WO2014003201A1 - 遮熱材 - Google Patents

遮熱材 Download PDF

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Publication number
WO2014003201A1
WO2014003201A1 PCT/JP2013/068305 JP2013068305W WO2014003201A1 WO 2014003201 A1 WO2014003201 A1 WO 2014003201A1 JP 2013068305 W JP2013068305 W JP 2013068305W WO 2014003201 A1 WO2014003201 A1 WO 2014003201A1
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WO
WIPO (PCT)
Prior art keywords
heat shielding
shielding material
magnesium hydroxide
crystal
aspect ratio
Prior art date
Application number
PCT/JP2013/068305
Other languages
English (en)
French (fr)
Inventor
中村　司
等 真鍋
大輔 工藤
茂男 宮田
Original Assignee
協和化学工業株式会社
株式会社海水化学研究所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 協和化学工業株式会社, 株式会社海水化学研究所 filed Critical 協和化学工業株式会社
Priority to US14/408,710 priority Critical patent/US20150177430A1/en
Priority to CN201380034111.8A priority patent/CN104411897A/zh
Priority to MX2014015875A priority patent/MX2014015875A/es
Priority to CA2881314A priority patent/CA2881314A1/en
Priority to KR20147033781A priority patent/KR20150024823A/ko
Priority to EP13809005.5A priority patent/EP2868825A4/en
Priority to JP2014522720A priority patent/JPWO2014003201A1/ja
Priority to RU2015102757A priority patent/RU2015102757A/ru
Publication of WO2014003201A1 publication Critical patent/WO2014003201A1/ja
Priority to ZA2014/09501A priority patent/ZA201409501B/en

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G9/00—Cultivation in receptacles, forcing-frames or greenhouses; Edging for beds, lawn or the like
    • A01G9/14—Greenhouses
    • A01G9/1438—Covering materials therefor; Materials for protective coverings used for soil and plants, e.g. films, canopies, tunnels or cloches
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78—Heat insulating elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/02—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of crystals, e.g. rock-salt, semi-conductors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B2001/7691—Heat reflecting layers or coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/24—Structural elements or technologies for improving thermal insulation
    • Y02A30/254—Roof garden systems; Roof coverings with high solar reflectance
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/14—Measures for saving energy, e.g. in green houses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]

Definitions

  • the present invention relates to a heat shielding material having excellent infrared reflectivity and excellent transparency to visible light.
  • the method of suppressing the indoor temperature rise by the sunlight in summer by applying a heat-shielding paint on the roof or sticking a resin film containing a heat-shielding material on a window glass is rapidly spreading.
  • a thermal barrier film or sheet is used in order to prevent the temperature from rising more than necessary in the house and to keep crops growing well.
  • the heat shielding material used in such a heat shielding product is a metal flake of aluminum or silver, titanium oxide, zinc oxide, pearl pigment, or the like.
  • heat shielding materials reflect infrared rays that cause the temperature rise, prevent the indoor temperature from rising in summer, and prevent the indoor temperature from dropping in winter.
  • these heat shielding materials have the disadvantages that they are poor in transparency, have a rough molded product surface, and are easily colored. Therefore, when it is pasted on the window, the visibility becomes worse.
  • the growth of plants in agricultural houses may be hindered due to the low visible light transmission required for plants.
  • An object of the present invention is to provide a heat shielding material that is excellent in the reflectivity of infrared rays, which is a cause of temperature rise, and has excellent transparency to visible light.
  • Another object of the present invention is to provide a resin composition and a molded product containing the heat shielding material.
  • the present inventor has found that high aspect ratio plate-like crystalline magnesium hydroxide has excellent infrared reflectivity and excellent transmittance for visible light, and has completed the present invention. That is, the present invention is a heat shielding material comprising, as an active ingredient, plate-like crystalline magnesium hydroxide having a crystal width of 1 ⁇ m or more and a crystal thickness of 0.2 ⁇ m or less.
  • the present invention also relates to a resin composition containing 100 parts by weight of resin and 1 to 50 parts by weight of the heat shielding material. Moreover, this invention is a molded article which shape
  • the heat shielding material of the present invention contains high aspect ratio plate-like crystalline magnesium hydroxide having a large crystal width and a thin crystal thickness as an active ingredient.
  • the high aspect ratio plate-like crystalline magnesium hydroxide has a crystal width of 1 ⁇ m or more, preferably 2 ⁇ m or more, more preferably 3 ⁇ m or more.
  • the crystal thickness is 0.2 ⁇ m or less, preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less.
  • the plate-like crystalline magnesium hydroxide is excellent in orientation in the resin and has high light reflectance. As a result, the infrared rays that cause the temperature rise are well reflected, and the transmittance is lowered.
  • the aspect ratio is defined by the ratio of the width / thickness of the crystal.
  • the thinner the crystal is the better the visible light transmittance and the better the transparency.
  • Conventional magnesium hydroxide crystals have a width of about 1 ⁇ m or less and a thickness of about 0.5 ⁇ m or more. Therefore, the crystal orientation is poor and the thickness is thick, so the transparency is poor and the heat shielding effect is small.
  • the high aspect ratio plate-like crystalline magnesium hydroxide can be used after being surface-treated in order to improve compatibility with the resin and dispersibility.
  • the surface treatment agent a higher fatty acid or an alkali metal salt thereof, a phosphate ester, an anionic surfactant, a coupling agent such as silane, aluminum, or titanate is used.
  • the surface treatment is performed by dissolving 0.1 to 10% by weight of a surface treatment agent in an organic solvent such as water or alcohol with respect to the weight of the high aspect ratio plate-like crystalline magnesium hydroxide, and in a liquid medium such as water. It can be performed by a wet method in which the high aspect ratio plate-like crystalline magnesium hydroxide is added with stirring.
  • the plate-like crystalline magnesium hydroxide can be used by molding into a granule having a diameter of 0.5 to 5 mm, for example. Molding can be performed using conventionally known means such as extrusion granulation and rolling granulation.
  • the high aspect ratio plate-like crystalline magnesium hydroxide is a mixture of microcrystalline magnesium hydroxide and monocarboxylic acid / or a metal salt thereof at 100 ° C. or higher, preferably 150 to 250 ° C. with stirring, preferably 2 to 10 hours. It can be produced by hydrothermal treatment.
  • the monocarboxylic acid is a stage in which magnesium hydroxide is produced by a coprecipitation method in which an alkali such as NaOH in an equivalent amount or more is added to a water-soluble magnesium salt aqueous solution, and the reaction is preferably performed at 0 to 40 ° C.
  • a water-soluble magnesium salt such as magnesium halide, nitrate or monocarboxylate and coprecipitating with an alkali such as sodium hydroxide.
  • the monocarboxylic acid is added in a molar ratio with respect to magnesium hydroxide, preferably 0.01 or more, more preferably 0.1 to 1.0.
  • magnesium chloride, magnesium nitrate, and magnesium acetate can be raised, for example.
  • Preferred examples of the monocarboxylic acid include acetic acid, propionic acid, butanoic acid, glycolic acid, and lactic acid.
  • the resin composition of the present invention contains 100 parts by weight of resin and 1 to 50 parts by weight of the heat shielding material.
  • the resin is preferably at least one resin selected from the group consisting of thermoplastic resins, thermosetting resins and rubbers.
  • polyethylene polyethylene, copolymers of ethylene and ⁇ -olefin, copolymers of ethylene and vinyl acetate, ethyl acrylate or methyl acrylate, polypropylene, copolymers of propylene and other ⁇ -olefins, polybutene- 1, Poly-4-methylpentene-1, polystyrene, copolymer of styrene and acrylonitrile, ethylene and propylene diene rubber or butadiene, polyvinyl acetate, polyvinyl alcohol, polyacrylate, polymethacrylate, polyurethane, polyester, polyether, polyamide , Thermoplastic resins such as ABS, polycarbonate, polyphenylene sulfide, thermosetting resins such as phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, alkyd resin, EPDM, SBR, NBR, Copolymer rubber of ethylene and other ⁇ -olefins such as propylene
  • the resin composition is a thermal barrier paint.
  • the resin contains, for example, phenol resin paint, alkyd resin paint, amino alkyd resin paint, vinyl chloride resin paint, acrylic resin paint, epoxy resin paint, silicon resin paint, polyurethane resin paint, fluororesin paint, oil-based paint, etc. Can be made.
  • the content of the heat shielding material in the resin composition is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight with respect to 100 parts by weight of the resin.
  • the resin composition can be manufactured by a conventionally known kneading means after mixing the resin and the heat shielding material.
  • the resin and the heat shielding material can be manufactured by heating, melting and mixing with a biaxial extruder and then pelletizing.
  • the resin composition can be molded into a film, sheet, thick molded article or the like by a conventional molding machine or means such as extrusion molding, injection molding, vacuum molding, inflation molding, slit molding, etc. it can.
  • molded products include thermal barrier films to be attached to window glass, thermal barrier coatings used on roofs, agricultural thermal barrier films or sheets for adjusting house temperature, and resin molded products for outdoor use. it can.
  • the present invention includes a method of using a high aspect ratio plate-like crystalline magnesium hydroxide having a crystal width of 1 ⁇ m or more and a crystal thickness of 0.2 ⁇ m or less as an infrared heat shielding material.
  • the hydrothermally treated product was taken out, filtered under reduced pressure and washed with water, and then the filter cake was dispersed in water with a stirrer. After heating to about 80 ° C., 40 g of stearic acid (purity 90%) was neutralized with caustic soda, and 1 L of an aqueous solution dissolved by heating was added with stirring to perform surface treatment. Then, the cake obtained by pressure filtration and washing with water was granulated to a diameter of about 2 mm with a twin-screw extruder for granulation, and dried at about 120 ° C. in an oven.
  • This sheet is attached to the window portion of a paper box covered with a heat insulating agent with a 40 mm square window in only one direction, and an infrared lamp (185 W) is irradiated at a distance of 10.5 cm, the temperature in the box and the sheet The temperature of was measured.
  • Table 1 The results are shown in Table 1. As a result, it can be seen that the resin sheet containing the heat shielding material of the present invention has good transparency (because of high visible light transmittance) and suppresses an increase in room temperature.
  • Example 2 (Preparation of magnesium hydroxide) In Example 1, except that 1.6 mol of sodium propionate was used instead of sodium acetate under the production conditions of the high aspect ratio plate-like crystalline magnesium hydroxide, magnesium hydroxide was added in the same manner as in Example 1. Manufactured. This material before the surface treatment was identified as magnesium hydroxide as a result of X-ray diffraction. As a result of SEM measurement, each crystal had a plate-like crystal outer shape close to a hexagon, and had a thickness of 0.05 ⁇ m and a lateral width of 4.5 ⁇ m. Therefore, the aspect ratio is 90. The BET specific surface area was 8.2 m 2 / g.
  • Example 1 Sheet molding A sheet was formed from the obtained granulated material in the same manner as in Example 1, and a heat shielding test was performed. The results are shown in Table 1. Also in Example 2, it turns out that the tendency similar to Example 1 is shown. Comparative Example 1 After surface-treating commercially available magnesium hydroxide (thickness 0.3 ⁇ m, lateral width 0.9 ⁇ m, BET specific surface area 6 m 2 / g, aspect ratio 3) with sodium stearate in the same manner as in Example 1, Table 1 shows the results of the heat shielding test performed in the same manner as in Example 1.
  • Comparative Example 2 A LLDPE sheet was prepared in the same manner as in Example 1 using a pearl pigment-based commercially available heat shielding material in which titanium oxide was formed on the surface of mica having a width of about 15 ⁇ m. The evaluation results are shown in Table 1. As is apparent from Table 1, it can be seen that the commercially available heat shielding material has poor transparency.
  • the heat insulating material of the present invention has excellent infrared reflectivity and excellent visible light transmission.
  • the resin composition and molded product of the present invention have a high-quality appearance with excellent transparency and surface gloss.
  • the heat shielding material of the present invention can be applied to any application for the purpose of heat insulation.
  • heat-shielding films to be attached to glass on windows of houses and automobiles heat-shielding paints used on roofs, etc.
  • heat-shielding films or sheets for agriculture to adjust the temperature in the house resin molded products such as furniture for outdoor use Etc.

Abstract

本発明の目的は、温度上昇の原因である赤外線の反射に優れ、可視光線に対しては透過性に優れた遮熱材を提供することにある。　本発明は、結晶の横幅が１μｍ以上で、且つ結晶の厚さが０．２μｍ以下の高アスペクト比板状結晶水酸化マグネシウムを有効成分とする遮熱材である。

Description

遮熱材
　本発明は、赤外線の反射能に優れ、かつ可視光線に対する透過性に優れた遮熱材に関する。
　エネルギー価格がますます高くなる傾向にあり、省エネルギーは広範の分野で共通の課題となっている。夏における太陽光線による室内温度上昇を、遮熱塗料を屋根に塗布したり、窓ガラスに遮熱材の入った樹脂フィルムを貼ることにより、抑制する方法が急速に広がっている。また、農業分野でも、可視光線は透過するが、ハウス内の必要以上の温度上昇を防いで、作物の育成を良好に保つために、遮熱フィルムとかシートが使用されている。
　このような遮熱製品に使用されている遮熱材は、アルミニウムとか銀の金属薄片、酸化チタン、酸化亜鉛、パール顔料等である。これら遮熱材は、温度上昇の原因である赤外線を反射し、夏は室内の温度上昇を防ぎ、冬は室内温度の低下を防ぐものである。しかしこれらの遮熱材は、透明性が悪く、成形品表面が荒く、着色し易いという欠点がある。したがって、窓に貼ると視界が悪くなる。また農業用ハウス内の植物の生育が、植物にとって必要とされる可視光線の透過が少ないため、阻害されることがある。また透明や無色の塗料が作りにくい等の問題がある。
　本発明の目的は、温度上昇の原因である赤外線の反射能に優れ、可視光線に対しては透過性に優れた遮熱材を提供することにある。また本発明の目的は、該遮熱材を含有する樹脂組成物および成形品を提供することにある。
　本発明者は、高アスペクト比板状結晶水酸化マグネシウムが、赤外線の反射能に優れ、かつ可視光線に対する透過性に優れることを見出し本発明を完成した。
　即ち本発明は、結晶の横幅が１μｍ以上で、且つ結晶の厚さが０．２μｍ以下の板状結晶水酸化マグネシウムを有効成分とする遮熱材である。また本発明は、１００重量部の樹脂および１~５０重量部の前記遮熱材を含有する樹脂組成物である。また本発明は、前記樹脂組成物を成形した成形品である。また本発明は、結晶の横幅が１μｍ以上で、且つ結晶の厚さが０．２μｍ以下の板状結晶水酸化マグネシウムを赤外線の遮熱材として用いる方法である。
＜遮熱材＞
（高アスペクト比板状結晶水酸化マグネシウム）
　本発明の遮熱材は、結晶の横幅が大きく且つ結晶の厚さが薄い高アスペクト比板状結晶水酸化マグネシウムを有効成分とする。高アスペクト比板状結晶水酸化マグネシウムは、結晶の横幅が、１μｍ以上、好ましくは２μｍ以上、より好ましくは３μｍ以上である。また結晶の厚さが、０．２μｍ以下、好ましくは０．１μｍ以下、より好ましくは０．０５μｍ以下である。
　上記板状結晶水酸化マグネシウムは、樹脂中での配向性に優れ、光の反射率が高い。その結果、温度上昇の原因である赤外線を良く反射し、その透過率を低下させる。アスペクト比は、結晶の横幅／厚みの比で定義される。
　高アスペクト比板状結晶水酸化マグネシウムの結晶の横幅が大きいほど、配向性（成型面と結晶の横方向が平行になる）が良くなり、鏡面反射に近づき遮熱効果が向上する。他方、結晶の厚さが薄くなるほど可視光線の透過率が向上し、透明性が良くなる。従来の水酸化マグネシウムの結晶は、横幅が約１μｍ以下で、且つ厚さが約０．５μｍ以上である。そのため、結晶の配向性が貧弱で且つ、厚さが厚いため透明性が悪く遮熱効果は小さい。
　高アスペクト比板状結晶水酸化マグネシウムは、樹脂との相溶性、分散性の向上のために、表面処理して用いることができる。表面処理剤としては、高級脂肪酸またはそのアルカリ金属塩、リン酸エステル、アニオン系界面活性剤、シラン、アルミニウム、チタネート等のカップリング剤等を用いる。表面処理は、高アスペクト比板状結晶水酸化マグネシウムの重量に対し、０．１~１０重量％の表面処理剤を、水若しくはアルコール等の有機溶媒に溶解し、水等の液状媒体中で、攪拌下に高アスペクト比板状結晶水酸化マグネシウムに添加する湿式法で行うことができる。或いは、板状結晶水酸化マグネシウム粉末をヘンシェルミキサーのごとき攪拌機により攪拌下に、前記表面処理剤を添加するいわゆる乾式法で行うこともできる。
　板状結晶水酸化マグネシウムは、その嵩比重を向上させて、樹脂との混練時の加工性をよくするため、例えば直径が０．５~５ｍｍの粒状に成形して用いることもできる。成形は、押出造粒、転動造粒等の従来公知の手段を用いて行うことができる。
（高アスペクト比板状結晶水酸化マグネシウムの製造）
　高アスペクト比板状結晶水酸化マグネシウムは、微結晶水酸化マグネシウムとモノカルボン酸／またはその金属塩の共存下、１００℃以上、好ましくは１５０~２５０℃で攪拌下に好ましくは、２~１０時間水熱処理することにより製造することができる。
　モノカルボン酸は、水溶性マグネシウム塩水溶液に、当量以上のＮａＯＨ等のアルカリを添加し、好ましくは０~４０℃で反応させる共沈法で水酸化マグネシウムを製造する段階で、共沈反応前にマグネシウムのハロゲン化物、硝酸塩、モノカルボン酸塩等の水溶性マグネシウム塩に添加して、水酸化ナトリウム等のアルカリで共沈させた後、水熱処理することもできる。モノカルボン酸は水酸化マグネシウムに対して、モル比で好ましくは０．０１以上、より好ましくは０．１~１．０添加する。
　水溶性マグネシウム塩として好ましくは、例えば塩化マグネシウム、硝酸マグネシウム、酢酸マグネシウムを上げることができる。モノカルボン酸として好ましくは、例えば酢酸、プロピオン酸、ブタン酸、グリコール酸、乳酸を上げることができる。
＜樹脂組成物＞
　また本発明の樹脂組成物は、１００重量部の樹脂および１~５０重量部の前記遮熱材を含有する。
　樹脂として、熱可塑性樹脂、熱硬化性樹脂およびゴムからなる群より選ばれる少なくとも一種の樹脂が好ましい。樹脂として、ポリエチレン、エチレンとα−オレフィンとの共重合体、エチレンと酢酸ビニル、アクリル酸エチルまたはアクリル酸メチルとの共重合体、ポリプロピレン、プロピレンと他のα−オレフィンの共重合体、ポリブテン−１、ポリ４−メチルペンテン−１、ポリスチレン、スチレンとアクリロニトリル、エチレンとプロピレンジエンゴムまたはブタジエンとの共重合体、ポリ酢酸ビニル、ポリビニルアルコール、ポリアクリレート、ポリメタクリレート、ポリウレタン、ポリエステル、ポリエーテル、ポリアミヂ、ＡＢＳ、ポリカーボネート、ポリフェニレンサルファイド等の熱可塑性樹脂、フェノール樹脂、メラミン樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、アルキッド樹脂等の熱硬化性樹脂、ＥＰＤＭ，ＳＢＲ，ＮＢＲ，エチレンと他のα−オレフィン例えばプロピレン、オクテン等との共重合ゴム、ブチルゴム、クロロプレンゴム、イソプレンゴム、クロロスルフォン化ゴム、シリコンゴム、フッ素ゴム、塩素化ブチルゴム、臭素化ブチルゴム、エピクロルヒドリンゴム、塩素化ポリエチレンゴム等が例示される。
　樹脂組成物として遮熱塗料が挙げられる。その場合、樹脂として、例えばフェーノル樹脂塗料、アルキド樹脂塗料、アミノアルキド樹脂塗料、塩化ビニル樹脂塗料、アクリル樹脂塗料、エポキシ樹脂塗料、ケイ素樹脂塗料、ポリウレタン樹脂塗料、フッ素樹脂塗料、油性塗料等を含有させることができる。
　遮熱材の樹脂組成物中の含有量は、１００重量部の樹脂に対し、０．１~１００重量部、好ましくは１~５０重量部である。
　樹脂組成物は、樹脂と前記遮熱材を混合後、従来公知の混練手段で製造することができる。例えば樹脂と遮熱材とを、２軸押し出し機で加熱溶融混合した後、ペレット化して製造することができる。
＜成形品＞
　樹脂組成物を、押出成形、射出成形、真空成形、インフレーシヨン成形、スリット成形等の慣用の成形機、手段により、フィルム、シート、肉厚成形品等に成形して成形品を得ることができる。成形品として、窓のガラスに貼りつける遮熱フィルム、屋根等に使用する遮熱塗料、ハウス内温度を調節するための農業用遮熱フィルム若しくはシート、屋外使用の樹脂成形品等を挙げることができる。
＜遮熱材として用いる方法＞
　本発明は、結晶の横幅が１μｍ以上で、且つ結晶の厚さが０．２μｍ以下の高アスペクト比板状結晶水酸化マグネシウムを赤外線の遮熱材として用いる方法を包含する。
　以下、実施例により本発明を説明するが、本発明はこれらの実施例のみに限定されるものではない。
実施例１
（水酸化マグネシウムの調製）
　試薬１級の塩化マグネシウムと酢酸ソーダの混合水溶液（Ｍｇ＝２モル／Ｌ、酢酸ソーダ＝１．２モル／Ｌ、３０℃）２０Ｌに攪拌下、８モル／Ｌの試薬１級の水酸化ナトリウム水溶液（３０℃）８Ｌを加え共沈反応させた。この反応物を容量５０Ｌのオートクレーブに入れ、１７０℃で８時間水熱処理をした。水熱処理物を取り出し、減圧濾過、水洗後、ろ過ケーキを、攪拌機で水に分散させた。約８０℃に加熱後、４０ｇのステアリン酸（純度９０％）をカセイソーダで中和し、加熱溶解した水溶液１Ｌを攪拌下に加え表面処理した。その後、圧濾過、水洗して得られたケーキを、造粒用２軸押し出し機で直径約２ｍｍに造粒し、オーブンで約１２０℃で乾燥した。
　表面処理前の試料を一部採取し、Ｘ線回折、ＳＥＭ、および液体窒素吸着法によるＢＥＴ比表面積の測定を行った。
　Ｘ線回折の結果、水酸化マグネシウムと同定された。ＳＥＭ測定の結果、個々の結晶は六角形に近い板状の結晶外形で、厚みは０．０７μｍ、横幅は３．２μｍであった。したがってアスペクト比は５０である。ＢＥＴ比表面積は１２ｍ２／ｇであった。
（シートの成形）
　ＬＬＤＰＥ（直鎖低密度ポリエチレン）１００重量部に対し、造粒物を１０重量部、酸化防止剤（イルガノックス１０１０）を０．１重量部混合後、ブラベンダーを用いて溶融混練した。混練物をプレス成形機を用い、厚さ１ｍｍ、タテ１３４ｍｍ、ヨコ９９ｍｍのシートに成形した。このシートについて、分光光度計を用いて、可視光線（３８０~７８０ｎｍ）透過率と近赤外線（７８０~２５００ｎｍ）反射率を測定した。その結果を表１に示す。
　このシートを１方向だけに４０ｍｍ四方の窓がある断熱剤で覆われた紙製箱の、窓部分に装着し、赤外線ランプ（１８５Ｗ）を１０．５ｃｍ離して照射し、箱内の温度およびシートの温度を測定した。その結果を表１に示す。その結果、本発明遮熱材を配合した樹脂シートが、透明性が良く（可視光線透過率が高いため）、且つ室内温度上昇が抑えられていることが分かる。
実施例２
（水酸化マグネシウムの調製）
　実施例１において、高アスペクト比板状結晶水酸化マグネシウムの製造条件において、酢酸ソーダの代わりに、プロピオン酸ソーダを１．６モル使用する以外は、実施例１と同様におこない、水酸化マグネシウムを製造した。表面処理前のこの物質は、Ｘ線回折の結果、水酸化マグネシウムと同定された。ＳＥＭ測定の結果、個々の結晶は六角形に近い板状結晶外形で、厚みは０．０５μｍ、横幅は４．５μｍであった。したがって、アスペクト比は９０である。ＢＥＴ比表面積は８．２ｍ２／ｇであった。
（シートの成形）
　得られた造粒物を実施例１と同様にして、シートを成形して遮熱試験を行った。結果を表１に示す。実施例２においても、実施例１と同様な傾向を示していることが分かる。
比較例１
　市販の水酸化マグネシウム（厚さが０．３μｍ、横幅が０．９μｍ、ＢＥＴ比表面積が６ｍ２／ｇ、アスペクト比が３）を実施例１と同様にしてステアリン酸ソーダで表面処理した後、実施例１と同様にして、遮熱試験を行った結果を表１に示す。表１から明らかなように、市販の水酸化マグネシウムでは、透明性が悪く、近赤外線の反射率、遮熱性が本発明の遮熱材より劣ることが分かる。
比較例２
　横幅約１５μｍの雲母の表面に酸化チタンを形成させたパール顔料系市販遮熱材を用い、実施例１と同様にしてＬＬＤＰＥのシートを作成した。その評価結果を表１に示す。表１から明らかなように、市販の遮熱材は透明性が悪いことが分かる。
Figure JPOXMLDOC01-appb-T000001
発明の効果
　本発明の遮熱材は、赤外線の反射能に優れ、可視光線の透過性に優れる。また本発明の樹脂組成物および成形品は、透明性に優れ、表面の光沢に優れた高級感のある外観を有する。
　本発明の遮熱材は、遮熱を目的とする如何なる用途にも適用できる。例えば、家とか自動車等の窓のガラスに貼りつける遮熱フィルム、屋根等に使用する遮熱塗料、ハウス内温度を調節するための農業用遮熱フィルム若しくはシート、屋外使用の家具等樹脂成形品等を挙げることができる。

Claims (8)

  1. 　結晶の横幅が１μｍ以上で、且つ結晶の厚さが０．２μｍ以下の高アスペクト比板状結晶水酸化マグネシウムを有効成分とする遮熱材。
  2. 　高アスペクト比板状結晶水酸化マグネシウムの横幅が２μｍ以上で、且つ厚さが０．１μｍ以下である請求項１記載の遮熱材。
  3. 　高アスペクト比板状結晶水酸化マグネシウムの横幅が３μｍ以上で、且つ厚さが０．１μｍ以下である、請求項１記載の遮熱材。
  4. 　高アスペクト比板状結晶水酸化マグネシウムの横幅が３μｍ以上で、且つ厚さが０．０５μｍ以下である請求項１記載の遮熱材。
  5. 　１００重量部の樹脂および１~５０重量部の請求項１に記載の遮熱材を含有する樹脂組成物。
  6. 　請求項１に記載の樹脂組成物を成形した成形品。
  7. 　フィルムである請求項６に記載の成形品。
  8. 　結晶の横幅が１μｍ以上で、且つ結晶の厚さが０．２μｍ以下の高アスペクト比板状結晶水酸化マグネシウムを赤外線の遮熱材として用いる方法。
PCT/JP2013/068305 2012-06-29 2013-06-27 遮熱材 WO2014003201A1 (ja)

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