JPWO2011096392A1 - Film forming method and film forming body - Google Patents
Film forming method and film forming body Download PDFInfo
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- JPWO2011096392A1 JPWO2011096392A1 JP2011552782A JP2011552782A JPWO2011096392A1 JP WO2011096392 A1 JPWO2011096392 A1 JP WO2011096392A1 JP 2011552782 A JP2011552782 A JP 2011552782A JP 2011552782 A JP2011552782 A JP 2011552782A JP WO2011096392 A1 JPWO2011096392 A1 JP WO2011096392A1
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- 229920002647 polyamide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D3/00—Roof covering by making use of flat or curved slabs or stiff sheets
- E04D3/35—Roofing slabs or stiff sheets comprising two or more layers, e.g. for insulation
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
- E04D13/00—Special arrangements or devices in connection with roof coverings; Protection against birds; Roof drainage ; Sky-lights
- E04D13/008—Provisions for reducing rain noise
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04G—SCAFFOLDING; FORMS; SHUTTERING; BUILDING IMPLEMENTS OR AIDS, OR THEIR USE; HANDLING BUILDING MATERIALS ON THE SITE; REPAIRING, BREAKING-UP OR OTHER WORK ON EXISTING BUILDINGS
- E04G23/00—Working measures on existing buildings
- E04G23/02—Repairing, e.g. filling cracks; Restoring; Altering; Enlarging
- E04G23/0281—Repairing or restoring roofing or roof covering
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Roof Covering Using Slabs Or Stiff Sheets (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
- Working Measures On Existing Buildindgs (AREA)
Abstract
金属屋根が設けられた既存建築物において、簡便かつ効果的に雨音を低減することができ、さらに太陽光直射による温度上昇を抑制することができる方法を提供する。既存建築物における金属屋根の屋外側表面に対し、ウレタンプレポリマーに由来する樹脂マトリクス１００重量部に、無機質粉粒体３０〜３００重量部が分散してなる、厚み５０〜１０００μｍの中塗層を形成し、当該中塗層の上には、赤外線反射性粉体及び／または赤外線透過性粉体を含み、形成被膜の水に対する接触角が７０°以下となる上塗層を形成する。Provided is a method capable of reducing rain noise easily and effectively in an existing building provided with a metal roof, and further suppressing an increase in temperature due to direct sunlight. An intermediate coating layer having a thickness of 50 to 1000 μm, in which 30 to 300 parts by weight of inorganic powder particles are dispersed in 100 parts by weight of a resin matrix derived from a urethane prepolymer with respect to the outdoor side surface of a metal roof in an existing building. On the intermediate coating layer, an overcoat layer containing an infrared reflecting powder and / or an infrared transmitting powder and having a contact angle with respect to water of the formed coating of 70 ° or less is formed.
Description
本発明は、既存建築物の金属屋根における被膜形成方法に関するものである。 The present invention relates to a method for forming a coating on a metal roof of an existing building.
従来、住宅、工場、倉庫等の建築物における屋根材としては、粘土瓦、セメント瓦、スレート瓦、アスファルトシングル、金属板等の各種材料が用いられている。このうち、粘土瓦等の瓦材は古くから用いられている材料であるが、一枚当りの重量が大きく、建築物への負荷が大きくなってしまうこととなり、耐震面等の点ではやや不利である。 Conventionally, various materials such as clay tiles, cement tiles, slate tiles, asphalt singles, metal plates, and the like are used as roofing materials in buildings such as houses, factories, and warehouses. Of these, tiles such as clay tiles are materials that have been used for a long time, but the weight per piece is large and the load on the building becomes large, which is somewhat disadvantageous in terms of seismic surfaces. It is.
これに対し、金属板からなる屋根材は、瓦材等よりも比較的軽量であり、近年、各種建築物において多く採用されている状況である。このような金属屋根としては、鋼板の表面に塗装を施したものが汎用的に用いられている。しかし、このような金属屋根を用いた建築物では、降雨時の雨音が大きくなりやすく、住環境等の観点からすればあまり好ましいものではない。 On the other hand, the roof material made of a metal plate is relatively lighter than the tile material or the like, and has been widely used in various buildings in recent years. As such a metal roof, what coated the surface of the steel plate is used universally. However, in a building using such a metal roof, the sound of rain during the rain tends to be large, which is not preferable from the viewpoint of the living environment.
金属屋根における雨音を低減する手法として、例えば特開２０００−６４５１２号公報（特許文献１）には、金属屋根の裏面（屋内側）に、合成樹脂発泡体、ゴム発泡体等からなる断熱材を設ける手法が記載されている。また、特開２００５−９２０５号公報（特許文献２）には、金属製の屋根葺材と制振性接着剤層と下地材とからなる金属屋根構造において、損失係数が特定値となる制振性接着剤を用いることによって、雨音を低減する手法が記載されている。 As a technique for reducing rain noise on a metal roof, for example, Japanese Patent Laid-Open No. 2000-64512 (Patent Document 1) discloses a heat insulating material made of synthetic resin foam, rubber foam, or the like on the back surface (indoor side) of the metal roof. A method of providing the above is described. Japanese Patent Laying-Open No. 2005-9205 (Patent Document 2) discloses a damping property in which a loss factor is a specific value in a metal roof structure made of a metal roof covering material, a damping adhesive layer, and a base material. A technique for reducing rain noise by using an adhesive is described.
しかし、これら特許文献に記載の手法は、いずれも金属屋根の屋内側の構造に関するものであり、既存建築物においてこれらの手法を採用しようとすると、屋根裏構造の改変等が必要となり、工事が大掛かりとなるおそれがある。 However, all of the methods described in these patent documents relate to the indoor structure of a metal roof. If these methods are to be adopted in an existing building, it is necessary to modify the attic structure, etc. There is a risk of becoming.
これに対し、特開２００３−２３８８９７号公報（特許文献３）には、塗膜硬さが柔らかい塗料を塗布した後、塗膜硬さが硬い塗料を積層塗布してなる防音塗装工法が記載されている。このような特許文献３の工法は、金属屋根の屋外側に適用するものであり、金属屋根の改装を兼ねて実施することも可能である。 On the other hand, Japanese Patent Application Laid-Open No. 2003-238897 (Patent Document 3) describes a soundproof coating method in which a paint having a soft coating film hardness is applied and then a paint having a hard coating film hardness is applied by lamination. ing. Such a construction method of Patent Document 3 is applied to the outdoor side of a metal roof, and can also be carried out in combination with renovation of the metal roof.
しかしながら、上記特許文献３のように、単に塗膜硬さの柔らかい塗料と硬い塗料を積層するだけでは、雨音低減等の点において十分な性能が得られない場合がある。 However, as in Patent Document 3, sufficient performance may not be obtained in terms of rain noise reduction or the like simply by laminating a paint with a soft coating film hardness and a hard paint.
一方、近年、環境保護、省エネルギー等の観点から、建築物内で使用する冷房について、その電力消費を抑えようとする動きがある。このような動きに対応するため、屋根材において太陽光による温度上昇を抑える技術が提案されている。例えば、特開２００４−１０９０３号公報（特許文献４）には、セラミック中空粒子を高比率で含む塗料を屋根材に対して塗装することが記載されている。 On the other hand, in recent years, from the viewpoints of environmental protection, energy saving, etc., there is a movement to reduce the power consumption of cooling used in buildings. In order to cope with such a movement, a technique for suppressing a temperature rise due to sunlight in a roofing material has been proposed. For example, Japanese Unexamined Patent Application Publication No. 2004-10903 (Patent Document 4) describes that a roof material is coated with a paint containing ceramic hollow particles at a high ratio.
ところが、上記特許文献４のような塗料を屋根材に適用しても、十分な雨音低減効果はあまり期待できない。 However, even if the paint as in Patent Document 4 is applied to the roofing material, a sufficient rain noise reduction effect cannot be expected.
本発明は、上述のような問題点に鑑みなされたもので、金属屋根が設けられた既存建築物において、簡便かつ効果的に雨音を低減することができ、さらに太陽光直射による温度上昇を抑制することができる方法を得ることである。 The present invention has been made in view of the above problems, and in existing buildings provided with a metal roof, it is possible to easily and effectively reduce rain noise, and to increase the temperature due to direct sunlight. It is to obtain a method that can be suppressed.
このような課題を解決するため、本発明者は鋭意検討の結果、既存建築物の金属屋根の屋外側表面に対し、特定の中塗層と上塗層による被膜を形成すれば、降雨時の雨滴が金属屋根に接したときの騒音レベルを低く抑えることができ、さらに太陽光直射時の温度上昇を抑制することができることを見出し、本発明を完成するに到った。 In order to solve such problems, the present inventor, as a result of earnest study, on the outdoor side surface of the metal roof of the existing building, if a coating with a specific intermediate coating layer and overcoating layer is formed, it is It has been found that the noise level when raindrops come into contact with a metal roof can be kept low, and that the temperature rise during direct sunlight can be suppressed, and the present invention has been completed.
すなわち、本発明は以下の方法に関するものである。
１．既存建築物における金属屋根の屋外側表面に対し、ウレタンプレポリマーに由来する樹脂マトリクス１００重量部に、無機質粉粒体３０〜３００重量部が分散してなる、厚み５０〜１０００μｍの中塗層を形成し、当該中塗層の上には、赤外線反射性粉体及び／または赤外線透過性粉体を含み、形成被膜の水に対する接触角が７０°以下となる上塗層を形成することを特徴とする被膜形成方法。
２．上記１．記載の被膜形成方法により得られる被膜形成体。That is, the present invention relates to the following method.
1. An intermediate coating layer having a thickness of 50 to 1000 μm, in which 30 to 300 parts by weight of inorganic powder particles are dispersed in 100 parts by weight of a resin matrix derived from a urethane prepolymer with respect to the outdoor side surface of a metal roof in an existing building. And forming an overcoat layer on the intermediate coating layer, which includes an infrared reflective powder and / or an infrared transmissive powder and has a contact angle with water of the formed coating of 70 ° or less. A film forming method.
2. Above 1. The film formation body obtained by the film formation method of description.
本発明によれば、金属屋根が設けられた既存建築物において、簡便かつ効果的に雨音を低減することができる。さらに本発明では、太陽光直射による屋根材の温度上昇を抑えることができるため、夏季等における冷房消費を軽減することも可能となる。本発明方法は、金属屋根の改装を兼ねることもでき、建築物の美観性向上にも寄与するものである。 ADVANTAGE OF THE INVENTION According to this invention, rain sound can be reduced simply and effectively in the existing building provided with the metal roof. Furthermore, in this invention, since the temperature rise of the roofing material by direct sunlight can be suppressed, it becomes possible to reduce the cooling consumption in summer etc. The method of the present invention can also serve as a renovation of a metal roof, and contributes to improving the aesthetics of a building.
以下、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
本発明の被膜形成方法は、既存建築物における金属屋根の屋外側表面に対して適用するものである。 The film forming method of the present invention is applied to the outdoor side surface of a metal roof in an existing building.
金属屋根を構成する基材としては、例えば、鋼板、ステンレス板、アルミニウム板、アルミニウム合金板、銅板等の金属板、ガルタイトやガルバリウム等の亜鉛−アルミニウムめっき鋼板、アルミニウムめっき鋼板、亜鉛めっき鋼板等のめっき金属板等が挙げられる。これらは各種塗料等により被覆されたものであってもよい。このような基材の厚みは、通常０．２〜２ｍｍ程度である。 As a base material constituting the metal roof, for example, a steel plate, a stainless steel plate, an aluminum plate, an aluminum alloy plate, a metal plate such as a copper plate, a zinc-aluminum plated steel plate such as galtite or galvalume, an aluminum plated steel plate, a galvanized steel plate, etc. Examples thereof include a plated metal plate. These may be coated with various paints. The thickness of such a substrate is usually about 0.2 to 2 mm.
本発明は、特に、低明度の既存塗膜を有する基材に適用した場合に、有利な効果を得ることができる。このような既存塗膜の明度（Ｌ＊）は、好ましくは８０以下、より好ましくは６０以下である。なお、明度（Ｌ＊）は、ＣＩＥ Ｌ＊ａ＊ｂ＊色空間における値であり、分光光度計により測定されるものである。The present invention can obtain an advantageous effect particularly when applied to a substrate having an existing coating film with low brightness. The lightness (L * ) of such an existing coating film is preferably 80 or less, more preferably 60 or less. The lightness (L * ) is a value in the CIE L * a * b * color space and is measured by a spectrophotometer.
本発明では、上記基材の上に直接中塗層を設けてもよいが、防錆塗料等による下塗層を設けることもできる。本発明では、このような下塗層を設けることにより、長期間にわたって本発明の効果を得ることが可能となる。勿論、本発明において、このような下塗層は、雨音低減効果、温度上昇抑制効果等を阻害するものではない。 In the present invention, an intermediate coating layer may be provided directly on the substrate, but an undercoat layer made of an anticorrosive paint or the like can also be provided. In the present invention, by providing such an undercoat layer, the effects of the present invention can be obtained over a long period of time. Of course, in the present invention, such an undercoat layer does not inhibit the rain noise reduction effect, the temperature rise suppression effect, or the like.
防錆塗料としては、樹脂、防錆顔料等を必須成分とするものが使用できる。このうち、樹脂としては、例えば、塩化ビニル樹脂、エポキシ樹脂、アクリル樹脂、ウレタン樹脂、アクリルシリコン樹脂、アルキド系樹脂等が挙げられる。また、樹脂の形態としては、溶液型、分散型、あるいはこれらの混合物等が使用可能である。 As the anti-corrosion paint, a resin, an anti-corrosion pigment and the like as essential components can be used. Among these, examples of the resin include vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, and alkyd resin. Moreover, as a form of resin, a solution type, a dispersion type, or a mixture thereof can be used.
防錆顔料としては、市販または公知の材料を使用することができる。具体的には、例えば、リン酸亜鉛、リン酸鉄、リン酸アルミニウム等のリン酸系防錆顔料、亜リン酸亜鉛、亜リン酸鉄、亜リン酸アルミニウム等の亜リン酸系防錆顔料、モリブデン酸カルシウム、モリンブデン酸アルミニウム、モリブデン酸バリウム等のモリブデン酸系防錆顔料、酸化バナジウム等のバナジウム系防錆顔料、ストロンチウムクロメート、ジンクロメート、カルシウムクロメート、カリウムクロメート、バリウムクロメート等のクロメート系防錆顔料が挙げられる。防錆顔料は、樹脂固形分１００重量部に対し、通常５〜１５０重量部、好ましくは１０〜１００重量部程度の比率で混合すればよい。 A commercially available or well-known material can be used as an antirust pigment. Specifically, for example, phosphoric acid-based anticorrosive pigments such as zinc phosphate, iron phosphate, and aluminum phosphate, and phosphorous acid-based anticorrosive pigments such as zinc phosphite, iron phosphite, and aluminum phosphite. , Molybdate anticorrosive pigments such as calcium molybdate, aluminum molybdate and barium molybdate, vanadium anticorrosive pigments such as vanadium oxide, chromate anticorrosives such as strontium chromate, zinc chromate, calcium chromate, potassium chromate and barium chromate Examples include rust pigments. The rust preventive pigment may be mixed at a ratio of usually 5 to 150 parts by weight, preferably about 10 to 100 parts by weight with respect to 100 parts by weight of the resin solid content.
下塗層は、上述のような防錆塗料を塗付、乾燥することにより形成することができる。塗装方法としては、スプレー塗り、ローラー塗り、刷毛塗り等を適宜採用すればよい。乾燥は、常温下（０〜４０℃程度）で行えばよい。下塗層の厚みは、通常５〜２００μｍ、好ましくは１０〜１００μｍ程度である。 The undercoat layer can be formed by applying and drying the anticorrosive paint as described above. As a coating method, spray coating, roller coating, brush coating, or the like may be employed as appropriate. What is necessary is just to perform drying under normal temperature (about 0-40 degreeC). The thickness of the undercoat layer is usually about 5 to 200 μm, preferably about 10 to 100 μm.
本発明では、上述の如く必要に応じ下塗層を設けた基材に対し、中塗層を設ける。この中塗層は、ウレタンプレポリマーに由来する樹脂マトリクスに、無機質粉粒体が分散してなる中塗材によって形成されるものである。このような材料を採用することにより、本発明では、中塗層の厚膜化、強度向上等を図ることができ、雨音低減性、温度上昇抑制性、付着性等においても優れた効果を発揮することが可能となる。 In the present invention, an intermediate coating layer is provided on a substrate provided with an undercoat layer as necessary as described above. This intermediate coating layer is formed by an intermediate coating material in which inorganic powder particles are dispersed in a resin matrix derived from a urethane prepolymer. By adopting such a material, in the present invention, it is possible to increase the thickness of the intermediate coating layer, improve the strength, etc., and have excellent effects in rain noise reduction, temperature rise suppression, adhesion, etc. It becomes possible to demonstrate.
中塗材におけるウレタンプレポリマーに由来する樹脂マトリクスは、ウレタンプレポリマーの反応生成物を含む高分子が連続相を形成したものである。本発明では、このような特定の樹脂マトリクスを採用することにより、雨音低減効果等を高めることが可能となる。 The resin matrix derived from the urethane prepolymer in the intermediate coating material is a polymer in which a polymer containing a reaction product of the urethane prepolymer forms a continuous phase. In the present invention, by adopting such a specific resin matrix, it is possible to enhance the rain noise reduction effect and the like.
このうち、ウレタンプレポリマーは、ポリオール化合物と過剰のポリイソシアネート化合物とを反応させることによって得られ、分子末端にイソシアネート基を有するものである。 Among these, the urethane prepolymer is obtained by reacting a polyol compound and an excess polyisocyanate compound, and has an isocyanate group at the molecular end.
ウレタンプレポリマーを構成するポリオール化合物としては、例えば、ポリエーテルポリオール、ポリエステルポリオール等が挙げられる。これらの重量平均分子量は通常３００〜５０００（好ましくは５００〜３０００）である。 Examples of the polyol compound constituting the urethane prepolymer include polyether polyol and polyester polyol. These weight average molecular weights are 300-5000 (preferably 500-3000) normally.
また、ポリイソシアネート化合物としては、一般のポリウレタンの製造に用いられる脂肪族、脂環族または芳香族ポリイソシアネートが挙げられる。具体的には、例えばテトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、１，４−シクロヘキサンジイソシアネート、４，４’−ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、メタキシリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート等が挙げられる。 Moreover, as a polyisocyanate compound, the aliphatic, alicyclic, or aromatic polyisocyanate used for manufacture of a general polyurethane is mentioned. Specifically, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, meta Examples include xylylene diisocyanate and 4,4′-diphenylmethane diisocyanate.
ポリオール化合物とポリイソシアネート化合物との反応比率は、ポリオール化合物中の水酸基に対して、ポリイソシアネート化合物中のイソシアネート基が過剰となる比率に設定すればよく、通常はＮＣＯ／ＯＨが１．２〜２．２程度となるように設定することが望ましい。 What is necessary is just to set the reaction ratio of a polyol compound and a polyisocyanate compound to the ratio by which the isocyanate group in a polyisocyanate compound becomes excess with respect to the hydroxyl group in a polyol compound, and NCO / OH is usually 1.2-2. It is desirable to set to about 2.
中塗材における樹脂マトリクスは、少なくとも上記ウレタンプレポリマーと活性水素含有化合物との反応物を含むものである。このうち、活性水素含有化合物は、上記ウレタンプレポリマーのイソシアネート基と反応可能な化合物である。このような活性水素含有化合物としては、例えば、アミノ基含有化合物、水酸基含有化合物等が使用できる。 The resin matrix in the intermediate coating material contains at least a reaction product of the urethane prepolymer and the active hydrogen-containing compound. Among these, the active hydrogen-containing compound is a compound that can react with the isocyanate group of the urethane prepolymer. Examples of such active hydrogen-containing compounds include amino group-containing compounds and hydroxyl group-containing compounds.
具体的にアミノ基含有化合物としては、例えば、芳香族、脂肪族あるいは複素環式ポリアミン類、及びこれらのエポキシド付加変性物、アミド化変性物、マンニッヒ化変性物等が挙げられる。 Specific examples of the amino group-containing compound include aromatic, aliphatic or heterocyclic polyamines, and epoxide addition-modified products, amidation-modified products, and Mannich-modified products.
水酸基含有化合物としては、ポリエーテルポリオール、ポリエステルポリオール、アクリルポリオール等のポリオール化合物の他、水酸基含有ビニル化合物、水酸基含有エポキシ化合物等が挙げられる。ウレタンプレポリマーと水酸基含有ビニル化合物とを反応させた場合は、残余のビニル基どうしをさらに反応させることができる。ウレタンプレポリマーと水酸基含有エポキシ化合物とを反応させた場合は、さらにアミノ基含有化合物等を加えることにより、残余のエポキシ基を反応させることができる。水酸基含有化合物としては、特にアクリルポリオールが好適である。 Examples of the hydroxyl group-containing compound include a hydroxyl group-containing vinyl compound and a hydroxyl group-containing epoxy compound in addition to polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol. When the urethane prepolymer and the hydroxyl group-containing vinyl compound are reacted, the remaining vinyl groups can be further reacted with each other. When the urethane prepolymer and the hydroxyl group-containing epoxy compound are reacted, the remaining epoxy group can be reacted by further adding an amino group-containing compound or the like. As the hydroxyl group-containing compound, acrylic polyol is particularly suitable.
無機質粉粒体としては、例えば、重質炭酸カルシウム、沈降性炭酸カルシウム、カオリン、タルク、クレー、陶土、チャイナクレー、硫酸バリウム、炭酸バリウム、珪砂、珪石、珪藻土、酸化チタン、酸化亜鉛、酸化アルミニウム等が挙げられ、これらの１種または２種以上を使用することができる。無機質粉粒体の平均粒子径は、好ましくは０．１〜１００μｍ（より好ましくは０．２〜５０μｍ、さらに好ましくは０．３〜２０μｍ）程度である。 Examples of inorganic powders include heavy calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, porcelain clay, china clay, barium sulfate, barium carbonate, quartz sand, quartzite, diatomaceous earth, titanium oxide, zinc oxide, aluminum oxide These can be used, and one or more of these can be used. The average particle diameter of the inorganic granular material is preferably about 0.1 to 100 μm (more preferably 0.2 to 50 μm, still more preferably 0.3 to 20 μm).
中塗層における無機質粉粒体としては、平均粒子径０．５〜１００μｍ（好ましくは１〜５０μｍ、より好ましくは２〜２０μｍ）の無機質粉粒体が、無機質粉粒体の総量に対し、５０重量％以上（より好ましくは７０重量％以上）含まれることが望ましい。無機質粉粒体がこのような構成であれば、厚膜化、雨音低減性、温度上昇抑制性等の点で有利となる。 As an inorganic granular material in the intermediate coating layer, an inorganic granular material having an average particle diameter of 0.5 to 100 μm (preferably 1 to 50 μm, more preferably 2 to 20 μm) is 50 with respect to the total amount of the inorganic granular material. It is desirable that it is contained by weight% or more (more preferably 70 weight% or more). If the inorganic granular material has such a structure, it is advantageous in terms of thickening, rain noise reduction, temperature rise suppression, and the like.
中塗層における無機質粉粒体は、ウレタンプレポリマーに由来する樹脂マトリクス１００重量部に対し、３０〜３００重量部（好ましくは５０〜２５０重量部、より好ましくは８０〜２３０重量部）の比率とする。無機質粉粒体の比率がこのような範囲内であれば、中塗層の厚膜化、強度向上等の点で好適であり、雨音低減性、付着強度等においても十分な効果を得ることが可能となる。 The inorganic granular material in the intermediate coating layer has a ratio of 30 to 300 parts by weight (preferably 50 to 250 parts by weight, more preferably 80 to 230 parts by weight) with respect to 100 parts by weight of the resin matrix derived from the urethane prepolymer. To do. If the ratio of the inorganic powder particles is within such a range, it is suitable in terms of increasing the thickness of the intermediate coating layer, improving the strength, etc., and obtaining sufficient effects in rain noise reduction, adhesion strength, etc. Is possible.
さらに、このような中塗層を用いることにより、温度上昇抑制性の点においても、十分な効果を得ることが可能となる。この温度上昇抑制効果は、中塗層が太陽光を効率良く遮蔽することにより奏されるものと考えられる。その作用機構は明らかではないが、中塗層に比較的高比率で無機質粉粒体が含まれるとともに、中塗層が厚膜化されることで、中塗層において光の屈折作用が複合的かつ十分に発揮されることによるものと推測される。 Furthermore, by using such an intermediate coating layer, it is possible to obtain a sufficient effect in terms of temperature rise suppression. This temperature rise suppressing effect is considered to be achieved when the intermediate coating layer efficiently shields sunlight. The mechanism of action is not clear, but the intermediate coating layer contains inorganic particles at a relatively high ratio, and the intermediate coating layer is thickened, so that the refractive action of light is combined in the intermediate coating layer. And it is presumed to be due to its full performance.
中塗層において、無機粉粒体が少なすぎる場合は、厚膜の被膜が得られ難く、また被膜強度も不十分となるため、雨音低減性、温度上昇抑制性、付着性等に支障をきたすおそれがある。無機質粉粒体が多すぎる場合は、雨音低減性において十分な効果が得られ難くなる。 In the intermediate coating layer, if there are too few inorganic particles, it is difficult to obtain a thick film and the film strength is insufficient, which may hinder rain noise reduction, temperature rise suppression, adhesion, etc. There is a risk of it coming. When there are too many inorganic powder granules, it is difficult to obtain a sufficient effect in rain noise reduction.
このような中塗層は、ウレタンプレポリマー、活性水素含有化合物、及び無機質粉粒体を含む中塗材、あるいは、ウレタンプレポリマーと水酸基含有エポキシ化合物との反応生成物、アミノ基含有化合物、及び無機質粉粒体を含む中塗材等を塗付、乾燥することにより形成することができる。なお、中塗材は、水性タイプや溶剤（有機溶剤）タイプであっても構わない。具体的に、前者の形態の中塗材では、ウレタンプレポリマー及び活性水素化合物を、塗装時に混合し、被膜形成過程において両者を反応させることにより、樹脂マトリクスを形成することができる。この形態の中塗材において、ウレタンプレポリマーと活性水素化合物との固形分重量比は、好ましくは５０／１００〜４００／１００、より好ましくは７０／１００〜２００／１００、さらに好ましくは９０／１００〜１５０／１００である。後者の形態の中塗材では、ウレタンプレポリマーと水酸基含有エポキシ化合物との反応生成物、及びアミノ基含有化合物を、塗装時に混合し、被膜形成過程において両者を反応させることにより、樹脂マトリクスを形成することができる。 Such an intermediate coating layer is an intermediate coating material containing a urethane prepolymer, an active hydrogen-containing compound, and an inorganic powder, or a reaction product of an urethane prepolymer and a hydroxyl group-containing epoxy compound, an amino group-containing compound, and an inorganic material. It can be formed by applying and drying an intermediate coating material containing a powder or the like. The intermediate coating material may be an aqueous type or a solvent (organic solvent) type. Specifically, in the former form of the intermediate coating material, a urethane prepolymer and an active hydrogen compound are mixed at the time of coating, and both are allowed to react in the film formation process, thereby forming a resin matrix. In the intermediate coating material of this form, the solid content weight ratio of the urethane prepolymer and the active hydrogen compound is preferably 50/100 to 400/100, more preferably 70/100 to 200/100, and still more preferably 90/100 to 150/100. In the latter form of the intermediate coating material, a reaction product of a urethane prepolymer and a hydroxyl group-containing epoxy compound and an amino group-containing compound are mixed at the time of coating, and a resin matrix is formed by reacting both in the film formation process. be able to.
中塗材の塗装方法としては、スプレー塗り、ローラー塗り、刷毛塗り等を適宜採用すればよい。乾燥は、常温下で行えばよい。 As a method for applying the intermediate coating material, spray coating, roller coating, brush coating, or the like may be employed as appropriate. Drying may be performed at room temperature.
中塗層の厚みは、通常５０〜１０００μｍ、好ましくは１００〜５００μｍである。中塗層の厚みが５０μｍに満たない場合は、十分な雨音低減効果、温度上昇抑制効果が得られ難くなる。１０００μｍよりも厚みが大きい場合は、中塗層による荷重が大きくなり、建築物に対する重量負荷軽減の点で不利となる。 The thickness of the intermediate coating layer is usually 50 to 1000 μm, preferably 100 to 500 μm. When the thickness of the intermediate coating layer is less than 50 μm, it is difficult to obtain sufficient rain noise reduction effect and temperature rise suppression effect. When the thickness is larger than 1000 μm, the load due to the intermediate coating layer is increased, which is disadvantageous in terms of reducing the weight load on the building.
本発明では、上記中塗層の上に、赤外線反射性粉体及び／または赤外線透過性粉体を含み、形成被膜の水に対する接触角（以下単に「接触角」ともいう。）が７０°以下となる上塗層を設ける。本発明では、上記中塗層と、この上塗層を積層することによって、優れた雨音低減効果、温度上昇抑制効果等を長期にわたり得ることができる。また、上記中塗層と上塗層を積層することにより、金属屋根への雨の侵入を防止したり、金属屋根の音鳴り防止（音鳴り低減）効果（温度上昇を抑制し、金属屋根の膨張伸縮を抑制）を得ることができ、有用である。 In the present invention, an infrared reflective powder and / or an infrared transmissive powder is included on the intermediate coating layer, and the contact angle of the formed film with water (hereinafter also simply referred to as “contact angle”) is 70 ° or less. An overcoat layer is provided. In the present invention, by laminating the intermediate coating layer and the top coating layer, it is possible to obtain an excellent rain noise reduction effect, temperature rise suppression effect, and the like over a long period of time. In addition, by laminating the above-mentioned intermediate coating layer and top coating layer, it prevents rain from entering the metal roof, and prevents the metal roof from sounding (reducing noise) (suppressing the temperature rise, Suppressing expansion and contraction) can be obtained, which is useful.
このうち、雨音低減効果について、その作用機構は明らかではないが、概ね以下のような点が寄与しているものと推測される。すなわち、上塗層の接触角が低いことにより、落下してきた雨滴が屋根に接触した際の跳ね返りが抑制され、さらに中塗材のクッション性等が相乗的に作用することにより、雨音が低減できるものと考えられる。本発明では、上塗層の接触角が低いことにより、降雨時に上塗層表面で水膜が形成され、その水膜によっても雨滴の跳ね返りが抑制されるものと考えられる。 Among these, although the action mechanism is not clear about the rain noise reduction effect, it is presumed that the following points generally contribute. That is, when the contact angle of the topcoat layer is low, the rebound when the raindrops that fall is in contact with the roof is suppressed, and the cushioning property of the intermediate coating material acts synergistically to reduce rain noise. It is considered a thing. In the present invention, since the contact angle of the topcoat layer is low, it is considered that a water film is formed on the surface of the topcoat layer during rain, and the splash of raindrops is also suppressed by the water film.
温度上昇抑制効果については、前述の中塗層の作用に加え、上塗層に赤外線反射性粉体及び／または赤外線透過性粉体が含まれることで、上塗層自体の蓄熱が抑制される作用が効いているものと考えられる。 Regarding the temperature rise suppression effect, in addition to the above-described action of the intermediate coating layer, the thermal conductivity of the upper coating layer itself is suppressed by including an infrared reflective powder and / or an infrared transmissive powder in the upper coating layer. It is considered that the action is effective.
上塗層は、接触角が７０°以下となるものであるが、好ましくは６０°以下、より好ましくは５０°以下となるものである。接触角が７０°を超える場合は、雨音低減性において十分な効果を得ることが困難となる。なお、形成被膜の水に対する接触角は、接触角計にて測定される値である。 The topcoat layer has a contact angle of 70 ° or less, preferably 60 ° or less, more preferably 50 ° or less. When the contact angle exceeds 70 °, it is difficult to obtain a sufficient effect in rain noise reduction. In addition, the contact angle with respect to the water of a formation film is a value measured with a contact angle meter.
このような上塗層は、上記条件を満たす上塗材を塗付、乾燥することにより形成できる。具体的に上塗材としては、結合材、並びに、赤外線反射性粉体及び／または赤外線透過性粉体を含むものが使用できる。上塗材は、このような成分に加え、必要に応じ各種添加剤を含むものであってもよい。 Such an overcoat layer can be formed by applying and drying an overcoat material that satisfies the above conditions. Specifically, as the overcoating material, a binder and a material containing an infrared reflecting powder and / or an infrared transmitting powder can be used. The top coating material may contain various additives as necessary in addition to such components.
上塗材における結合材としては、例えば水酸基、カルボキシル基、アミノ基、アミド基等の親水性基を有する樹脂、ポリアルキレンオキサイド、ポリオキサゾリン、ポリアミド等の親水性セグメントを有する樹脂、あるいは、各種樹脂に親水性付与成分を配合したもの等が挙げられる。上塗材における樹脂としては、例えば、酢酸ビニル樹脂、アルキッド樹脂、塩化ビニル樹脂、アクリル樹脂、ウレタン樹脂、アクリルシリコン樹脂、フッ素樹脂等、あるいはこれらの複合系等を主骨格とするものが使用できる。この中でも、特に、アクリル樹脂、ウレタン樹脂、アクリルシリコン樹脂、及びフッ素樹脂から選ばれる１種以上が好適である。樹脂の形態は、水系、溶剤系の何れであってもよい。 Examples of the binder in the top coating material include resins having hydrophilic groups such as hydroxyl groups, carboxyl groups, amino groups, and amide groups, resins having hydrophilic segments such as polyalkylene oxides, polyoxazolines, and polyamides, or various resins. The thing etc. which mix | blended the hydrophilic property provision component are mentioned. As the resin in the top coating material, for example, a vinyl acetate resin, an alkyd resin, a vinyl chloride resin, an acrylic resin, a urethane resin, an acrylic silicon resin, a fluororesin, or the like or a composite system of these can be used. Among these, at least one selected from acrylic resin, urethane resin, acrylic silicon resin, and fluororesin is particularly preferable. The form of the resin may be either water-based or solvent-based.
親水性付与成分としては、例えば、無機酸化物ゾル、アルコキシシラン化合物等が挙げられる。このうち、無機酸化物ゾルとしては、例えば、酸化アルミニウムゾル、酸化ケイ素ゾル、酸化ジルコニウムゾル、酸化アンチモンゾル等が挙げられるが、特に、無機酸化物ゾルやアルコキシシラン化合物は、温度上昇抑制にとって、有利である。 Examples of the hydrophilicity-imparting component include inorganic oxide sols and alkoxysilane compounds. Among these, examples of the inorganic oxide sol include an aluminum oxide sol, a silicon oxide sol, a zirconium oxide sol, an antimony oxide sol, and the like. It is advantageous.
アルコキシシラン化合物としては、テトラアルコキシシラン、テトラアルコキシシランの縮合物、及びこれらの変性物等が使用できる。アルコキシシラン化合物の平均縮合度は、通常１〜１００、好ましくは４〜２０程度である。 As the alkoxysilane compound, tetraalkoxysilane, a condensate of tetraalkoxysilane, and modified products thereof can be used. The average degree of condensation of the alkoxysilane compound is usually about 1 to 100, preferably about 4 to 20.
本発明において好適な親水性付与成分としては、炭素数が１〜２のアルコキシル基と炭素数が３〜１２のアルコキシル基を含有するテトラアルコキシシラン縮合物が挙げられ、特にその化合物全体のアルコキシル基のうち、５〜５０当量％が炭素数３〜１２のアルコキシル基となるようにしたものが好適である。炭素数３〜１２のアルコキシル基としては、例えば、ｎ−プロポキシ基、ｎ−ブトキシ基、ｎ−ペンチルオキシ基、ｎ−ヘキシルオキシ基、ｎ−オクチルオキシ基、ｎ−ドデシルオキシ基等の直鎖アルコキシル基、イソプロポキシ基、イソブトキシ基、ｔ−ブトキシ基、ｓｅｃ−ブトキシ基、イソペンチルオキシ基、ネオペンチルオキシ基、イソヘキシルオキシ基、３−メチルペンチルオキシ基、１−メチルヘキシルオキシ基、１−エチルペンチルオキシ基、２，３−ジメチルブトキシ基、１，５−ジメチルヘキシルオキシ基、２−エチルヘキシルオキシ基、１−メチルヘプチルオキシ基、ｔ−オクチルオキシ基等の分岐アルコキシル基等が挙げられる。このうち、分岐アルコキシル基が好適である。このような化合物は、例えば、炭素数１〜２のアルコキシル基を有するテトラアルコキシシラン縮合物を、炭素数３〜１２のアルコールでエステル交換反応により変性する方法等により得られる。 Suitable hydrophilicity-imparting components in the present invention include tetraalkoxysilane condensates containing an alkoxyl group having 1 to 2 carbon atoms and an alkoxyl group having 3 to 12 carbon atoms, and in particular the alkoxyl group of the entire compound. Among these, those in which 5 to 50 equivalent% are alkoxy groups having 3 to 12 carbon atoms are preferable. Examples of the alkoxyl group having 3 to 12 carbon atoms include straight chain such as n-propoxy group, n-butoxy group, n-pentyloxy group, n-hexyloxy group, n-octyloxy group, and n-dodecyloxy group. Alkoxyl group, isopropoxy group, isobutoxy group, t-butoxy group, sec-butoxy group, isopentyloxy group, neopentyloxy group, isohexyloxy group, 3-methylpentyloxy group, 1-methylhexyloxy group, 1 -Branched alkoxyl groups such as ethylpentyloxy group, 2,3-dimethylbutoxy group, 1,5-dimethylhexyloxy group, 2-ethylhexyloxy group, 1-methylheptyloxy group, t-octyloxy group, etc. . Of these, a branched alkoxyl group is preferred. Such a compound can be obtained, for example, by a method of modifying a tetraalkoxysilane condensate having an alkoxyl group having 1 to 2 carbon atoms by transesterification with an alcohol having 3 to 12 carbon atoms.
このような親水性付与成分は、上塗材における樹脂固形分１００重量部に対し、通常０．１〜５０重量部（好ましくは０．５〜２０重量部）の比率で混合すればよい。 Such a hydrophilicity imparting component may be mixed at a ratio of usually 0.1 to 50 parts by weight (preferably 0.5 to 20 parts by weight) with respect to 100 parts by weight of the resin solid content in the top coating material.
上塗層における赤外線反射性粉体としては、例えば、アルミニウムフレーク、酸化チタン、硫酸バリウム、酸化亜鉛、炭酸カルシウム、酸化珪素、酸化マグネシウム、酸化ジルコニウム、酸化イットリウム、酸化インジウム、アルミナ、鉄クロム複合酸化物、マンガンビスマス複合酸化物、マンガンイットリウム複合酸化物等が挙げられる。 Examples of the infrared reflective powder in the overcoat layer include aluminum flakes, titanium oxide, barium sulfate, zinc oxide, calcium carbonate, silicon oxide, magnesium oxide, zirconium oxide, yttrium oxide, indium oxide, alumina, and iron chromium composite oxide. Products, manganese bismuth composite oxide, manganese yttrium composite oxide, and the like.
一方、赤外線透過性粉体としては、例えば、ペリレン顔料、アゾ顔料、黄鉛、弁柄、朱、チタニウムレッド、カドミウムレッド、キナクリドンレッド、イソインドリノン、ベンズイミダゾロン、フタロシアニングリーン、フタロシアニンブルー、コバルトブルー、インダスレンブルー、群青、紺青等が挙げられ、これらの１種または２種以上を用いることができる。一般に、赤外線反射性粉体を使用するのみでは、表出可能な色相に限界があるが、これら赤外線透過性粉体を適宜組み合わせることにより、様々な色相の被膜を形成することが可能となる。 On the other hand, examples of the infrared transmitting powder include perylene pigment, azo pigment, chrome lead, dial, vermilion, titanium red, cadmium red, quinacridone red, isoindolinone, benzimidazolone, phthalocyanine green, phthalocyanine blue, and cobalt. Examples thereof include blue, indanthrene blue, ultramarine blue, and bitumen, and one or more of these can be used. Generally, there is a limit to the hue that can be expressed only by using an infrared reflective powder, but it is possible to form coatings of various hues by appropriately combining these infrared transparent powders.
赤外線反射性粉体及び／または赤外線透過性粉体の混合量（両成分の合計量）は、樹脂固形分１００重量部に対し、好ましくは１〜２００重量部、より好ましくは２〜１００重量部である。このような混合量であれば、上塗層を所望の色彩に設定することができ、また中塗層の保護等を図ることもできる。上塗層における粉体としては、上述の赤外線反射性粉体及び／または赤外線透過性粉体のみを含むことが望ましい。 The mixing amount of the infrared reflecting powder and / or the infrared transmitting powder (total amount of both components) is preferably 1 to 200 parts by weight, more preferably 2 to 100 parts by weight with respect to 100 parts by weight of the resin solid content. It is. With such a mixing amount, the top coat layer can be set to a desired color, and the intermediate coat layer can be protected. The powder in the top coat layer preferably contains only the above-described infrared reflective powder and / or infrared transmissive powder.
本発明における上塗層は、上述のような上塗材を塗付、乾燥することにより形成することができる。塗装方法としては、スプレー塗り、ローラー塗り、刷毛塗り等を適宜採用すればよい。乾燥は、常温下で行えばよい。上塗層の厚みは、通常２００μｍ以下、好ましくは１０〜１５０μｍである。 The overcoat layer in the present invention can be formed by applying and drying the above-mentioned overcoat material. As a coating method, spray coating, roller coating, brush coating, or the like may be employed as appropriate. Drying may be performed at room temperature. The thickness of the overcoat layer is usually 200 μm or less, preferably 10 to 150 μm.
本発明では、既存建築物における金属屋根の屋外側表面に、中塗層及び上塗層、または下塗層、中塗層及び上塗層が順に積層され、かつ上塗層は、積層被膜の最表面に設けられる。本発明の効果を著しく阻害しない範囲であれば、必要に応じ、中塗層と上塗層の間等に中間的な層を設けることもできる。 In the present invention, an intermediate coat layer and an overcoat layer, or an undercoat layer, an intermediate coat layer and an overcoat layer are sequentially laminated on the outdoor side surface of a metal roof in an existing building, and the overcoat layer is formed of a laminated film. Provided on the outermost surface. As long as the effect of the present invention is not significantly impaired, an intermediate layer may be provided between the intermediate coating layer and the top coating layer as necessary.
以下に実施例及び比較例を示し、本発明の特徴をより明確にする。 Examples and Comparative Examples are shown below to clarify the features of the present invention.
（中塗材の製造）
・中塗材１
ウレタン変性エポキシ樹脂（イソシアネート末端ウレタンプレポリマー（ポリエーテルポリオール（重量平均分子量１０００）と２，４−トリレンジイソシアネートとの反応生成物）のグリシドール付加物、不揮発分７０重量％）１３０重量部に対し、重質炭酸カルシウムＡ（平均粒子径３μｍ）１２０重量部、炭化水素系溶剤２４重量部、シリコーン系消泡剤１重量部、変性ポリアミン（固形分１００重量％）９量部を均一に混合することにより、中塗材１を製造した。(Manufacture of intermediate coating materials)
・ Inner coating material 1
For 130 parts by weight of urethane-modified epoxy resin (isocyanate-terminated urethane prepolymer (glycidol addition product of polyether polyol (weight average molecular weight 1000) and 2,4-tolylene diisocyanate) and non-volatile content 70% by weight)) , 120 parts by weight of heavy calcium carbonate A (average particle size 3 μm), 24 parts by weight of a hydrocarbon solvent, 1 part by weight of a silicone-based antifoaming agent, and 9 parts by weight of a modified polyamine (solid content 100% by weight) are mixed uniformly. Thus, the intermediate coating material 1 was produced.
・中塗材２
可溶形アクリルポリオールＡ（水酸基価５０ＫＯＨｍｇ／ｇ、ガラス転移温度３４℃、固形分４６重量％）１０４重量部に対し、重質炭酸カルシウムＡ（平均粒子径３μｍ）１１０重量部、炭化水素系溶剤１０重量部、シリコーン系消泡剤１重量部、イソシアネート末端ウレタンプレポリマーＡ（ポリエーテルポリオール（重量平均分子量２０００）と２，４−トリレンジイソシアネートとの反応生成物、不揮発分１００重量％、ＮＣＯ含有量３重量％）５２重量部を均一に混合することにより、中塗材２を製造した。・ Intercoat material 2
Soluble acrylic polyol A (hydroxyl value 50 KOH mg / g, glass transition temperature 34 ° C., solid content 46 wt%) 104 parts by weight heavy calcium carbonate A (average particle size 3 μm) 110 parts by weight, hydrocarbon solvent 10 parts by weight, 1 part by weight of silicone-based antifoaming agent, isocyanate-terminated urethane prepolymer A (reaction product of polyether polyol (weight average molecular weight 2000) and 2,4-tolylene diisocyanate, nonvolatile content 100% by weight, NCO The intermediate coating material 2 was produced by uniformly mixing 52 parts by weight) (content 3% by weight).
・中塗材３
可溶形アクリルポリオールＡ１０４重量部に対し、重質炭酸カルシウムＡ２２５重量部、炭化水素系溶剤２５重量部、シリコーン系消泡剤１重量部、イソシアネート末端ウレタンプレポリマーＡ５２重量部を均一に混合することにより、中塗材３を製造した。・ Inner coating material 3
To 225 parts by weight of heavy calcium carbonate A, 25 parts by weight of a hydrocarbon solvent, 1 part by weight of a silicone-based antifoaming agent, and 52 parts by weight of an isocyanate-terminated urethane prepolymer A are uniformly mixed with 104 parts by weight of a soluble acrylic polyol A. Thus, an intermediate coating material 3 was produced.
・中塗材４
可溶形アクリルポリオールＡ１０４重量部に対し、重質炭酸カルシウムＡ９５重量部、酸化チタンＡ（平均粒子径０．３μｍ）２５重量部、炭化水素系溶剤１０重量部、シリコーン系消泡剤１重量部、イソシアネート末端ウレタンプレポリマーＡ５２重量部を均一に混合することにより、中塗材４を製造した。・ Intercoat material 4
95 parts by weight of heavy calcium carbonate A, 25 parts by weight of titanium oxide A (average particle size 0.3 μm), 10 parts by weight of hydrocarbon solvent, 1 part by weight of silicone-based antifoaming agent, based on 104 parts by weight of soluble acrylic polyol A The intermediate coating material 4 was produced by uniformly mixing 52 parts by weight of the isocyanate-terminated urethane prepolymer A.
・中塗材５
可溶形アクリルポリオールＡ１０４重量部に対し、重質炭酸カルシウムＡ３５０重量部、炭化水素系溶剤４０重量部、シリコーン系消泡剤１重量部、イソシアネート末端ウレタンプレポリマーＡ５２重量部を均一に混合することにより、中塗材５を製造した。・ Intercoat material 5
To 104 parts by weight of soluble acrylic polyol A, 350 parts by weight of heavy calcium carbonate, 40 parts by weight of hydrocarbon solvent, 1 part by weight of silicone-based antifoaming agent, and 52 parts by weight of isocyanate-terminated urethane prepolymer A Thus, an intermediate coating material 5 was produced.
・中塗材６
可溶形アクリルポリオールＡ１０４重量部に対し、重質炭酸カルシウムＡ１５重量部、炭化水素系溶剤２重量部、シリコーン系消泡剤１重量部、イソシアネート末端ウレタンプレポリマーＡ５２重量部を均一に混合することにより、中塗材６を製造した。・ Intercoat material 6
To 104 parts by weight of soluble acrylic polyol A, 15 parts by weight of heavy calcium carbonate, 2 parts by weight of hydrocarbon solvent, 1 part by weight of silicone-based antifoaming agent, and 52 parts by weight of isocyanate-terminated urethane prepolymer A Thus, an intermediate coating material 6 was produced.
・中塗材７
ダイマー酸変性エポキシ樹脂（固形分７０重量％）５５重量部に対し、重質炭酸カルシウムＡ１２０重量部、炭化水素系溶剤１５重量部、シリコーン系消泡剤１重量部、変性ポリアミン（固形分１００重量％）４５量部を均一に混合することにより、中塗材７を製造した。・ Inner coating material 7
Dimer acid-modified epoxy resin (solid content 70% by weight) 55 parts by weight, heavy calcium carbonate A 120 parts by weight, hydrocarbon solvent 15 parts by weight, silicone-based antifoaming agent 1 part by weight, modified polyamine (solid content 100% by weight) %) The intermediate coating material 7 was produced by uniformly mixing 45 parts by weight.
・中塗材８
可溶形ポリエーテルポリオール（水酸基価５０ＫＯＨｍｇ／ｇ、固形分５０重量％）９６重量部に対し、重質炭酸カルシウムＡ（平均粒子径３μｍ）１１０重量部、炭化水素系溶剤１０重量部、シリコーン系消泡剤１重量部、イソシアネート末端ウレタンプレポリマーＡ（ポリエーテルポリオール（重量平均分子量２０００）と２，４−トリレンジイソシアネートとの反応生成物、不揮発分１００重量％、ＮＣＯ含有量３重量％）５２重量部を均一に混合することにより、中塗材８を製造した。・ Inner coating material 8
110 parts by weight of heavy calcium carbonate A (average particle size 3 μm), 10 parts by weight of hydrocarbon solvent, silicone based on 96 parts by weight of soluble polyether polyol (hydroxyl value 50 KOH mg / g, solid content 50% by weight) 1 part by weight of antifoaming agent, isocyanate-terminated urethane prepolymer A (reaction product of polyether polyol (weight average molecular weight 2000) and 2,4-tolylene diisocyanate, nonvolatile content 100% by weight, NCO content 3% by weight) The intermediate coating material 8 was manufactured by uniformly mixing 52 parts by weight.
（上塗材の製造）
・上塗材１
非水分散形アクリルポリオールＡ（水酸基価５０ＫＯＨｍｇ／ｇ、ガラス転移温度３８℃、固形分５０重量％）１８８重量部に対し、フタロシアニングリーン７重量部、フタロシアニンブルー３重量部、ペリレンレッド５重量部、ベンズイミダゾロンイエロー４重量部、炭化水素系溶剤２３重量部、シリコーン系消泡剤１重量部、イソシアヌレート構造含有ポリイソシアネートＡ（不揮発分１００重量％、ＮＣＯ含有量２１重量％）６重量部、下記親水性付与成分３重量部を均一に混合することにより、上塗材１を製造した。(Manufacture of top coating materials)
・ Coating material 1
Non-water-dispersed acrylic polyol A (hydroxyl value 50 KOH mg / g, glass transition temperature 38 ° C., solid content 50 wt%) 188 parts by weight, phthalocyanine green 7 parts by weight, phthalocyanine blue 3 parts by weight, perylene red 5 parts by weight, Benzimidazolone yellow 4 parts by weight, hydrocarbon solvent 23 parts by weight, silicone-based antifoaming agent 1 part by weight, isocyanurate structure-containing polyisocyanate A (non-volatile content 100% by weight, NCO content 21% by weight) 6 parts by weight, The top coating material 1 was manufactured by uniformly mixing 3 parts by weight of the following hydrophilicity-imparting component.
・親水性付与成分
メチルシリケート縮合物（重量平均分子量１０００、平均縮合度８、不揮発分１００％）１００重量部に対して、イソブチルアルコール５２重量部と、触媒としてジブチルスズジラウレート０．０３重量部を添加し、混合後、７５℃で８時間脱メタノール反応を行い、親水性付与成分を製造した。この親水性付与成分におけるメチル基とイソブチル基との当量比率は６２：３８であった。・ Hydrophilicity imparting component 52 parts by weight of isobutyl alcohol and 0.03 part by weight of dibutyltin dilaurate as a catalyst are added to 100 parts by weight of methyl silicate condensate (weight average molecular weight 1000, average condensation degree 8, non-volatile content 100%). Then, after mixing, a demethanol reaction was performed at 75 ° C. for 8 hours to produce a hydrophilicity-imparting component. The equivalent ratio of methyl group to isobutyl group in the hydrophilicity imparting component was 62:38.
・接触角測定
１５０ｍｍ×７０ｍｍ×１ｍｍのアルミニウム板に対し、上塗材１を乾燥膜厚が４０μｍとなるようにスプレー塗装し、標準状態（温度２３℃、相対湿度５０％）で７日間乾燥後、屋外にて１ヶ月間放置した。以上の方法で得られた試験板について、協和界面科学株式会社製ＣＡ−Ａ型接触角測定装置を用いて接触角を測定した。その結果、上塗材１の接触角は３５°であった。-Contact angle measurement On an aluminum plate of 150 mm x 70 mm x 1 mm, the top coating material 1 is spray-coated so that the dry film thickness is 40 μm, and dried for 7 days in a standard state (temperature 23 ° C., relative humidity 50%). I left it outdoors for a month. About the test plate obtained by the above method, the contact angle was measured using the CA-A type contact angle measuring apparatus by Kyowa Interface Science Co., Ltd. As a result, the contact angle of the top coating material 1 was 35 °.
・上塗材２
非水分散形アクリルポリオールＡ１８８重量部に対し、フタロシアニングリーン１８重量部、炭化水素系溶剤２３重量部、シリコーン系消泡剤１重量部、イソシアヌレート構造含有ポリイソシアネートＡ６重量部、親水性付与成分３重量部を均一に混合することにより、上塗材２を製造した。
上塗材２について、上記上塗材１と同様の方法で接触角を測定したところ、上塗材２の接触角は３７°であった。・ Coating material 2
18 parts by weight of phthalocyanine green, 23 parts by weight of hydrocarbon-based solvent, 1 part by weight of silicone-based antifoaming agent, 6 parts by weight of isocyanurate structure-containing polyisocyanate A, and hydrophilicity imparting component 3 for 188 parts by weight of non-aqueous dispersion type acrylic polyol A The top coat material 2 was produced by mixing the parts by weight uniformly.
When the contact angle of the topcoat material 2 was measured by the same method as that for the topcoat material 1, the contact angle of the topcoat material 2 was 37 °.
・上塗材３
非水分散形アクリルポリオールＡ１８８重量部に対し、フタロシアニンブルー１８重量部、炭化水素系溶剤２３重量部、シリコーン系消泡剤１重量部、イソシアヌレート構造含有ポリイソシアネートＡ６重量部、親水性付与成分３重量部を均一に混合することにより、上塗材３を製造した。
上塗材３について、上記上塗材１と同様の方法で接触角を測定したところ、上塗材３の接触角は３６°であった。・ Coating material 3
18 parts by weight of phthalocyanine blue, 23 parts by weight of hydrocarbon solvent, 1 part by weight of silicone-based antifoaming agent, 6 parts by weight of isocyanurate structure-containing polyisocyanate A, and hydrophilicity imparting component 3 for 188 parts by weight of non-aqueous dispersion type acrylic polyol A The top coating material 3 was manufactured by mixing the weight parts uniformly.
When the contact angle of the top coating material 3 was measured by the same method as that for the top coating material 1, the contact angle of the top coating material 3 was 36 °.
・上塗材４
非水分散形アクリルポリオールＢ（水酸基価５０ＫＯＨｍｇ／ｇ、ガラス転移温度３２℃、固形分５０重量％）１８８重量部に対し、マンガンビスマス複合酸化物１８重量部、炭化水素系溶剤２３重量部、シリコーン系消泡剤１重量部、イソシアヌレート構造含有ポリイソシアネートＡ６重量部、親水性付与成分１重量部を均一に混合することにより、上塗材４を製造した。
上塗材４について、上記上塗材１と同様の方法で接触角を測定したところ、上塗材４の接触角は５４°であった。・ Coating material 4
Non-aqueous dispersion type acrylic polyol B (hydroxyl value 50 KOHmg / g, glass transition temperature 32 ° C., solid content 50% by weight) 188 parts by weight, manganese bismuth composite oxide 18 parts by weight, hydrocarbon solvent 23 parts by weight, silicone The top coating material 4 was manufactured by uniformly mixing 1 part by weight of the antifoaming agent, 6 parts by weight of polyisocyanate A containing isocyanurate structure, and 1 part by weight of the hydrophilicity-imparting component.
When the contact angle of the top coating material 4 was measured by the same method as that for the top coating material 1, the contact angle of the top coating material 4 was 54 °.
・上塗材５
非水分散形アクリルポリオールＢ１８８重量部に対し、フタロシアニングリーン７重量部、フタロシアニンブルー３重量部、ペリレンレッド５重量部、ベンズイミダゾロンイエロー４重量部、炭化水素系溶剤３０重量部、シリコーン系消泡剤１重量部、イソシアヌレート構造含有ポリイソシアネートＡ６重量部、親水性付与成分１重量部を均一に混合することにより、上塗材５を製造した。
上塗材５について、上記上塗材１と同様の方法で接触角を測定したところ、上塗材５の接触角は５６°であった。・ Topcoat 5
7 parts by weight of phthalocyanine green, 3 parts by weight of phthalocyanine blue, 5 parts by weight of perylene red, 4 parts by weight of benzimidazolone yellow, 30 parts by weight of hydrocarbon-based solvent, silicone-based defoaming with respect to 188 parts by weight of non-aqueous dispersion type acrylic polyol B The top coating material 5 was manufactured by uniformly mixing 1 part by weight of the agent, 6 parts by weight of polyisocyanate A containing isocyanurate structure, and 1 part by weight of the hydrophilicity-imparting component.
When the contact angle of the topcoat material 5 was measured by the same method as that for the topcoat material 1, the contact angle of the topcoat material 5 was 56 °.
・上塗材６
非水分散形アクリルポリオールＡ１８８重量部に対し、フタロシアニングリーン７重量部、フタロシアニンブルー３重量部、ペリレンレッド５重量部、ベンズイミダゾロンイエロー４重量部、炭化水素系溶剤２６重量部、シリコーン系消泡剤１重量部、イソシアヌレート構造含有ポリイソシアネートＡ６重量部を均一に混合することにより、上塗材６を製造した。
上塗材６について、上記上塗材１と同様の方法で接触角を測定したところ、上塗材６の接触角は８３°であった。・ Coating material 6
7 parts by weight of phthalocyanine green, 3 parts by weight of phthalocyanine blue, 5 parts by weight of perylene red, 4 parts by weight of benzimidazolone yellow, 26 parts by weight of hydrocarbon-based solvent, silicone-based defoaming with respect to 188 parts by weight of non-aqueous dispersion type acrylic polyol A The top coating material 6 was manufactured by uniformly mixing 1 part by weight of the agent and 6 parts by weight of polyisocyanate A containing the isocyanurate structure.
When the contact angle of the top coating material 6 was measured by the same method as that for the top coating material 1, the contact angle of the top coating material 6 was 83 °.
・上塗材７
非水分散形アクリルポリオールＡ１８８重量部に対し、カーボンブラック１８重量部、炭化水素系溶剤２６重量部、シリコーン系消泡剤１重量部、イソシアヌレート構造含有ポリイソシアネートＡ６重量部を均一に混合することにより、上塗材７を製造した。
上塗材７について、上記上塗材１と同様の方法で接触角を測定したところ、上塗材７の接触角は８２°であった。・ Topcoat 7
Uniform mixing of 18 parts by weight of carbon black, 26 parts by weight of a hydrocarbon solvent, 1 part by weight of a silicone-based antifoaming agent and 6 parts by weight of polyisocyanate A having an isocyanurate structure with 188 parts by weight of the non-aqueous dispersion type acrylic polyol A Thus, a top coating material 7 was produced.
When the contact angle of the top coating material 7 was measured by the same method as that for the top coating material 1, the contact angle of the top coating material 7 was 82 °.
（試験例１）
＜騒音レベル試験＞
既存塗膜を有するアルミニウム板（３００ｍｍ×３００ｍｍ×１ｍｍ、Ｌ＊＝４８）に対し、防錆下塗材を乾燥膜厚が３０μｍとなるようにスプレー塗装し、標準状態で１８時間乾燥後、中塗材１を乾燥膜厚が２００μｍとなるようにスプレー塗装し、標準状態で２４時間乾燥した。次いで、上塗材１を乾燥膜厚が４０μｍとなるようにスプレー塗装し、標準状態で７日間乾燥後、屋外にて１ヶ月間放置した。(Test Example 1)
<Noise level test>
On an aluminum plate (300 mm x 300 mm x 1 mm, L * = 48) with an existing coating film, spray-coat the rust-preventive primer so that the dry film thickness is 30 μm, and after drying for 18 hours in the standard state, the intermediate coating material 1 was spray-coated so that the dry film thickness was 200 μm, and dried in a standard state for 24 hours. Next, the top coating material 1 was spray-coated so that the dry film thickness was 40 μm, dried in a standard state for 7 days, and then left outdoors for 1 month.
以上の方法で得られた試験板を水平に設置し、その上方３ｍからシャワーノズルを用いて水を連続的に１分間散水した。このとき、試験板の裏面から１０ｃｍ離れたところに設置した騒音計により騒音レベルを測定した。騒音レベルは、以下の評価基準に従って評価した。
Ａ：８０ｄＢ未満
Ｂ：８０ｄＢ以上８５ｄＢ未満
Ｃ：８５ｄＢ以上９０ｄＢ未満
Ｄ：９０ｄＢ以上The test plate obtained by the above method was installed horizontally, and water was continuously sprinkled for 1 minute using a shower nozzle from 3 m above. At this time, the noise level was measured with a noise meter installed 10 cm away from the back surface of the test plate. The noise level was evaluated according to the following evaluation criteria.
A: Less than 80 dB B: 80 dB or more and less than 85 dB C: 85 dB or more and less than 90 dB D: 90 dB or more
＜密着性試験＞
上記「騒音レベル試験」と同様の手順にて試験板を作製した（但しアルミニウム板は１５０ｍｍ×７０ｍｍ×１ｍｍのものを用いた）。<Adhesion test>
A test plate was prepared in the same procedure as in the above “noise level test” (however, an aluminum plate having a size of 150 mm × 70 mm × 1 mm was used).
以上の方法で得られた試験板を５０℃の温水に７２時間浸漬した後、ＪＩＳ Ｋ ５６００−５−６に準じた碁盤目テープ法にて密着性を評価した。評価基準は以下の通りである。
Ａ：欠損部面積が５％未満
Ｂ：欠損部面積が５％以上１５％未満
Ｃ：欠損部面積が１５％以上The test plate obtained by the above method was immersed in warm water of 50 ° C. for 72 hours, and then the adhesion was evaluated by a cross-cut tape method according to JIS K 5600-5-6. The evaluation criteria are as follows.
A: The defect area is less than 5% B: The defect area is 5% or more and less than 15% C: The defect area is 15% or more
＜温度上昇抑制性試験＞
上記「騒音レベル試験」と同様の手順にて試験板を作製した。<Temperature rise inhibition test>
A test plate was prepared in the same procedure as in the above “noise level test”.
以上の方法で得られた試験板に対し、赤外線ランプを２０ｃｍの距離から照射し、温度上昇が平衡に達したときの試験体裏面温度を測定した。評価基準は以下の通りである。
Ａ：試験体裏面温度が６５℃未満
Ｂ：試験体裏面温度が６５℃以上７０℃未満
Ｃ：試験体裏面温度が７０℃以上７５℃未満
Ｄ：試験体裏面温度が７５℃以上The test plate obtained by the above method was irradiated with an infrared lamp from a distance of 20 cm, and the test specimen back surface temperature when the temperature rise reached equilibrium was measured. The evaluation criteria are as follows.
A: Specimen back surface temperature of less than 65 ° C B: Specimen back surface temperature of 65 ° C or more and less than 70 ° C C: Specimen back surface temperature of 70 ° C or more and less than 75 ° C D: Specimen back surface temperature of 75 ° C or more
＜促進劣化後の騒音レベル試験＞
上記「騒音レベル試験」と同様の手順にて試験板を作製した（但しアルミニウム板は３００ｍｍ×１５０ｍｍ×１ｍｍのものを各２枚ずつ用いた）。<Noise level test after accelerated deterioration>
Test plates were prepared in the same procedure as the above “noise level test” (however, two aluminum plates each having a size of 300 mm × 150 mm × 1 mm were used).
以上の方法で得られた試験板を、促進耐候性試験機（メタルウェザー；ダイプラウィンテス株式会社製）に２４０時間曝露した後、上記「騒音レベル試験」と同様の手順で騒音レベルを測定した。なお、この試験は、試験例２及び試験例１８について実施した。 The test plate obtained by the above method was exposed to an accelerated weathering tester (Metal Weather; manufactured by Daipura Wintes Co., Ltd.) for 240 hours, and then the noise level was measured in the same procedure as the above “noise level test”. . This test was conducted for Test Example 2 and Test Example 18.
試験結果を表１に示す。試験例１ではいずれの試験においても優れた結果が得られた。 The test results are shown in Table 1. In Test Example 1, excellent results were obtained in any test.
（試験例２〜８）
中塗材、上塗材として表１に示すものを使用した以外は、試験例１と同様の方法で試験板を作製し、各試験を行った。結果を表１に示す。試験例２〜８ではいずれの試験においても優れた結果が得られた。(Test Examples 2 to 8)
A test plate was prepared in the same manner as in Test Example 1 except that the intermediate coating material and the top coating material shown in Table 1 were used, and each test was performed. The results are shown in Table 1. In Test Examples 2 to 8, excellent results were obtained in any test.
（試験例９〜１１）
中塗材、上塗材として表２に示すものを使用した以外は、試験例１と同様の方法で試験板を作製し、各試験を行った。結果を表２に示す。試験例９〜１１では、試験例１〜８に比べ十分な結果を得ることができなかった。(Test Examples 9 to 11)
A test plate was prepared in the same manner as in Test Example 1 except that the intermediate coating material and the top coating material shown in Table 2 were used, and each test was performed. The results are shown in Table 2. In Test Examples 9 to 11, sufficient results could not be obtained as compared with Test Examples 1 to 8.
（試験例１２）
防錆下塗材を塗装した後、その上に直接上塗材１を塗装した以外は、試験例１と同様の方法で試験板を作製し、各試験を行った。結果を表２に示す。試験例１２では十分な結果を得ることができなかった。(Test Example 12)
A test plate was prepared in the same manner as in Test Example 1 except that the coating material 1 was directly coated thereon after coating the rust-proof primer, and each test was performed. The results are shown in Table 2. In Test Example 12, sufficient results could not be obtained.
（試験例１３）
防錆下塗材を塗装した後、その上に直接上塗材５を塗装した以外は、試験例１と同様の方法で試験板を作製し、各試験を行った。結果を表２に示す。試験例１３では十分な結果を得ることができなかった。(Test Example 13)
A test plate was prepared in the same manner as in Test Example 1 except that the top coat material 5 was directly coated thereon after the rust preventive primer was applied, and each test was performed. The results are shown in Table 2. In Test Example 13, sufficient results could not be obtained.
（試験例１４〜１６）
中塗材、上塗材として表２に示すものを使用した以外は、試験例１と同様の方法で試験板を作製し、各試験を行った。結果を表２に示す。試験例１４〜１６では十分な結果を得ることができなかった。(Test Examples 14 to 16)
A test plate was prepared in the same manner as in Test Example 1 except that the intermediate coating material and the top coating material shown in Table 2 were used, and each test was performed. The results are shown in Table 2. In Test Examples 14 to 16, sufficient results could not be obtained.
（試験例１７）
中塗材、上塗材として表２に示すものを使用するとともに、中塗材については乾燥膜厚が３０μｍとなるように塗装を行った。これ以外は、試験例１と同様の方法で試験板を作製し、各試験を行った。結果を表２に示す。試験例１７では十分な結果を得ることができなかった。(Test Example 17)
The intermediate coating material and the top coating material shown in Table 2 were used, and the intermediate coating material was coated so that the dry film thickness was 30 μm. Except for this, a test plate was prepared in the same manner as in Test Example 1, and each test was performed. The results are shown in Table 2. In Test Example 17, sufficient results could not be obtained.
（試験例１８）
中塗材、上塗材として表２に示すものを使用した以外は、試験例１と同様の方法で試験板を作製し、各試験を行った。結果を表２に示す。促進劣化後の騒音レベル試験の結果は、試験例１８より試験例２の方が良好であった。(Test Example 18)
A test plate was prepared in the same manner as in Test Example 1 except that the intermediate coating material and the top coating material shown in Table 2 were used, and each test was performed. The results are shown in Table 2. As a result of the noise level test after the accelerated deterioration, Test Example 2 was better than Test Example 18.
Claims (2)
The film formation body obtained by the film formation method of Claim 1.
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| CN103290932B (en) * | 2013-05-21 | 2017-04-12 | 石家庄日加精细矿物制品有限公司 | Preparation method of reflective energy-saving material for building surface |
| JP6423656B2 (en) * | 2013-09-05 | 2018-11-14 | ベック株式会社 | Makeup method |
| JP2015209475A (en) * | 2014-04-25 | 2015-11-24 | クラリアント・インターナシヨナル・リミテツド | Black pigment composition for heat shield coating material, heat shield coating material using the same, and use of the same for color matching and coating |
| JP6496293B2 (en) * | 2016-10-27 | 2019-04-03 | クラリアント・インターナシヨナル・リミテツド | Black pigment composition for thermal barrier paint, thermal barrier paint using the same, and use thereof for toning and painting |
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| JP2003238897A (en) * | 2002-02-14 | 2003-08-27 | Nippon Tokushu Toryo Co Ltd | Heat and sound insulating paint and process |
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| EP1535953A4 (en) * | 2002-07-30 | 2005-11-02 | Toyo Kohan Co Ltd | Surface-roughened resin film, metal sheet coated with surface-roughened resin film, process for producing metal sheet coated with surface-roughened resin film, and metal can having surface coated with surface-roughened resin film and process for producing the same |
| JP2006281726A (en) * | 2005-04-05 | 2006-10-19 | Mannen:Kk | Non-conductive metal gloss plating, case for electronic device with non-conductive metal gloss plating, and method of forming non-conductive metal glass plating |
| JP2008221802A (en) * | 2007-03-15 | 2008-09-25 | Toyoda Gosei Co Ltd | Resin product and its manufacturing method |
| JP5564211B2 (en) * | 2008-08-04 | 2014-07-30 | エスケー化研株式会社 | Film forming method and film forming body |
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| JP2002121477A (en) * | 2000-10-19 | 2002-04-23 | Nissan Motor Co Ltd | Sound-proof coating composition for vehicle and sound- proof coating structure |
| JP2003238897A (en) * | 2002-02-14 | 2003-08-27 | Nippon Tokushu Toryo Co Ltd | Heat and sound insulating paint and process |
| JP2004204578A (en) * | 2002-12-26 | 2004-07-22 | Nippon Tokushu Toryo Co Ltd | Heat and sound insulating method, and heat and sound insulating structure |
| JP2007238640A (en) * | 2006-03-03 | 2007-09-20 | Sk Kaken Co Ltd | Coating composition |
| JP2008133460A (en) * | 2006-10-27 | 2008-06-12 | Asahi Glass Co Ltd | Method for producing urethane resin for vibration damping material and urethane prepolymer for vibration damping material |
| JP2010235884A (en) * | 2009-03-31 | 2010-10-21 | Cci Corp | Vibration damping coating composition for roof and roof structure |
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| WO2011096392A1 (en) | 2011-08-11 |
| CN102753768A (en) | 2012-10-24 |
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| SG183132A1 (en) | 2012-09-27 |
| JP2015092058A (en) | 2015-05-14 |
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| CN102753768B (en) | 2015-11-25 |
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