JP2007145989A - Coating composition - Google Patents
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Abstract
Description
本発明は、遮熱性を有する新規な塗料組成物に関する。 The present invention relates to a novel coating composition having a heat shielding property.
近年、都市部においては、コンクリート建造物や冷房等から排出される人工放射熱などにより、都市独特の気候が作り出されている。特に夏期において都市部における屋外の温度上昇は著しく、ヒートアイランド現象と呼ばれる問題を引き起こしている。これに対し、建築物内部においては、冷房の使用によって屋内温度を下げることが頻繁に行われるが、冷房の多用は消費電力エネルギーを増加させるだけでなく、室外機からの排気によって屋外の温度上昇を助長している。 In recent years, in urban areas, a climate unique to cities has been created by means of artificial radiant heat discharged from concrete buildings and air conditioning. Especially in summer, the outdoor temperature rise in urban areas is remarkable, causing a problem called the heat island phenomenon. On the other hand, in buildings, the indoor temperature is often lowered by using cooling, but the heavy use of cooling not only increases the power consumption energy but also increases the outdoor temperature by exhausting from the outdoor unit. Is conducive.
建築物の温度上昇を抑制する方法として、屋根、屋上、外壁等の建築物外装面基材に遮熱塗料を塗装する方法が知られている。このような遮熱塗料の一例として、特許文献１には、ビヒクル及び顔料を主成分とする塗料において、粒径５０μｍ以下の特定太陽熱遮蔽顔料を塗料固形分中２〜６０重量％含む太陽熱遮蔽塗料組成物が記載されている。但し、特許文献１に記載の塗料組成物は、白色系の色相を有するものである。そのため、明度を下げた色相を得るにはカーボンブラック等の着色顔料を併用しなければならず、その場合には遮熱性が損なわれてしまうという問題が生じる。 As a method for suppressing the temperature rise of a building, a method of applying a thermal barrier paint to a building exterior surface base material such as a roof, a rooftop, or an outer wall is known. As an example of such a heat-shielding paint, Patent Document 1 discloses a solar heat-shielding paint containing 2 to 60% by weight of a specific solar heat-shielding pigment having a particle size of 50 μm or less in a paint mainly composed of a vehicle and a pigment. A composition is described. However, the coating composition described in Patent Document 1 has a white hue. Therefore, in order to obtain a hue with reduced brightness, a color pigment such as carbon black must be used in combination, and in that case, there arises a problem that the heat shielding property is impaired.
塗料の明度を下げつつも遮熱性を確保する技術に関しては、以下の特許文献が挙げられる。例えば特許文献２には、白色顔料に加え、太陽熱遮蔽顔料として、粒径５０μｍ以下のＳｉまたはＳｉと各種金属との合金を用いて明度を下げた太陽光遮蔽塗料組成物が記載されている。また、特許文献３には、近赤外領域で反射を示すアゾメチアゾ系黒顔料と、酸化チタン等の白顔料を混合した遮熱性塗料が記載されている。
しかしながら、このような特許文献に記載の塗料では、その塗膜が長期にわたり屋外で曝露されると光沢の低下や色相の変化等を引き起こす場合があり、耐候性等の点において改善の余地がある。
The following patent documents are mentioned regarding the technique which ensures heat-shielding property, reducing the brightness of a coating material. For example, Patent Document 2 describes a solar light shielding coating composition whose brightness is lowered by using Si or an alloy of Si and various metals having a particle diameter of 50 μm or less as a solar heat shielding pigment in addition to a white pigment. Patent Document 3 describes a heat-shielding paint in which an azomethiazo black pigment that reflects in the near infrared region and a white pigment such as titanium oxide are mixed.
However, in such paints described in the patent literature, when the coating film is exposed outdoors for a long time, it may cause a decrease in gloss or a change in hue, and there is room for improvement in terms of weather resistance and the like. .
本発明は、このような問題点に鑑みなされたものであり、明度を下げた色相においても十分な遮熱機能を発揮することができ、耐候性にも優れる塗料組成物を得ることを目的とするものである。 The present invention has been made in view of such problems, and an object of the present invention is to obtain a coating composition that can exhibit a sufficient heat-shielding function even in a hue with reduced lightness and has excellent weather resistance. To do.
本発明者らは、上記のような従来技術の問題点に鑑み鋭意研究を行った結果、塗料を構成する顔料として、特定白色顔料の表面に特定黒色顔料が固着されたものを使用することに想到し、本発明を完成させるに至った。 As a result of intensive studies in view of the problems of the prior art as described above, the present inventors have used a specific black pigment fixed to the surface of a specific white pigment as a pigment constituting the paint. The present invention has been conceived and the present invention has been completed.
すなわち本発明の塗料組成物は以下の特徴を有するものである。
１．塗料用樹脂の固形分１００重量部に対し顔料を１〜２００重量部含有し、その塗膜の明度（Ｌ＊）が３０〜９５である塗料組成物において、前記顔料として、
白色顔料の表面にビスマス複合酸化物からなる黒色顔料が固着された平均粒子径０．５〜５μｍの顔料
を含むことを特徴とする塗料組成物。
That is, the coating composition of the present invention has the following characteristics.
1. In the coating composition containing 1 to 200 parts by weight of the pigment with respect to 100 parts by weight of the solid content of the resin for coatings, and having a lightness (L * ) of the coating film of 30 to 95, as the pigment,
A coating composition comprising a pigment having an average particle size of 0.5 to 5 μm, wherein a black pigment composed of a bismuth composite oxide is fixed to the surface of a white pigment.
本発明の塗料組成物は、十分な遮熱機能を発揮することができ、しかも優れた耐候性を有するものである。本発明の塗料組成物がこのような効果を奏する理由は明確ではないが、概ね以下の作用が寄与しているものと推測される。すなわち、第１には、本発明塗料組成物で使用する顔料は着色力が強く、塗料を所望の色相に調色しようとする場合、白色顔料と黒色顔料をそれぞれ別々に混合する場合に比べ顔料混合量が少量で済むこと、第２には、塗膜の温度上昇による塗膜劣化が抑制できること、第３には、酸化チタン等の白色顔料に起因するラジカル発生を抑制することができること等である。本発明では、これらの相乗作用により、優れた耐候性が発現されるものと考えられる。 The coating composition of the present invention can exhibit a sufficient heat shielding function and has excellent weather resistance. The reason why the coating composition of the present invention exhibits such an effect is not clear, but it is presumed that the following actions contribute in general. That is, firstly, the pigment used in the coating composition of the present invention has a strong coloring power, and the pigment is more pigmented than when the white pigment and the black pigment are separately mixed when the coating is toned to a desired hue. A small amount of mixing, secondly, it is possible to suppress coating film deterioration due to temperature rise of the coating film, and thirdly, it is possible to suppress generation of radicals due to white pigments such as titanium oxide. is there. In this invention, it is thought that the outstanding weather resistance is expressed by these synergistic actions.
以下、本発明を実施するための最良の形態とともに詳細に説明する。 Hereinafter, it explains in detail with the best form for carrying out the present invention.
本発明の塗料組成物は、塗料用樹脂と顔料を必須成分として含むものである。このうち塗料用樹脂としては、例えば、アクリル樹脂、ポリエステル樹脂、ポリエーテル樹脂、ポリウレタン樹脂、アクリルシリコン樹脂、フッ素樹脂、酢酸ビニル樹脂、エポキシ樹脂等、あるいはこれらの複合系等を挙げることができる。これらは１種または２種以上で使用することができる。このような塗料用樹脂の形態としては、溶剤可溶性樹脂、非水分散性樹脂、水溶性樹脂、水分散性樹脂、無溶剤型樹脂等が挙げられる。塗料用樹脂のガラス転移温度は、通常−２０〜８０℃（好ましくは−１０〜６０℃）程度である。 The coating composition of the present invention contains a coating resin and a pigment as essential components. Among these, examples of the resin for paint include acrylic resins, polyester resins, polyether resins, polyurethane resins, acrylic silicon resins, fluororesins, vinyl acetate resins, epoxy resins, and composites thereof. These can be used alone or in combination of two or more. Examples of the form of the coating resin include solvent-soluble resins, non-water dispersible resins, water-soluble resins, water-dispersible resins, and solvent-free resins. The glass transition temperature of the coating resin is usually about -20 to 80 ° C (preferably -10 to 60 ° C).
このうち、溶剤可溶性樹脂及び／または非水分散性樹脂としては、非水系溶剤を媒体とするものであって、当該全溶剤のうち５０重量％以上（好ましくは６０重量％以上）が脂肪族炭化水素である所謂弱溶剤形樹脂が好適である。かかる弱溶剤形樹脂は、芳香族炭化水素系溶剤を主溶剤とする強溶剤形樹脂に比べ、低毒性であり、作業上の安全性が高く、さらには既存塗膜上に塗装を行った際のリフティング発生を抑制できる等の特徴を有するものである。脂肪族炭化水素としては、例えば、ｎ−ヘキサン、ｎ−ペンタン、ｎ−オクタン、ｎ−ノナン、ｎ−デカン、ｎ−ウンデカン、ｎ−ドデカン等が挙げられ、この他、テルピン油やミネラルスピリット等の脂肪族炭化水素系溶剤を使用することもできる。特に、トルエン、キシレンを含まず、引火点２１℃以上の第２石油類に該当するものが、安全衛生上好ましい。 Among these, the solvent-soluble resin and / or the non-aqueous dispersible resin is a non-aqueous solvent as a medium, and 50% by weight or more (preferably 60% by weight or more) of the total solvent is aliphatic carbonized. A so-called weak solvent resin which is hydrogen is preferred. Such weak solvent resins are less toxic and have higher work safety compared to strong solvent resins that use aromatic hydrocarbon solvents as the main solvent, and when applied to existing coatings. It has a feature that the occurrence of lifting can be suppressed. Examples of the aliphatic hydrocarbon include n-hexane, n-pentane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, and the like. In addition, terpine oil, mineral spirit, etc. Other aliphatic hydrocarbon solvents can also be used. In particular, those which do not contain toluene and xylene and correspond to the second petroleum having a flash point of 21 ° C. or higher are preferable in terms of safety and health.
本発明における塗料用樹脂は架橋反応性を有するものであってもよい。塗料用樹脂が架橋反応型樹脂である場合は、塗膜の強度、耐水性、耐候性、密着性等を高めることができる。架橋反応型樹脂は、それ自体で架橋反応を生じるもの、あるいは別途混合する架橋剤によって架橋反応を生じるもののいずれであってもよい。このような架橋反応性は、例えば、水酸基とイソシアネート基、カルボニル基とヒドラジド基、エポキシ基とアミノ基、アルド基とセミカルバジド基、ケト基とセミカルバジド基、アルコキシル基どうし、カルボキシル基と金属イオン、カルボキシル基とカルボジイミド基、カルボキシル基とエポキシ基、カルボキシル基とアジリジン基、カルボキシル基とオキサゾリン基等の反応性官能基を組み合わせることによって付与することができる。この中でも水酸基−イソシアート基架橋反応型樹脂が好適である。 The coating resin in the present invention may have crosslinking reactivity. When the coating resin is a cross-linking resin, the strength, water resistance, weather resistance, adhesion and the like of the coating film can be improved. The cross-linking reaction type resin may be one that causes a cross-linking reaction by itself or one that causes a cross-linking reaction by a cross-linking agent that is separately mixed. Such crosslinking reactivity includes, for example, hydroxyl group and isocyanate group, carbonyl group and hydrazide group, epoxy group and amino group, aldo group and semicarbazide group, keto group and semicarbazide group, alkoxyl group, carboxyl group and metal ion, carboxyl group It can be imparted by combining a reactive functional group such as a group and a carbodiimide group, a carboxyl group and an epoxy group, a carboxyl group and an aziridine group, a carboxyl group and an oxazoline group. Among these, a hydroxyl group-isocyanate group crosslinking reaction type resin is preferable.
本発明組成物では、白色顔料の表面にビスマス複合酸化物からなる黒色顔料が固着された平均粒子径０．５〜５μｍの顔料（以下「複合顔料」ともいう）を含有する。本発明では、このような複合顔料を含有することにより、塗料を所望の明度に調整しつつ、太陽光による塗膜の蓄熱を抑制することが可能となる。さらに、本発明では、このような複合顔料を着色材として使用することにより、耐候性に優れた塗料組成物を得ることができる。 The composition of the present invention contains a pigment having an average particle diameter of 0.5 to 5 μm (hereinafter also referred to as “composite pigment”) in which a black pigment made of a bismuth composite oxide is fixed on the surface of a white pigment. In this invention, it becomes possible to suppress the thermal storage of the coating film by sunlight, adjusting a coating material to desired brightness by containing such a composite pigment. Furthermore, in this invention, the coating composition excellent in the weather resistance can be obtained by using such a composite pigment as a coloring material.
複合顔料における白色顔料は、可視領域から近赤外領域にわたって高い光反射性を有する材料である。このような白色顔料としては、酸化チタン、酸化亜鉛、アルミナ、シリカ、クレー、炭酸カルシウム、硫酸バリウム等が挙げられる。この中でも酸化チタン（特にルチル型酸化チタン）が好適である。白色顔料の平均粒子径は、通常０．４〜３μｍ、好ましくは０．５〜２μｍである。 The white pigment in the composite pigment is a material having high light reflectivity from the visible region to the near infrared region. Examples of such white pigments include titanium oxide, zinc oxide, alumina, silica, clay, calcium carbonate, and barium sulfate. Among these, titanium oxide (particularly rutile type titanium oxide) is preferable. The average particle diameter of the white pigment is usually 0.4 to 3 μm, preferably 0.5 to 2 μm.
一般的に白色顔料としては、平均粒子径約０．３μｍ程度の酸化チタンがよく知られている。これに対し、上述の如き平均粒子径の白色顔料を使用すれば、近赤外領域において優れた光反射性を発揮することができ、遮熱性の点で有利となる。さらに、白色顔料がこのような平均粒子径であれば、これに黒色顔料を固着して得られる複合顔料の着色力を高めることができる。また、通常の酸化チタン等に比べ、相対的に顔料の比表面積が小さくなるため、ラジカル発生に起因する樹脂劣化を抑制することもできる。なお、本発明における平均粒子径は、透過型電子顕微鏡の観察によるものであり、各粒子の円相当径を直径としたときの粒子径分布（個数基準）を求めることによって得られる値である。 In general, titanium oxide having an average particle diameter of about 0.3 μm is well known as a white pigment. On the other hand, if a white pigment having an average particle diameter as described above is used, excellent light reflectivity can be exhibited in the near infrared region, which is advantageous in terms of heat shielding. Further, when the white pigment has such an average particle diameter, the coloring power of the composite pigment obtained by fixing the black pigment to the white pigment can be increased. In addition, since the specific surface area of the pigment is relatively smaller than that of ordinary titanium oxide or the like, it is possible to suppress resin deterioration caused by radical generation. In addition, the average particle diameter in this invention is based on observation with a transmission electron microscope, and is a value obtained by obtaining a particle diameter distribution (number basis) when the equivalent circle diameter of each particle is taken as the diameter.
複合顔料における黒色顔料としては、ビスマス複合酸化物を使用する。このビスマス複合酸化物は、可視領域では光反射性が低く、近赤外領域では光反射性が高いという特性を有し、漆黒性に富む材料である。上述の白色顔料の表面にこのようなビスマス複合酸化物を固着させることにより、遮熱性、着色性、耐候性に優れた顔料を得ることができる。このようなビスマス複合酸化物は、ビスマスとその他の金属との複合酸化物であり、具体的にはＢｉＭｎ２Ｏ５等が挙げられる。ビスマス複合酸化物の平均粒子径は、通常０．１〜２μｍ程度である。 As the black pigment in the composite pigment, a bismuth composite oxide is used. This bismuth composite oxide has a characteristic that light reflectivity is low in the visible region and light reflectivity is high in the near infrared region, and is a material rich in jet black. By fixing such a bismuth composite oxide on the surface of the above white pigment, a pigment having excellent heat shielding properties, colorability, and weather resistance can be obtained. Such a bismuth composite oxide is a composite oxide of bismuth and other metals, and specifically includes BiMn 2 O 5 and the like. The average particle size of the bismuth composite oxide is usually about 0.1 to 2 μm.
複合顔料の製造方法は、白色顔料の表面に黒色顔料を固着できる方法であれば特に限定されず、公知の方法を使用することができる。例えば、白色顔料表面に黒色顔料をそのまま固着することもできるし、また固着剤を用いて固着することもできる。この際必要であれば熱処理、加圧処理、酸化還元処理等何らかの処理を行うこともできる。固着剤としては、特に限定されず、白色顔料と黒色顔料の種類により適宜選定することができるが、例えばアルコキシシラン等のシリル基含有化合物等が挙げられる。複合顔料における白色顔料と黒色顔料の重量比率は、通常１００：２〜１００：１００、好ましくは１００：５〜１００：５０程度である。 The manufacturing method of a composite pigment will not be specifically limited if a black pigment can be fixed to the surface of a white pigment, A well-known method can be used. For example, the black pigment can be fixed as it is on the surface of the white pigment, or can be fixed using a fixing agent. At this time, if necessary, some kind of treatment such as heat treatment, pressure treatment, oxidation-reduction treatment, etc. can be performed. The fixing agent is not particularly limited and can be appropriately selected depending on the type of white pigment and black pigment. Examples thereof include silyl group-containing compounds such as alkoxysilanes. The weight ratio of the white pigment to the black pigment in the composite pigment is usually about 100: 2 to 100: 100, preferably about 100: 5 to 100: 50.
複合顔料の平均粒子径は、通常０．５〜５μｍ、好ましくは０．８〜４μｍである。複合顔料の平均粒子径がこのような範囲内であれば、遮熱性、着色力、耐候性等において優れた効果を得ることができる。 The average particle size of the composite pigment is usually 0.5 to 5 μm, preferably 0.8 to 4 μm. When the average particle diameter of the composite pigment is within such a range, excellent effects in heat shielding properties, coloring power, weather resistance and the like can be obtained.
本発明組成物では、上記以外の顔料を併用することもできる。この場合、顔料としては、赤外線反射性顔料及び／または赤外線透過性顔料が好適である。具体的に、赤外線反射性顔料としては、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、アルミナ等が挙げられる。一方、赤外線透過性顔料としては、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。これら顔料を適宜組み合わせることにより、様々な色相の塗膜を形成することが可能となる。 In the composition of the present invention, pigments other than those described above can be used in combination. In this case, an infrared reflecting pigment and / or an infrared transmitting pigment is suitable as the pigment. Specifically, examples of the infrared reflective pigment include aluminum flake, titanium oxide, barium sulfate, zinc oxide, calcium carbonate, silicon oxide, magnesium oxide, zirconium oxide, yttrium oxide, indium oxide, and alumina. On the other hand, examples of infrared transmissive pigments include perylene pigments, azo pigments, yellow lead, petals, vermilion, titanium red, cadmium red, quinacridone red, isoindolinone, benzimidazolone, phthalocyanine green, phthalocyanine blue, and cobalt blue. , Indanthrene blue, ultramarine blue, bitumen and the like, and one or more of these can be used. By appropriately combining these pigments, it is possible to form coating films having various hues.
本発明組成物において、これら顔料の比率は、塗料用樹脂の固形分１００重量部に対し、通常１〜２００重量部、好ましくは２〜１００重量部である。顔料比率がこのような範囲内であれば、所望の色に塗料を調色することができ、塗膜の割れ防止性等においても有利な効果を得ることができる。 In the composition of the present invention, the ratio of these pigments is usually 1 to 200 parts by weight, preferably 2 to 100 parts by weight, based on 100 parts by weight of the solid content of the coating resin. If the pigment ratio is within such a range, the paint can be toned in a desired color, and advantageous effects can be obtained in terms of preventing cracking of the coating film.
本発明組成物は、その塗膜の色相において明度（Ｌ＊）が３０〜９５となるものである。本発明では、塗膜のＬ＊がこのような範囲内である場合に有利な効果を得ることができる。とりわけ、Ｌ＊が３５〜９０（さらには４０〜８０）である場合にはより顕著な効果を得ることができる。本発明組成物の塗膜におけるａ＊、ｂ＊は特に限定されるものではないが、特にａ＊が−２０〜２０（さらには−１０〜１０）、ｂ＊が−３０〜３０（さらには−２０〜２０）である場合が好適である。なお、本発明におけるＬ＊、ａ＊、ｂ＊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 composition of the present invention has a lightness (L * ) of 30 to 95 in the hue of the coating film. In the present invention, an advantageous effect can be obtained when L * of the coating film is within such a range. In particular, when L * is 35 to 90 (or 40 to 80), a more remarkable effect can be obtained. The a * and b * in the coating film of the composition of the present invention are not particularly limited, but in particular, a * is -20 to 20 (more preferably -10 to 10), and b * is -30 to 30 (more -20 to 20) is preferred. In the present invention, L * , a * , and b * are values in the CIE L * a * b * color space and are measured by a spectrophotometer.
本発明組成物では、上記成分に加え、シリケート化合物を混合することができる。シリケート化合物の混合により、塗膜表面の親水性が高まり、塗膜表面への汚染物質の付着を抑制することができ、ひいては塗膜の遮熱性能を高めることができる。シリケート化合物としては、特に、炭素数１〜２の直鎖アルキル基と炭素数３以上の分岐アルキル基が９５：５〜５０：５０（好ましくは９０：１０〜５５：４５、より好ましくは８５：１５〜６０：４０）の当量比率で混在する変性シリケート化合物が好適である。 In the composition of the present invention, in addition to the above components, a silicate compound can be mixed. By mixing the silicate compound, the hydrophilicity of the coating film surface is increased, the adhesion of contaminants to the coating film surface can be suppressed, and as a result, the heat shielding performance of the coating film can be enhanced. As the silicate compound, in particular, a linear alkyl group having 1 to 2 carbon atoms and a branched alkyl group having 3 or more carbon atoms are 95: 5 to 50:50 (preferably 90:10 to 55:45, more preferably 85: A modified silicate compound mixed in an equivalent ratio of 15 to 60:40) is preferred.
このような変性シリケート化合物における直鎖アルキル基としては、メチル基、エチル基から選ばれる１種以上が使用できる。この中でもメチル基が好適である。一方、分岐アルキル基としては、イソプロピル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、イソヘプチル基、イソペンチル基、ネオペンチル基、ｔ−ペンチル基、１−メチルブチル基、２−メチルブチル基、１，２−ジメチルプロピル基、１−エチルプロピル基、１−メチルペンチル基、２−メチルペンチル基、３−メチルペンチル基、４−メチルペンチル基、１，１−ジメチルブチル基、２，２−ジメチルブチル基、３，３−ジメチルブチル基、１，２−ジメチルブチル基、２，３−ジメチルブチル基、１，３−ジメチルブチル基、１−エチルブチル基、２−エチルブチル基、１，１，２−トリメチルプロピル基、１，２，２−トリメチルプロピル基、１−エチル−１−メチルプロピル基、１−エチル−２−メチルプロピル基、イソオクチル基等が挙げられる。本発明では、この中でも炭素数３〜６の分岐アルキル基が好適であり、とりわけ炭素数４の分岐ブチル基が好適である。 As the linear alkyl group in such a modified silicate compound, one or more selected from a methyl group and an ethyl group can be used. Of these, a methyl group is preferred. On the other hand, as the branched alkyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isoheptyl group, isopentyl group, neopentyl group, t-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1, 2-dimethylpropyl group, 1-ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl Group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2- Trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, Sookuchiru group, and the like. In the present invention, among them, a branched alkyl group having 3 to 6 carbon atoms is preferable, and a branched butyl group having 4 carbon atoms is particularly preferable.
シリケート化合物の混合比率は、塗料用樹脂の固形分１００重量部に対して、ＳｉＯ２換算で０．１〜２０重量部（好ましくは０．３〜１０重量部、より好ましくは０．５〜５重量部）となる範囲内で設定すればよい。なお、ここに言うＳｉＯ２換算とは、アルコキシシランやシリケートなどのＳｉ−Ｏ結合をもつ化合物を、完全に加水分解した後に、９００℃で焼成した際にシリカ（ＳｉＯ２）となって残る重量分にて表したものである。 The mixing ratio of the silicate compound, based on 100 parts by weight of the solid content of the coating resin, 0.1 to 20 parts by weight in terms of SiO 2 (preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 It may be set within the range of (weight part). Weight Note that the terms of SiO 2 referred here, a compound having a SiO bond, such as alkoxysilanes and silicates, after complete hydrolysis, which remains with the silica (SiO 2) upon firing at 900 ° C. Expressed in minutes.
本発明組成物には、通常塗料に使用可能な各種添加剤を配合することも可能である。かかる添加剤としては、例えば、硬化剤、可塑剤、造膜助剤、凍結防止剤、防腐剤、防黴剤、防藻剤、消泡剤、レベリング剤、顔料分散剤、沈降防止剤、たれ防止剤、触媒、硬化促進剤、脱水剤、艶消し剤、紫外線吸収剤、酸化防止剤等が挙げられる。本発明組成物は、上記各成分を常法により混合することで得ることができる。 Various additives that can be usually used for paints can be blended in the composition of the present invention. Examples of such additives include curing agents, plasticizers, film-forming aids, antifreezing agents, antiseptics, antifungal agents, algaeproofing agents, antifoaming agents, leveling agents, pigment dispersants, antisettling agents, Examples thereof include an inhibitor, a catalyst, a curing accelerator, a dehydrating agent, a matting agent, an ultraviolet absorber, and an antioxidant. The composition of the present invention can be obtained by mixing the above-mentioned components by a conventional method.
本発明組成物は、遮熱性が要求される部位に対し適用することができる。具体的には、例えば屋根、屋上、外壁等の建築物外装面の表面仕上げに使用することができる。このような外装面の基材としては、特に限定されず、例えば、コンクリート、モルタル、金属、プラスチック、あるいはスレート板、押出成形板、サイディングボード等の各種ボード類等が挙げられる。塗装方法としては、ハケ塗り、スプレー塗装、ローラー塗装等の方法を適宜採用することができる。各種ボード類については、予め工場等でプレコートすることもできる。 The composition of the present invention can be applied to a site where heat shielding properties are required. Specifically, it can be used for surface finishing of building exterior surfaces such as roofs, rooftops, and outer walls. Such a base material for the exterior surface is not particularly limited, and examples thereof include concrete, mortar, metal, plastic, or various boards such as a slate plate, an extruded plate, and a siding board. As a coating method, methods such as brush coating, spray coating, and roller coating can be appropriately employed. Various boards can be pre-coated at a factory or the like in advance.
上述の外装面基材は、何らかの表面処理層を有するものであってもよい。かかる表面処理層は、一般的にシーラー、サーフェーサー、フィラー等と呼ばれる表面処理材によって形成することができる。本発明では、赤外線反射性顔料を含有する表面処理材が好適である。このような表面処理材を用いることにより、外装面基材の蓄熱を抑制し、遮熱効果を高めることができる。 The aforementioned exterior surface base material may have some surface treatment layer. Such a surface treatment layer can be formed of a surface treatment material generally called a sealer, a surfacer, a filler or the like. In the present invention, a surface treatment material containing an infrared reflective pigment is suitable. By using such a surface treatment material, heat storage of the exterior surface base material can be suppressed, and the heat shielding effect can be enhanced.
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が、本発明はこの実施例に限定されない。 Examples and Comparative Examples are shown below to clarify the features of the present invention, but the present invention is not limited to these Examples.
（複合顔料の製造）
・複合顔料（１）
平均粒子径１μｍの酸化チタン１００重量部に対し、メチルトリエトキシシラン３重量部を混合撹拌した後、黒色顔料としてビスマスマンガン系複合酸化物（ＢｉＭｎ２Ｏ５）３０重量部を混合撹拌し、１０５℃で６０分乾燥させることにより平均粒子径２μｍの複合顔料（１）を製造した。
(Manufacture of composite pigments)
・ Composite pigment (1)
After mixing and stirring 3 parts by weight of methyltriethoxysilane with 100 parts by weight of titanium oxide having an average particle diameter of 1 μm, 30 parts by weight of bismuth manganese-based composite oxide (BiMn 2 O 5 ) is mixed and stirred as a black pigment. The composite pigment (1) having an average particle size of 2 μm was produced by drying at 60 ° C. for 60 minutes.
・複合顔料（２）
平均粒子径１μｍの酸化チタン１００重量部に対し、メチルトリエトキシシラン３重量部を混合撹拌した後、黒色顔料として鉄クロム系複合酸化物３０重量部を混合撹拌し、１０５℃で６０分乾燥させることにより、平均粒子径２μｍの複合顔料（２）を製造した。
・ Composite pigment (2)
After mixing and stirring 3 parts by weight of methyltriethoxysilane with 100 parts by weight of titanium oxide having an average particle diameter of 1 μm, 30 parts by weight of iron-chromium composite oxide is mixed and stirred as a black pigment and dried at 105 ° C. for 60 minutes. Thus, a composite pigment (2) having an average particle diameter of 2 μm was produced.
（主剤の製造）
・主剤（１）
非水分散形アクリルポリオール（水酸基価５０ＫＯＨｍｇ／ｇ、ガラス転移温度３５℃、固形分５０重量％、媒体：ミネラルスピリット、脂肪族炭化水素７０重量％）２００重量部に対し、複合顔料（１）６０重量部、ミネラルスピリット４０重量部、アマイドワックス系増粘剤２重量部、シリコーン系消泡剤１重量部を常法にて均一に混合・撹拌することにより、主剤（１）を製造した。
(Manufacture of main agent)
・ Main agent (1)
Compound pigment (1) 60 with respect to 200 parts by weight of non-aqueous dispersion type acrylic polyol (hydroxyl value 50 KOHmg / g, glass transition temperature 35 ° C., solid content 50% by weight, medium: mineral spirit, aliphatic hydrocarbon 70% by weight) The main component (1) was produced by uniformly mixing and stirring parts by weight, 40 parts by weight of mineral spirit, 2 parts by weight of an amide wax thickener, and 1 part by weight of a silicone antifoaming agent in a conventional manner.
・主剤（２）
非水分散形アクリルポリオール（水酸基価５０ＫＯＨｍｇ／ｇ、ガラス転移温度３５℃、固形分５０重量％、媒体：ミネラルスピリット、脂肪族炭化水素７０重量％）２００重量部に対し、酸化チタン（平均粒子径１μｍ）４５重量部、ビスマスマンガン系複合酸化物１３．５重量部、ミネラルスピリット４２重量部、アマイドワックス系増粘剤２重量部、シリコーン系消泡剤１重量部を常法にて均一に混合・撹拌することにより、主剤（２）を製造した。
・ Main agent (2)
Titanium oxide (average particle diameter) with respect to 200 parts by weight of non-aqueous dispersion type acrylic polyol (hydroxyl value 50 KOHmg / g, glass transition temperature 35 ° C., solid content 50% by weight, medium: mineral spirit, aliphatic hydrocarbon 70% by weight) 1 μm) 45 parts by weight, 13.5 parts by weight of a bismuth manganese-based composite oxide, 42 parts by weight of mineral spirits, 2 parts by weight of an amide wax thickener, and 1 part by weight of a silicone-based antifoaming agent are uniformly mixed by a conventional method. -Main agent (2) was manufactured by stirring.
・主剤（３）
非水分散形アクリルポリオール（水酸基価５０ＫＯＨｍｇ／ｇ、ガラス転移温度３５℃、固形分５０重量％、媒体：ミネラルスピリット、脂肪族炭化水素７０重量％）２００重量部に対し、複合顔料（２）６０重量部、ミネラルスピリット４０重量部、アマイドワックス系増粘剤２重量部、シリコーン系消泡剤１重量部を常法にて均一に混合・撹拌することにより、主剤（３）を製造した。
・ Main agent (3)
Compound pigment (2) 60 with respect to 200 parts by weight of non-aqueous dispersion type acrylic polyol (hydroxyl value 50 KOH mg / g, glass transition temperature 35 ° C., solid content 50% by weight, medium: mineral spirit, aliphatic hydrocarbon 70% by weight) A main agent (3) was produced by uniformly mixing and stirring parts by weight, 40 parts by weight of mineral spirit, 2 parts by weight of an amide wax thickener, and 1 part by weight of a silicone-based antifoaming agent.
（硬化剤の製造）
・硬化剤（１）
イソシアヌレート構造含有ポリイソシアネート（不揮発分１００重量％、ＮＣＯ含有量２１重量％）４０重量部に対し、ソルベッソ１００（エクソンケミカル社製）６０重量部を均一に混合することにより、硬化剤（１）を製造した。
(Manufacture of curing agent)
・ Curing agent (1)
Curing agent (1) by uniformly mixing 60 parts by weight of Solvesso 100 (manufactured by Exxon Chemical Co.) with 40 parts by weight of polyisocyanate containing isocyanurate structure (non-volatile content: 100% by weight, NCO content: 21% by weight) Manufactured.
・硬化剤（２）
イソシアヌレート構造含有ポリイソシアネート（不揮発分１００重量％、ＮＣＯ含有量２１重量％）４０重量部に対し、ソルベッソ１００（エクソンケミカル社製）４０重量部、下記変性シリケート化合物２０重量部を均一に混合することにより、硬化剤（２）を製造した。
・ Curing agent (2)
40 parts by weight of isocyanurate structure-containing polyisocyanate (non-volatile content: 100% by weight, NCO content: 21% by weight) is uniformly mixed with 40 parts by weight of Solvesso 100 (manufactured by Exxon Chemical) and 20 parts by weight of the following modified silicate compound. Thus, a curing agent (2) was produced.
・変性シリケート化合物
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、変性シリケート化合物を製造した。この変性シリケート化合物におけるメチル基とイソブチル基との当量比率は６２：３８であり、９００℃にて焼成して得られたシリカ残量比率は４３重量％であった。
・ Modified silicate compound To 100 parts by weight of methyl silicate condensate (weight average molecular weight 1000, average degree of condensation 8, non-volatile content 100%), 52 parts by weight of isobutyl alcohol and 0.03 part by weight of dibutyltin dilaurate as a catalyst were added. After mixing, a demethanol reaction was carried out at 75 ° C. for 8 hours to produce a modified silicate compound. In this modified silicate compound, the equivalent ratio of methyl group to isobutyl group was 62:38, and the remaining silica ratio obtained by firing at 900 ° C. was 43% by weight.
（塗料の製造）
・塗料Ａ
上記方法にて製造した主剤（１）と硬化剤（１）を８６：１４の重量比率で均一に混合して塗料Ａを得た。
(Manufacture of paint)
・ Paint A
The main agent (1) and the curing agent (1) produced by the above method were uniformly mixed at a weight ratio of 86:14 to obtain a coating material A.
・塗料Ｂ
上記方法にて製造した主剤（２）と硬化剤（１）を８６：１４の重量比率で均一に混合して塗料Ｂを得た。
・ Paint B
The base agent (2) and the curing agent (1) produced by the above method were uniformly mixed at a weight ratio of 86:14 to obtain a coating material B.
・塗料Ｃ
上記方法にて製造した主剤（３）と硬化剤（１）を８６：１４の重量比率で均一に混合して塗料Ｃを得た。
・ Paint C
The base agent (3) and the curing agent (1) produced by the above method were uniformly mixed at a weight ratio of 86:14 to obtain paint C.
（試験例１）
フィルムアプリケータ（隙間０．１５ｍｍ）を用いて塗料をコート紙に塗付し、標準状態（温度２３℃、相対湿度５０％）で４８時間乾燥させた後、その塗膜の色相を分光光度計により測定した。その結果、各塗料のＬ＊、ａ＊、ｂ＊はそれぞれ以下に示す通りとなった。塗料ＡのＬ＊が最も低く、複合顔料（１）の着色力が高いことが明らかとなった。
(Test Example 1)
The paint is applied to the coated paper using a film applicator (gap 0.15 mm), dried in a standard state (temperature 23 ° C., relative humidity 50%) for 48 hours, and then the hue of the coating film is measured with a spectrophotometer. It was measured by. As a result, L * , a * , and b * of each paint were as shown below. It became clear that L * of paint A was the lowest and the coloring power of the composite pigment (1) was high.
表１
―――――――――――――――――――――――――
│ │ Ｌ＊ ａ＊ ｂ＊ │
―――――――――――――――――――――――――
│ 塗料Ａ │ ４７．８ ０．９ ０．１ │
―――――――――――――――――――――――――
│ 塗料Ｂ │ ５０．１ ２．２ １．９ │
―――――――――――――――――――――――――
│ 塗料Ｃ │ ４９．６ ０．７ −０．１ │
―――――――――――――――――――――――――
Table 1
―――――――――――――――――――――――――
│ │ L * a * b * │
―――――――――――――――――――――――――
│ Paint A │ 47.8 0.9 0.1 │
―――――――――――――――――――――――――
│ Paint B │ 50.1 2.2 1.9 │
―――――――――――――――――――――――――
│ Paint C │ 49.6 0.7 -0.1 │
―――――――――――――――――――――――――
（試験例２）
塗料Ｂ及び塗料Ｃについては、塗料Ａとの色差が０．３以下となるように調色した。すなわち、塗料Ｂではビスマスマンガン系複合酸化物を追加混合し、塗料Ｃでは鉄クロム系複合酸化物及びフタロシアニンブルーを追加混合した。塗料Ａ、及び調色後の塗料Ｂ、Ｃについて、以下の試験を行った。
(Test Example 2)
About the coating material B and the coating material C, it color-matched so that the color difference with the coating material A might be 0.3 or less. That is, in paint B, a bismuth manganese composite oxide was additionally mixed, and in paint C, an iron chromium composite oxide and phthalocyanine blue were additionally mixed. The following tests were conducted for paint A and paints B and C after toning.
・遮熱性試験
アルミニウム板に対し、エポキシ系下塗材を乾燥膜厚が３０μｍとなるように塗装し、標準状態で８時間乾燥させた後、上記の方法によって得た塗料を乾燥膜厚が４０μｍとなるように塗装し、標準状態で７日間乾燥させることにより試験体を作製した。この試験体の塗膜に対し、赤外線ランプを４０ｃｍ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。試験結果を表２に示す。
・ Heat shielding test An aluminum base plate was coated with an epoxy-based primer to a dry film thickness of 30 μm, dried in a standard state for 8 hours, and then the paint obtained by the above method had a dry film thickness of 40 μm. A test specimen was prepared by coating the film and drying it under standard conditions for 7 days. The coating film of the test specimen was irradiated with an infrared lamp from a distance of 40 cm, and the test specimen back surface temperature when the temperature rise reached equilibrium was measured. The test results are shown in Table 2.
・耐候性試験
アルミニウム板に対し、エポキシ系下塗材を乾燥膜厚が３０μｍとなるように塗装し、標準状態で８時間乾燥させた後、上記の方法によって得た各塗料を乾燥膜厚が４０μｍとなるように塗装し、標準状態で７日間乾燥させることにより試験体を作製した。この試験体について、促進耐候性試験機としてアイスーパーＵＶテスター（岩崎電気株式会社製）を用い、光照射６時間・結露２時間（計８時間）を１サイクルとして４０サイクルまで促進試験を行い、促進前後の光沢保持率を算出した。試験結果を表２に示す。
-Weather resistance test An aluminum base plate was coated with an epoxy-based primer to a dry film thickness of 30 μm, dried in a standard state for 8 hours, and then each paint obtained by the above method had a dry film thickness of 40 μm. A test specimen was prepared by coating the film and drying it under standard conditions for 7 days. About this test body, an accelerated test was conducted up to 40 cycles using an iSuper UV tester (manufactured by Iwasaki Electric Co., Ltd.) as an accelerated weathering tester, with light irradiation 6 hours and condensation 2 hours (total 8 hours) as one cycle. The gloss retention before and after acceleration was calculated. The test results are shown in Table 2.
表２
─────────────────────────
│ │ 塗料Ａ │ 塗料Ｂ │ 塗料Ｃ │
─────────────────────────
│遮熱性試験│ ５７℃ │ ５８℃ ｜ ５８℃ ｜
─────────────────────────
│耐候性試験│ ９４％ │ ８９％ ｜ ８７％ ｜
─────────────────────────
Table 2
─────────────────────────
│ │ Paint A │ Paint B │ Paint C │
─────────────────────────
│ Thermal insulation test │ 57 ℃ │ 58 ℃ ｜ 58 ℃ ｜
─────────────────────────
│Weather resistance test │ 94% │ 89% │ 87% │
─────────────────────────
（試験例３）
上述の主剤（１）と硬化剤（２）を８６：１４の重量比率で均一に混合して塗料Ｄを得た。この塗料Ｄと上記塗料Ａについて、以下の試験を行った。
(Test Example 3)
The above-mentioned main agent (1) and curing agent (2) were uniformly mixed at a weight ratio of 86:14 to obtain paint D. The following tests were performed on the paint D and the paint A.
アルミニウム板に対し、エポキシ系下塗材を乾燥膜厚が３０μｍとなるように塗装し、標準状態で８時間乾燥させた後、塗料を乾燥膜厚が４０μｍとなるように塗装し、標準状態で７日間乾燥させることにより試験体を作製した。この試験体の塗膜全面に１５重量％カーボンブラック水分散ペースト液を均一に噴霧し、５０℃の恒温室中に２時間放置した。その後、ソニケーターを用いて、１０分間超音波洗浄を行い標準状態で２４時間放置した。以上の処理を行った試験体の塗膜に対し、赤外線ランプを４０ｃｍ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。その結果、塗料Ａ、塗料Ｄの裏面温度はそれぞれ６４℃、５７℃となった。 An aluminum base plate is coated with an epoxy-based primer to a dry film thickness of 30 μm, dried in a standard state for 8 hours, and then painted to a dry film thickness of 40 μm. A specimen was prepared by drying for one day. A 15% by weight carbon black aqueous dispersion paste was uniformly sprayed on the entire surface of the coating film of this test specimen, and left in a thermostatic chamber at 50 ° C. for 2 hours. Thereafter, ultrasonic cleaning was performed for 10 minutes using a sonicator, and the mixture was left in a standard state for 24 hours. An infrared lamp was irradiated from a distance of 40 cm to the coating film of the test body subjected to the above treatment, and the back surface temperature of the test body when the temperature rise reached equilibrium was measured. As a result, the back surface temperatures of paint A and paint D were 64 ° C. and 57 ° C., respectively.
Claims (1)
白色顔料の表面にビスマス複合酸化物からなる黒色顔料が固着された平均粒子径０．５〜５μｍの顔料
を含むことを特徴とする塗料組成物。 In the coating composition containing 1 to 200 parts by weight of the pigment with respect to 100 parts by weight of the solid content of the resin for coatings, and having a lightness (L * ) of the coating film of 30 to 95, as the pigment,
A coating composition comprising a pigment having an average particle size of 0.5 to 5 μm, wherein a black pigment composed of a bismuth composite oxide is fixed to the surface of a white pigment.
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| JP2008106092A (en) * | 2006-10-23 | 2008-05-08 | Agc Coat-Tech Co Ltd | Heat ray-highly reflecting coating material composition and coated article |
| WO2009006268A1 (en) * | 2007-06-28 | 2009-01-08 | E. I. Du Pont De Nemours And Company | Black pigment compositions, thick film black pigment compositions, conductive single layer thick film compositions, and black and conductive electrodes formed therefrom |
| JP2009242768A (en) * | 2008-02-29 | 2009-10-22 | Admatechs Co Ltd | Light ray reflective coating material and manufacturing method thereof |
| JP2010285587A (en) * | 2009-06-15 | 2010-12-24 | I C K Kk | Urethane-based coating film material and method for application |
| JP2011068737A (en) * | 2009-09-25 | 2011-04-07 | Toyo Ink Mfg Co Ltd | Aqueous dispersion having solar heat shield effect and method for producing aqueous coating composition |
| JP2012126766A (en) * | 2010-12-13 | 2012-07-05 | I C K Kk | Urethane-based coating film material and execution method |
| JP2013023624A (en) * | 2011-07-22 | 2013-02-04 | Kikusui Chemical Industries Co Ltd | Film composition |
| JP2013177615A (en) * | 2013-04-30 | 2013-09-09 | Agc Coat-Tech Co Ltd | Heat ray highly reflective paint composition and coated article |
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| JP2008106092A (en) * | 2006-10-23 | 2008-05-08 | Agc Coat-Tech Co Ltd | Heat ray-highly reflecting coating material composition and coated article |
| WO2009006268A1 (en) * | 2007-06-28 | 2009-01-08 | E. I. Du Pont De Nemours And Company | Black pigment compositions, thick film black pigment compositions, conductive single layer thick film compositions, and black and conductive electrodes formed therefrom |
| US7749321B2 (en) | 2007-06-28 | 2010-07-06 | E. I. Du Pont De Nemours And Company | Black pigment compositions, thick film black pigment compositions, conductive single layer thick film compositions, and black and conductive electrodes formed therefrom |
| JP2010531804A (en) * | 2007-06-28 | 2010-09-30 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Black pigment composition, thick film black pigment composition, conductive single layer thick film composition, and black conductive electrode formed therefrom |
| US7931746B2 (en) | 2007-06-28 | 2011-04-26 | E.I. Du Pont De Nemours And Company | Black pigment compositions, thick film black pigment compositions, conductive single layer thick film compositions, and black and conductive electrodes formed therefrom |
| JP2009242768A (en) * | 2008-02-29 | 2009-10-22 | Admatechs Co Ltd | Light ray reflective coating material and manufacturing method thereof |
| JP2010285587A (en) * | 2009-06-15 | 2010-12-24 | I C K Kk | Urethane-based coating film material and method for application |
| JP2011068737A (en) * | 2009-09-25 | 2011-04-07 | Toyo Ink Mfg Co Ltd | Aqueous dispersion having solar heat shield effect and method for producing aqueous coating composition |
| JP2012126766A (en) * | 2010-12-13 | 2012-07-05 | I C K Kk | Urethane-based coating film material and execution method |
| JP2013023624A (en) * | 2011-07-22 | 2013-02-04 | Kikusui Chemical Industries Co Ltd | Film composition |
| JP2013177615A (en) * | 2013-04-30 | 2013-09-09 | Agc Coat-Tech Co Ltd | Heat ray highly reflective paint composition and coated article |
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