so that the reaction temperature was kept at 15 degrees Celsius and the pH did not exceed 7.5. The addition of lime nitrogen was completed in about 7 hours, and then the mixture was stirred for about 1 hour as it was, then the introduction of carbon dioxide gas was stopped, and the produced water-insoluble matter was divided into several portions and filtered through a Nutsche. After washing with a total of 3 L of water, the wet cake was spread on a tray in a thickness of about 2 cm and dried in a hot air circulation dryer at 130 degrees for 6 hours. The obtained diamide lime mixture was 7.5 Kg, and the composition was as follows. Carbon 10.1 wt% Calcium carbonate 80.5 wt% Calcium hydroxide 5.2 wt% Silicic acid (SiO2) 1.9 wt% Aluminum oxide 0.9 wt% Magnesium oxide 0.7 wt% Moisture 0.7 wt%

[0051]

[Example 1] Polypropylene resin F- manufactured by Idemitsu Petrochemical Co., Ltd.
25 parts by weight of 3900, 45 parts by weight of E-2700, J
5 kg of resin containing 30 parts by weight of -5700, zinc oleate lubricant (manufactured by Eikohsei Co., Ltd .: trade name EZ-203C)
250 g of diamide lime produced by the above method was mixed with a Henschel mixer to obtain a mixed powder. The same-direction twin-screw extruder manufactured by Ikegai Tekko Co., Ltd. was set to a cylinder temperature of 180 ° C. and a strand mold temperature of 200 ° C. to obtain a pellet compound in which particles were uniformly dispersed.

The pellet compound was placed on a 40 mm short-axis extruder manufactured by Thermoplastics Co., Ltd. and a 300 mm width coat hanger manifold type T-die mold was installed.
The pellet compound was set at 80 ° C. and 200 ° C., and extrusion molding was performed to obtain a sheet having a sheet thickness of 379 μm. A test piece is cut out from this sheet, and a sample temperature of 40 ° C. is used with JIR-E500 manufactured by JEOL Ltd. 5
When the infrared spectral emissivity at a wavelength of μm to 20 μm was measured, it was as shown in FIG. 1 and showed an emissivity of 80% or more in the wavelength range of 5 μm to 20 μm. Note that FIG.
-In any measurement of FIG. 5, the conditions of infrared spectroscopic emissivity measurement are as follows. RESOL: 32cm-1 AMPGAIN: × 32 P.INT: 16cm-1 SCAN: 50 S.SPEED: MCT

[0053]

Example 2 A sheet having a sheet thickness of 85 μm was obtained in the same manner as in Example 1 except that the content of diamide lime was 500 g. A test piece is cut out from this sheet, and a sample temperature of 40 ° C. is used with JIR-E500 manufactured by JEOL Ltd. 5
When the infrared spectral emissivity at a wavelength of μm to 20 μm was measured, it was as shown in FIG. 2, and showed an emissivity of 80% or more in the wavelength range of 5 μm to 20 μm.

[0054]

Example 3 A sheet having a sheet thickness of 347 μm was obtained in the same manner as in Example 1 except that the compounding amount of diamide lime was 1 kg. The test piece was cut out from this sheet, and the infrared spectral emissivity at a wavelength of 5 μm to 20 μm was measured using JIR-E500 manufactured by JEOL Ltd. at a sample temperature of 40 ° C., as shown in FIG. The emissivity was 80% or more in the wavelength range of 20 μm.

[0055]

Example 4 A sheet having a sheet thickness of 330 μm was obtained in the same manner as in Example 1 except that the amount of diamide lime blended was 2.5 kg. The test piece was cut out from this sheet, and the infrared spectral emissivity at a wavelength of 5 μm to 20 μm was measured using JIR-E500 manufactured by JEOL Ltd. at a sample temperature of 40 ° C., as shown in FIG. 20
The emissivity was 80% or more in the wavelength range of μm.

[0056]

Comparative Example 1 Example 1 except that no diamide lime was added.
A sheet having a sheet thickness of 60 μm was obtained in the same manner as in. A test piece was cut out from this sheet, and the sample temperature was 40 ° C., and JIR-E500 manufactured by JEOL Ltd. was used to measure 5 μm to 2 μm.
When the infrared spectral emissivity at a wavelength of 0 μm was measured, it was as shown in FIG.

[0057]

[Comparative Example 2] A sheet was formed in the same manner as in Example 1 with a diamide lime content of 3 kg, but the sheet was easily cut and it was difficult to form a uniform sheet.

[Brief description of drawings]

FIG. 1 is a sheet of Example 1 of the present invention at 5 ° at 40 ° C.
It is a spectral radiation spectrum in a wavelength range of m to 20 μm.

FIG. 2 is a sheet of Example 2 of the present invention at 5 ° C. at 5 °
It is a spectral radiation spectrum in a wavelength range of m to 20 μm.

FIG. 3 is a sheet of Example 3 of the present invention having a thickness of 5μ at 40 ° C.
It is a spectral radiation spectrum in a wavelength range of m to 20 μm.

FIG. 4 is a sheet of Example 4 of the present invention at 5 ° at 40 ° C.
It is a spectral radiation spectrum in a wavelength range of m to 20 μm.

FIG. 5 is a sheet of the present Comparative Example 1 having a thickness of 5 μm at 40 ° C.
It is a spectral radiation spectrum in a wavelength range of ˜20 μm.

Continued front page    F-term (reference) 4F071 AA02 AA14 AA20 AB03 AB18                       AB21 AB32 AE22 AF53 AH00                       AH19 BB06 BC01 BC12                 4J002 AC081 AC111 BB001 BB031                       BB121 BB151 BB171 BP011                       DA016 DE086 DE236 FD010                       FD050 FD090 FD170 FD206

Claims (5)

[Claims] 1. A far-infrared ray-generating plastic sheet containing diamide lime. 2. The far infrared ray generating plastic sheet according to claim 1, which contains 5 to 50 parts by weight of diamide lime with respect to 100 parts by weight of the base resin. 3. The far infrared ray generating plastic sheet according to claim 1 or 2, wherein the base resin is a polyolefin resin. 4. The far infrared ray generating plastic sheet according to claim 1, wherein the base resin is a polypropylene-based thermoplastic elastomer resin. 5. A sheet having a thickness of 30 μm to 500 μm,
The far-infrared ray-generating plastic sheet according to any one of claims 1 to 4, wherein generation of far-infrared ray is 80% or more in a wavelength range of 5 µm to 20 µm.