JP5201405B2 - Infrared reflective black pigment, paint and resin composition using the infrared reflective black pigment - Google Patents

Infrared reflective black pigment, paint and resin composition using the infrared reflective black pigment Download PDF

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JP5201405B2
JP5201405B2 JP2008235730A JP2008235730A JP5201405B2 JP 5201405 B2 JP5201405 B2 JP 5201405B2 JP 2008235730 A JP2008235730 A JP 2008235730A JP 2008235730 A JP2008235730 A JP 2008235730A JP 5201405 B2 JP5201405 B2 JP 5201405B2
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black pigment
infrared reflective
infrared
reflective black
paint
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JP2010065201A (en
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和俊 真田
伸介 丸山
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Toda Kogyo Corp
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Description

本発明は、有害な元素を含有せず、しかも、優れた赤外線反射性を有する熱遮蔽性塗料を得ることができる赤外線反射性黒色顔料に関する。   The present invention relates to an infrared-reflective black pigment that does not contain harmful elements and that can provide a heat-shielding paint having excellent infrared reflectivity.

屋外で用いられている道路、建築物、備蓄タンク、自動車、船舶等は、太陽の日射によって内部温度が上昇するため、建築物及び自動車等の外観塗装を白色から淡色にすることで太陽光を反射させ、ある程度熱遮蔽効果を高めることが行われている。   Roads, buildings, stockpile tanks, automobiles, ships, etc. used outdoors increase the internal temperature due to solar radiation, so sunlight is reduced by changing the exterior paint of buildings and automobiles from white to light. It is reflected to increase the heat shielding effect to some extent.

しかしながら、殊に、屋外建築物の屋根などは、汚れを目立たなくするために、濃彩色から黒色を呈している場合が多く、外観塗装が濃彩色から黒色を有する建築物及び自動車等の場合には、淡色から白色の外観塗装を有する建築物及び自動車等に比べて太陽光を吸収しやすく、屋内の温度が著しく上昇する傾向にある。物品の輸送、保存に当たって、内部が高温になることは好ましいものではない。   However, in particular, the roofs of outdoor buildings are often dark to black in order to make the dirt inconspicuous, and in the case of buildings and automobiles etc. whose exterior paint has a dark to black color. Compared to buildings and automobiles having a light-to-white appearance paint, it is easier to absorb sunlight, and the indoor temperature tends to rise remarkably. It is not preferable that the temperature of the interior becomes high during transportation and storage of the article.

そこで、地球温暖化防止のためのエネルギー節約という観点からも、濃彩色から黒色の外観を有する建築物及び自動車等の内部温度の上昇を抑制することが強く望まれている。   Therefore, from the viewpoint of energy saving for preventing global warming, it is strongly desired to suppress an increase in internal temperature of buildings and automobiles having a dark to black appearance.

従来より、濃彩色から黒色の外観塗装を有する建築物及び自動車等の内部温度の上昇を低減するために、熱遮蔽性黒色塗料が知られている（例えば特許文献１〜３参照）。また、黒色度に優れたストロンチウム鉄酸化物ペロブスカイトが知られている（例えば特許文献４参照）。また、黒色度に優れたマグネシウム、アルミニウム含有酸化鉄が知られている（例えば特許文献５参照）。しかしながら次のような課題を有している。   Conventionally, heat-shielding black paints are known in order to reduce an increase in internal temperature of buildings and automobiles having a dark-colored to black appearance coating (see, for example, Patent Documents 1 to 3). In addition, strontium iron oxide perovskite having excellent blackness is known (for example, see Patent Document 4). Further, magnesium and aluminum-containing iron oxides having excellent blackness are known (see, for example, Patent Document 5). However, it has the following problems.

特許文献１には、ＣｏＯ、Ｃｒ２Ｏ３及びＦｅ２Ｏ３からなるスピネル構造を有する黒色焼成顔料が記載されているが、Ｃｒを含有するものであり、また、赤外線領域波長７８０〜２５００ｎｍにおける平均反射率が３０％未満であり、十分な遮熱効果を有するとは言い難いものであった。 Patent Document 1 describes a black calcined pigment having a spinel structure composed of CoO, Cr 2 O 3 and Fe 2 O 3 , which contains Cr and has an infrared region wavelength of 780 to 2500 nm. The average reflectance was less than 30%, and it was difficult to say that it had a sufficient heat shielding effect.

また、特許文献２には、Ｆｅ２Ｏ３を必須成分とし、Ｃｒ２Ｏ３、Ｍｎ２Ｏ３又はＮｉＯを含む焼成顔料からなる黒色顔料が記載されているが、Ｃｒを含有するものであるので好ましくない。 Patent Document 2 describes a black pigment composed of a calcined pigment containing Fe 2 O 3 as an essential component and containing Cr 2 O 3 , Mn 2 O 3, or NiO, but contains Cr. Therefore, it is not preferable.

また、特許文献３には、希土類元素、アルカリ土類金属及び鉄からなる黒色複合酸化物が記載されているが、十分な遮熱効果を有するとは言い難いものであった。   Patent Document 3 describes a black complex oxide composed of rare earth elements, alkaline earth metals, and iron, but it is difficult to say that it has a sufficient heat shielding effect.

また、特許文献４には、黒色度に優れたストロンチウム鉄酸化物ペロブスカイトが記載されているが、可視光領域波長２５０〜７８０ｎｍにおける平均反射率が１０％以下であって、且つ、赤外線領域波長７８０〜２５００ｎｍにおける平均反射率が３０％未満であるので、十分な遮熱効果は得られていない。   Patent Document 4 describes a strontium iron oxide perovskite having excellent blackness, but has an average reflectance of 10% or less at a visible light region wavelength of 250 to 780 nm and an infrared region wavelength of 780. Since the average reflectance at ˜2500 nm is less than 30%, a sufficient heat shielding effect is not obtained.

また、特許文献５には、黒色度に優れたマグネシウム、アルミニウム含有スピネルが記載されているが、可視光領域波長２５０〜７８０ｎｍにおける平均反射率が１０％以下であって、且つ、赤外線領域波長７８０〜２５００ｎｍにおける平均反射率が３０％未満であるので、十分な遮熱効果は得られていない。   Patent Document 5 describes magnesium-aluminum-containing spinels with excellent blackness, but has an average reflectance of 10% or less at a visible light region wavelength of 250 to 780 nm and an infrared region wavelength of 780. Since the average reflectance at ˜2500 nm is less than 30%, a sufficient heat shielding effect is not obtained.

また、ＣｕＯは、黒色顔料として黒色度に優れかつ熱遮蔽性に優れるが、耐酸性に課題がある。一方でＣｕＯ−Ｃｒ２Ｏ３を主成分とする顔料は、日射反射率及び近赤外線反射率が低いとの実験データも開示されている（例えば特許文献６参照）。 Further, CuO is excellent in blackness and heat shielding property as a black pigment, but has a problem in acid resistance. On the other hand, experimental data that a pigment mainly composed of CuO—Cr 2 O 3 has low solar reflectance and near infrared reflectance is also disclosed (for example, see Patent Document 6).

上記課題を解決するため、本出願人は、有害な元素を含有せず、しかも優れた赤外線反射性を有する赤外線反射性黒色顔料を開発し既に特許出願を行っている（特許文献７参照）。この黒色顔料は、ＦｅとＣｏとＡｌを含有し、更に、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｔｉ、Ｚｎ、Ｓｎ、Ｚｒ、Ｓｉ及びＣｕから選ばれる一種以上の金属元素を含有する複合酸化物からなる黒色顔料であって、該黒色顔料の平均粒子径が０．０２〜２．０μｍである赤外線反射性黒色顔料であり、有害な元素を含有せず、しかも優れた赤外線反射性を有する。しかしながら、赤外線領域波長１５００ｎｍの反射率が不十分である。   In order to solve the above problems, the present applicant has developed an infrared reflective black pigment that does not contain harmful elements and has excellent infrared reflectivity, and has already filed a patent application (see Patent Document 7). This black pigment contains Fe, Co, and Al, and further includes a composite oxide containing one or more metal elements selected from Mg, Ca, Sr, Ba, Ti, Zn, Sn, Zr, Si, and Cu. The black pigment is an infrared reflective black pigment having an average particle diameter of 0.02 to 2.0 μm, does not contain harmful elements, and has excellent infrared reflectivity. However, the reflectance in the infrared region wavelength of 1500 nm is insufficient.

特開２０００−７２９９０号公報JP 2000-72990 A 特開２００１−３１１０４９号公報JP 2001-311049 A 特開２００４−８３６１６号公報JP 2004-83616 A 特開２０００−２６４６３９号公報JP 2000-264639 A 特開２００３−２３８１６４号公報JP 2003-238164 A 特開２００２−３３１６１１号公報JP 2002-331611 A 特開２００７−１９７５７０号公報JP 2007-197570 A

有害な元素を含有せず、しかも、優れた赤外線反射性を有し、赤外線領域波長１５００ｎｍにおいても高い反射率を有する熱遮蔽性塗料を得ることができる黒色顔料は、現在最も要求されているところである。さらにこれら黒色顔料が、塗料構成基材に対し優れた分散性、分散安定性を有し、塗料としての優れた貯蔵安定性を有することが好ましいことは言うに及ばない。   A black pigment that does not contain harmful elements, has excellent infrared reflectivity, and can obtain a heat-shielding coating material having high reflectivity even in the infrared region wavelength of 1500 nm is currently most demanded. is there. Furthermore, it goes without saying that these black pigments preferably have excellent dispersibility and dispersion stability with respect to the base material constituting the paint and have excellent storage stability as a paint.

本発明の目的は、有害な元素を含有せず、しかも優れた赤外線反射性を有し、赤外線領域波長１５００ｎｍにおいても高い反射率を有する赤外線反射性黒色顔料を提供することである。   An object of the present invention is to provide an infrared reflective black pigment which does not contain a harmful element, has excellent infrared reflectivity, and has a high reflectance even at an infrared region wavelength of 1500 nm.

前記目的は、次の通りの本発明によって達成できる。   The object can be achieved by the present invention as follows.

即ち、本発明は、実質的にＣｒを含有せず、少なくともＣｏ、Ｍｇ、Ｆｅ、Ａｌ及びＣｕを含有する複合酸化物からなる黒色顔料であって、Ｃｕ／（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）がモル比で１０〜９０％であり、該黒色顔料の平均粒子径が０．０２〜２．０μｍであることを特徴とする赤外線反射性黒色顔料である（本発明１）。   That is, the present invention is a black pigment composed of a composite oxide substantially free of Cr and containing at least Co, Mg, Fe, Al and Cu, wherein Cu / (Co + Mg + Fe + Al + Cu) is 10 to 10 in molar ratio. It is 90%, and the black pigment has an average particle diameter of 0.02 to 2.0 μm (invention 1).

また本発明は、請求項１記載の赤外線反射性黒色顔料の（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）／全金属元素がモル比で５０〜１００％であることを特徴とする赤外線反射性黒色顔料である（本発明２）。   Further, the present invention is an infrared reflective black pigment characterized in that (Co + Mg + Fe + Al + Cu) / total metal elements of the infrared reflective black pigment according to claim 1 is 50 to 100% in molar ratio (Invention 2). .

また本発明は、請求項１又は２記載の赤外線反射性黒色顔料の明度（Ｌ＊）が３０以下であることを特徴とする赤外線反射性黒色顔料である（本発明３）。 In addition, the present invention is an infrared reflective black pigment characterized in that the lightness (L * ) of the infrared reflective black pigment according to claim 1 or 2 is 30 or less (Invention 3).

また本発明は、請求項１乃至３のいずれか１項に記載の赤外線反射性黒色顔料の日射反射率が２５％以上であり、かつ赤外線領域波長１５００ｎｍの反射率が２３％以上であることを特徴とする赤外線反射性黒色顔料である（本発明４）。   In the present invention, the infrared reflective black pigment according to any one of claims 1 to 3 has a solar reflectance of 25% or more, and a reflectance at an infrared region wavelength of 1500 nm is 23% or more. It is a characteristic infrared reflective black pigment (Invention 4).

また本発明は、請求項１乃至４のいずれか１項に記載の赤外線反射性黒色顔料の表面がＳｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる一種以上の化合物で被覆されていることを特徴とする赤外線反射性黒色顔料である（本発明５）。   The present invention is also characterized in that the surface of the infrared reflective black pigment according to any one of claims 1 to 4 is coated with one or more compounds selected from Si, Al, Zr, and Ti. It is an infrared reflective black pigment (Invention 5).

また本発明は、請求項１乃至５のいずれか１項に記載の赤外線反射性黒色顔料を塗料構成基材中に配合したことを特徴とする塗料である（本発明６）。   Moreover, this invention is the coating material which mix | blended the infrared reflective black pigment of any one of Claim 1 thru | or 5 in the coating-material base material (this invention 6).

また本発明は、請求項１乃至５のいずれか１項に記載の赤外線反射性黒色顔料を用いて着色したことを特徴とする樹脂組成物である（本発明７）。   Moreover, this invention is the resin composition characterized by having colored using the infrared reflective black pigment of any one of Claims 1 thru | or 5. (Invention 7).

本発明に係る赤外線反射性黒色顔料は、有害な元素を含有しない黒色顔料であって、しかも優れた赤外線反射性を有し、赤外線領域波長１５００ｎｍにおいても高い反射率を有するので赤外線反射性黒色顔料として好適である。   The infrared reflective black pigment according to the present invention is a black pigment that does not contain harmful elements, has excellent infrared reflectivity, and has high reflectivity even in the infrared region wavelength of 1500 nm. It is suitable as.

本発明の構成をより詳しく説明すれば次の通りである。   The configuration of the present invention will be described in more detail as follows.

先ず、本発明に係る赤外線反射性黒色顔料について述べる。   First, the infrared reflective black pigment according to the present invention will be described.

本発明に係る赤外線反射性黒色顔料は、実質的にＣｒを含有せず、少なくともＣｏ、Ｍｇ、Ｆｅ、Ａｌ及びＣｕを含有する複合酸化物からなる黒色顔料であって、Ｃｕ／（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）がモル比で１０〜９０％である。黒色顔料中のＣｕ／（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）がモル比で１０％未満となると赤外線領域波長１５００ｎｍの反射率が十分に高いとは言えず、Ｃｕ／（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）がモル比で９０％を超えると真比重が大きくなり過ぎ、塗料としたとき黒色顔料が沈降分離する場合がある。実質的にＣｒを含有しないとは、不可避的に各種原料由来の不純物が混入する場合もあるけれども、この場合であっても、Ｃｒの含有量は１ｗｔ％以下であり、殊に、Ｃｒ６＋の含有量は１０ｐｐｍ以下である。 The infrared reflective black pigment according to the present invention is a black pigment that is substantially free of Cr and is composed of a composite oxide containing at least Co, Mg, Fe, Al, and Cu, and Cu / (Co + Mg + Fe + Al + Cu). The molar ratio is 10 to 90%. When the molar ratio of Cu / (Co + Mg + Fe + Al + Cu) in the black pigment is less than 10%, it cannot be said that the reflectance in the infrared region wavelength of 1500 nm is sufficiently high, and when the molar ratio of Cu / (Co + Mg + Fe + Al + Cu) exceeds 90% Becomes too large, and the black pigment may settle and separate when used as a paint. The fact that it does not substantially contain Cr may inevitably contain impurities derived from various raw materials, but even in this case, the Cr content is 1 wt% or less, and in particular, Cr 6+ The content is 10 ppm or less.

また本発明に係る赤外線反射性黒色顔料の平均粒子径は０．０２〜２．０μｍである。平均粒子径が２．０μｍを超える場合には、粒子サイズが大きすぎるため、着色力が低下する。平均粒子径が０．０２μｍ未満の場合には、ビヒクル中への分散が困難となる場合がある。好ましくは０．０２５〜１．５μｍ、より好ましくは０．０４〜１．２μｍである。   Moreover, the average particle diameter of the infrared reflective black pigment which concerns on this invention is 0.02-2.0 micrometers. When the average particle diameter is more than 2.0 μm, the particle size is too large and the coloring power is lowered. When the average particle size is less than 0.02 μm, dispersion in the vehicle may be difficult. Preferably it is 0.025-1.5 micrometers, More preferably, it is 0.04-1.2 micrometers.

本発明に係る赤外線反射性黒色顔料は、（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）／全金属元素がモル比で５０〜１００％が好ましい。これから分かるように、本発明に係る赤外線反射性黒色顔料は、Ｃｏ、Ｍｇ、Ｆｅ、Ａｌ及びＣｕを含有する複合酸化物からなる黒色顔料であってよく、さらに所定の量の他の金属元素を含む複合酸化物からなる黒色顔料であってよい。これらの場合、不可避的に各種原料由来の不純物が混入する場合もあるけれども、この場合であっても、Ｃｒの含有量は１ｗｔ％以下であり、殊に、Ｃｒ６＋の含有量は１０ｐｐｍ以下である。 In the infrared reflective black pigment according to the present invention, (Co + Mg + Fe + Al + Cu) / all metal elements are preferably 50 to 100% in molar ratio. As can be seen, the infrared reflective black pigment according to the present invention may be a black pigment made of a complex oxide containing Co, Mg, Fe, Al, and Cu, and a predetermined amount of another metal element. It may be a black pigment made of a complex oxide. In these cases, impurities derived from various raw materials may be inevitably mixed, but even in this case, the Cr content is 1 wt% or less, and in particular, the Cr 6+ content is 10 ppm or less. is there.

Ｃｏの含有量は、黒色顔料中の全金属元素に対して、１〜２０モル％が好ましく、２〜１６モル％がより好ましく、Ｍｇの含有量は、黒色顔料中の全金属元素に対して、１〜５０モル％が好ましく、２〜３０モル％がより好ましい。Ｆｅ及びＡｌの含有量は、共に黒色顔料中の全金属元素に対して、１〜５０モル％が好ましく、２〜４０モル％がより好ましい。   The Co content is preferably from 1 to 20 mol%, more preferably from 2 to 16 mol%, based on all metal elements in the black pigment, and the Mg content is based on all metal elements in the black pigment. 1-50 mol% is preferable, and 2-30 mol% is more preferable. The content of Fe and Al is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, based on all metal elements in the black pigment.

また本発明に係る赤外線反射性黒色顔料は、真比重（密度）が４．７〜６．１であることが好ましい。真比重が上記範囲内であれば、塗料構成基材に本発明に係る赤外線反射性黒色顔料を分散させたとき、塗料構成基材に対し優れた分散性、分散安定性、塗料としての優れた貯蔵安定性を有する。   The infrared reflective black pigment according to the present invention preferably has a true specific gravity (density) of 4.7 to 6.1. If the true specific gravity is within the above range, when the infrared reflective black pigment according to the present invention is dispersed in the paint constituent base material, the dispersibility, dispersion stability, and excellent paint as a paint constituent base material are excellent. Has storage stability.

本発明に係る赤外線反射性黒色顔料のＢＥＴ比表面積は、１〜１００ｍ２／ｇが好ましい。ＢＥＴ比表面積が１ｍ２／ｇ未満の場合には、粒子が粗大であったり、粒子及び粒子相互間で焼結が生じた粒子となっており、着色力が低下する。より好ましくは１．５〜７５ｍ２／ｇ、更により好ましくは１．８〜６０ｍ２／ｇである。 The BET specific surface area of the infrared reflective black pigment according to the present invention is preferably 1 to 100 m 2 / g. When the BET specific surface area is less than 1 m 2 / g, the particles are coarse or the particles are sintered between the particles and the coloring power is reduced. More preferably, it is 1.5-75 m < 2 > / g, More preferably, it is 1.8-60 m < 2 > / g.

本発明に係る赤外線反射性黒色顔料の明度（Ｌ＊）は、上限値が３０．０程度である。明度（Ｌ＊）が３０を超える場合には、黒色度に優れるとは言い難い。より好ましくは２６以下である。 The upper limit of the lightness (L * ) of the infrared reflective black pigment according to the present invention is about 30.0. When the lightness (L * ) exceeds 30, it is difficult to say that the blackness is excellent. More preferably, it is 26 or less.

本発明に係る赤外線反射性黒色顔料のａ＊は、−５〜＋１０が好ましい。ａ＊が前記範囲外の場合には、黒色度に優れるとは言い難い。より好ましくは−１〜＋５である。 The a * of the infrared reflective black pigment according to the present invention is preferably −5 to +10. When a * is outside the above range, it is difficult to say that the blackness is excellent. More preferably, it is -1 to +5.

本発明に係る赤外線反射性黒色顔料のｂ＊は、−５〜＋１０が好ましい。ｂ＊が前記範囲外の場合には、黒色度に優れるとは言い難い。より好ましくは−１〜＋５である。 The b * of the infrared reflective black pigment according to the present invention is preferably -5 to +10. When b * is outside the above range, it is difficult to say that the blackness is excellent. More preferably, it is -1 to +5.

本発明に係る赤外線反射性黒色顔料の赤外線反射性は、波長３００〜２１００ｎｍの平均反射率で示される日射反射率が２５％以上であることが好ましい。日射反射率が２５％未満では、日射反射率が十分に高いとは言えない。また赤外線領域波長１５００ｎｍの反射率が２３％以上であることが好ましい。赤外線領域波長１５００ｎｍの反射率が２３％未満では、赤外線領域波長１５００ｎｍの反射率が十分とは言えない。また赤外線領域波長１０００ｎｍの反射率が５７％を超えることが好ましい。   As for the infrared reflectivity of the infrared reflective black pigment according to the present invention, it is preferable that the solar reflectance shown by the average reflectivity at a wavelength of 300 to 2100 nm is 25% or more. If the solar reflectance is less than 25%, it cannot be said that the solar reflectance is sufficiently high. Moreover, it is preferable that the reflectance of infrared region wavelength 1500nm is 23% or more. If the reflectance at an infrared region wavelength of 1500 nm is less than 23%, the reflectance at an infrared region wavelength of 1500 nm cannot be said to be sufficient. Moreover, it is preferable that the reflectance of infrared region wavelength 1000nm exceeds 57%.

本発明においては、粒子表面をＳｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる１種又は２種以上の化合物によって被覆することが好ましい。後述の実施例で示すように粒子表面をＳｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる１種又は２種以上の化合物によって被覆することで、耐酸性が向上する。被覆量は赤外線反射性黒色顔料に対して０．１〜１０ｗｔ％が好ましい。   In the present invention, the particle surface is preferably coated with one or more compounds selected from Si, Al, Zr, and Ti. As shown in the examples described later, the acid resistance is improved by coating the particle surface with one or more compounds selected from Si, Al, Zr, and Ti. The coating amount is preferably 0.1 to 10 wt% with respect to the infrared reflective black pigment.

次に、本発明に係る赤外線反射性黒色顔料の製造法について述べる。   Next, the manufacturing method of the infrared reflective black pigment which concerns on this invention is described.

本発明に係る赤外線反射性黒色顔料は、各種原料を混合、焼成して得ることができる。   The infrared reflective black pigment according to the present invention can be obtained by mixing and firing various raw materials.

出発原料は、前記各金属元素の酸化物、炭酸塩、硝酸塩、硫酸塩などを用いることができる。   As the starting material, oxides, carbonates, nitrates, sulfates and the like of the respective metal elements can be used.

出発原料の混合は、均一に混合することができれば、特に限定されるものではなく、湿式混合でも乾式混合でもよい。また湿式合成であってもよい。   The mixing of the starting materials is not particularly limited as long as the starting materials can be uniformly mixed, and may be wet mixing or dry mixing. Also, wet synthesis may be used.

加熱焼成温度は８００〜１２００℃が好ましく、８００〜１１５０℃がより好ましい。加熱雰囲気は大気中である。   800-1200 degreeC is preferable and the heat-firing temperature has more preferable 800-1150 degreeC. The heating atmosphere is air.

加熱後の粉末は、常法に従って、水洗、粉砕を行えばよい。   The heated powder may be washed and pulverized according to a conventional method.

本発明においては、赤外線反射性黒色顔料の粒子表面をＳｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる１種又は２種以上の化合物によって被覆しておいてもよい。表面処理方法は、湿式あるいは乾式方法等の常法に従って行えばよい。例えば、湿式方法は湿式分散した赤外線反射性黒色顔料のスラリーに、Ｓｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる１種又は２種以上の可溶性化合物を、酸又はアルカリでｐＨ調整しながら添加・混合して被覆する方法、乾式方法はヘンシェルミキサーなどの装置中で赤外線反射性黒色顔料にＳｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる１種又は２種以上のカップリング剤などにより被覆処理する方法である。   In the present invention, the particle surface of the infrared reflective black pigment may be coated with one or more compounds selected from Si, Al, Zr, and Ti. The surface treatment method may be performed according to a conventional method such as a wet method or a dry method. For example, in the wet method, one or two or more soluble compounds selected from Si, Al, Zr, and Ti are added to and mixed with a slurry of a wet-dispersed infrared reflective black pigment while adjusting the pH with an acid or alkali. The coating method and the dry method are methods in which an infrared reflective black pigment is coated with one or more coupling agents selected from Si, Al, Zr, and Ti in an apparatus such as a Henschel mixer.

次に、本発明に係る赤外線反射性黒色顔料を配合した塗料について述べる。   Next, a paint containing the infrared reflective black pigment according to the present invention will be described.

本発明に係る塗料中における赤外線反射性黒色顔料の配合割合は、塗料構成基材１００重量部に対して０．５〜１００重量部の範囲で使用することができ、塗料のハンドリング性を考慮すれば、好ましくは１．０〜１００重量部である。   The blending ratio of the infrared reflective black pigment in the paint according to the present invention can be used in the range of 0.5 to 100 parts by weight with respect to 100 parts by weight of the paint base material, and the handleability of the paint is taken into consideration. For example, it is preferably 1.0 to 100 parts by weight.

塗料構成基材としては、樹脂、溶剤、必要により油脂、消泡剤、体質顔料、乾燥促進剤、界面活性剤、硬化促進剤、助剤等が配合される。   As the paint constituent base material, a resin, a solvent, and if necessary, fats and oils, an antifoaming agent, an extender pigment, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent and the like are blended.

樹脂としては、溶剤系塗料用や油性印刷インクに通常使用されているアクリル樹脂、アルキッド樹脂、ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、フェノール樹脂、メラミン樹脂、アミノ樹脂、塩化ビニル樹脂、シリコーン樹脂、ガムロジン、ライムロジン等のロジン系樹脂、マレイン酸樹脂、ポリアミド樹脂、ニトロセルロース、エチレン−酢酸ビニル共重合樹脂、ロジン変性フェノール樹脂、ロジン変性マレイン酸樹脂等のロジン変性樹脂、石油樹脂等を用いることができる。水系塗料用としては、水系塗料用や水性インクに通常使用されている水溶性アクリル樹脂、水溶性スチレン−マレイン酸樹脂、水溶性アルキッド樹脂、水溶性メラミン樹脂、水溶性ウレタンエマルジョン樹脂、水溶性エポキシ樹脂、水溶性ポリエステル樹脂等を用いることができる。   Resins include acrylic resin, alkyd resin, polyester resin, polyurethane resin, epoxy resin, phenol resin, melamine resin, amino resin, vinyl chloride resin, silicone resin, gum rosin that are usually used for solvent-based paints and oil-based printing inks. Rosin resins such as lime rosin, maleic acid resin, polyamide resin, nitrocellulose, ethylene-vinyl acetate copolymer resin, rosin modified phenolic resin, rosin modified maleic resin and other rosin modified resins, petroleum resins and the like can be used. . For water-based paints, water-soluble acrylic resins, water-soluble styrene-maleic acid resins, water-soluble alkyd resins, water-soluble melamine resins, water-soluble urethane emulsion resins, water-soluble epoxies commonly used for water-based paints and water-based inks Resins, water-soluble polyester resins, and the like can be used.

溶剤としては、溶剤系塗料用に通常使用されている大豆油、トルエン、キシレン、シンナー、ブチルアセテート、メチルアセテート、メチルイソブチルケトン、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ、プロピレングリコールモノメチルエーテル等のグリコールエーテル系溶剤、酢酸エチル、酢酸ブチル、酢酸アミル等のエステル系溶剤、ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素系溶剤、シクロヘキサン等の脂環族炭化水素系溶剤、ミネラルスピリット等の石油系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、メチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール等のアルコール系溶剤、脂肪族炭化水素等を用いることができる。   Solvents include soybean oil, toluene, xylene, thinner, butyl acetate, methyl acetate, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, propyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, etc. Glycol ether solvents, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, alicyclic hydrocarbon solvents such as cyclohexane, and petroleum-based solvents such as mineral spirits Solvents, ketone solvents such as acetone and methyl ethyl ketone, alcohol solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, aliphatic hydrocarbons, and the like can be used.

水系塗料用溶剤としては、水と水系塗料用に通常使用されているエチルアルコール、プロピルアルコール、ブチルアルコール等のアルコール系溶剤、メチルセロソルブ、エチルセロソルブ、プロピルセロソルブ、ブチルセロソルブ等のグリコールエーテル系溶剤、ジエチレングリコール、トリエチレングリコール、ポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリプロピレングリコール等のオキシエチレン又はオキシプロピレン付加重合体、エチレングリコール、プロピレングリコール、１，２，６−ヘキサントリオール等のアルキレングリコール、グリセリン、２−ピロリドン等の水溶性有機溶剤とを混合して使用することができる。   Water-based paint solvents include water and alcohol-based solvents usually used for water-based paints, such as ethyl alcohol, propyl alcohol, and butyl alcohol, methyl ether solvents such as methyl cellosolve, ethyl cellosolve, propyl cellosolve, and butyl cellosolve, and diethylene glycol. , Oxyethylene or oxypropylene addition polymers such as triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, alkylene glycol such as ethylene glycol, propylene glycol, 1,2,6-hexanetriol, glycerin, It can be used by mixing with a water-soluble organic solvent such as 2-pyrrolidone.

油脂としては、あまに油、きり油、オイチシカ油、サフラワー油等の乾性油を加工したボイル油を用いることができる。   As oils and fats, boil oils obtained by processing dry oils such as linseed oil, persimmon oil, sea lion oil, safflower oil and the like can be used.

消泡剤としては、ノプコ８０３４（商品名）、ＳＮデフォーマー４７７（商品名）、ＳＮデフォーマー５０１３（商品名）、ＳＮデフォーマー２４７（商品名）、ＳＮデフォーマー３８２（商品名）（以上、いずれもサンノプコ株式会社製）、アンチホーム０８（商品名）、エマルゲン９０３（商品名）（以上、いずれも花王株式会社製）等の市販品を使用することができる。   Antifoaming agents include Nopco 8034 (product name), SN deformer 477 (product name), SN deformer 5013 (product name), SN deformer 247 (product name), SN deformer 382 (product name) (all of these are San Nopco Commercially available products such as manufactured by Co., Ltd., Antihome 08 (trade name), Emulgen 903 (trade name) (all of which are manufactured by Kao Corporation) can be used.

次に、本発明に係る赤外線反射性黒色顔料を含有する樹脂組成物について述べる。   Next, the resin composition containing the infrared reflective black pigment according to the present invention will be described.

本発明に係る樹脂組成物中における赤外線反射性黒色顔料の配合割合は、樹脂１００重量部に対して０．０１〜２００重量部の範囲で使用することができ、樹脂組成物のハンドリング性を考慮すれば、好ましくは０．０５〜１５０重量部、更に好ましくは０．１〜１００重量部である。   The blending ratio of the infrared reflective black pigment in the resin composition according to the present invention can be used in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the resin, and the handling property of the resin composition is taken into consideration. Thus, the amount is preferably 0.05 to 150 parts by weight, more preferably 0.1 to 100 parts by weight.

本発明に係る樹脂組成物における構成基材としては、赤外線反射性黒色顔料と周知の熱可塑性樹脂とともに、必要により、滑剤、可塑剤、酸化防止剤、紫外線吸収剤、各種安定剤等の添加剤が配合される。   As a constituent substrate in the resin composition according to the present invention, an additive such as a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, and various stabilizers, if necessary, together with an infrared reflective black pigment and a known thermoplastic resin. Is blended.

樹脂としては、ポリエチレン、ポリプロピレン、ポリブテン、ポリイソブチレン等のポリオレフィン、ポリ塩化ビニル、ポリメチルペンテン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスチレン、スチレン−アクリル酸エステル共重合体、スチレン−酢酸ビニル共重合体、アクリロニトリル−ブタジエン−スチレン共重合体、アクリロニトリル−ＥＰＤＭ−スチレン共重合体、アクリル系樹脂、ポリアミド、ポリカーボネート、ポリアセタール、ポリウレタン等の熱可塑性樹脂、ロジン変性マレイン酸樹脂、フェノール樹脂、エポキシ樹脂、ポリエステル樹脂、シリコーン樹脂、ロジン・エステル、ロジン、天然ゴム、合成ゴム等を用いることができる。   Examples of the resin include polyolefins such as polyethylene, polypropylene, polybutene, and polyisobutylene, polyvinyl chloride, polymethylpentene, polyethylene terephthalate, polybutylene terephthalate, polystyrene, styrene-acrylic acid ester copolymer, styrene-vinyl acetate copolymer, Acrylonitrile-butadiene-styrene copolymer, acrylonitrile-EPDM-styrene copolymer, acrylic resin, polyamide, polycarbonate, polyacetal, polyurethane and other thermoplastic resins, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, Silicone resin, rosin ester, rosin, natural rubber, synthetic rubber and the like can be used.

添加剤の量は、赤外線反射性黒色顔料と樹脂との総和に対して５０重量％以下であればよい。添加剤の含有量が５０重量％を超える場合には、成形性が低下する。   The amount of the additive may be 50% by weight or less based on the sum of the infrared reflective black pigment and the resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.

本発明に係る樹脂組成物は、樹脂原料と赤外線反射性黒色顔料をあらかじめよく混合し、次に、混練機もしくは押出機を用いて加熱下で強いせん断作用を加えて、赤外線反射性黒色顔料の凝集体を破壊し、樹脂組成物中に赤外線反射性黒色顔料を均一に分散させた後、目的に応じた形状に成形加工して使用する。   The resin composition according to the present invention is prepared by mixing a resin raw material and an infrared reflective black pigment in advance, and then applying a strong shearing action under heating using a kneader or an extruder to produce an infrared reflective black pigment. The aggregate is broken and the infrared reflective black pigment is uniformly dispersed in the resin composition, and then molded into a shape suitable for the purpose.

また本発明に係る樹脂組成物は、マスターバッチペレットを経由して得ることもできる。   The resin composition according to the present invention can also be obtained via a master batch pellet.

本発明におけるマスターバッチペレットは、塗料及び樹脂組成物の構成基材としての結合材樹脂と前記赤外線反射性黒色顔料とを必要により、リボンブレンダー、ナウターミキサー、ヘンシェルミキサー、スーパーミキサー等の混合機で混合した後、周知の単軸混練押出機や二軸混練押出機等で混練、成形した後切断するか、又は、上記混合物をバンバリーミキサー、加圧ニーダー等で混練して得られた混練物を粉砕又は成形、切断することにより製造される。   The master batch pellet in the present invention requires a binder resin as a constituent substrate of the paint and the resin composition and the infrared reflective black pigment, and a mixer such as a ribbon blender, a Nauter mixer, a Henschel mixer, a super mixer, etc. Kneaded with a well-known single-screw kneading extruder or twin-screw kneading extruder, etc., then cut, or kneaded by mixing the above mixture with a Banbury mixer, pressure kneader, etc. It is manufactured by crushing, molding or cutting.

結合材樹脂と赤外線反射性黒色顔料の混練機への供給は、それぞれを所定比率で定量供給してもよいし、両者の混合物を供給してもよい。   As for the supply of the binder resin and the infrared reflective black pigment to the kneader, each of them may be supplied at a predetermined ratio, or a mixture of both may be supplied.

本発明におけるマスターバッチペレットは、平均長径１〜６ｍｍ、好ましくは２〜５ｍｍの範囲である。平均短径は２〜５ｍｍ、好ましくは２．５〜４ｍｍである。平均長径が１ｍｍ未満の場合には、ペレット製造時の作業性が悪く好ましくない。６ｍｍを超える場合には、希釈用結合材樹脂の大きさとの違いが大きく、十分に分散させるのが困難となる。また、その形状は種々のものができ、不定形及び球形等の粒状、円柱形、フレーク状等にできる。   The master batch pellet in the present invention has an average major axis of 1 to 6 mm, preferably 2 to 5 mm. The average minor axis is 2 to 5 mm, preferably 2.5 to 4 mm. When the average major axis is less than 1 mm, the workability at the time of producing the pellet is poor, which is not preferable. When the thickness exceeds 6 mm, the difference from the size of the binder resin for dilution is large, and it becomes difficult to sufficiently disperse. Moreover, the shape can be various, and can be indefinite and spherical, cylindrical, flakes, and the like.

本発明におけるマスターバッチペレットに使用する結合材樹脂としては、前記樹脂組成物用樹脂と同一の樹脂が使用できる。   As the binder resin used for the master batch pellet in the present invention, the same resin as the resin for resin composition can be used.

なお、マスターバッチペレット中の結合材樹脂の組成は、希釈用結合材樹脂と同一の樹脂を用いても、また、異なる樹脂を用いてもよいが、異なる樹脂を使用する場合には、樹脂同士の相溶性により決まる諸特性を考慮して決めればよい。   The composition of the binder resin in the masterbatch pellet may be the same resin as the diluent binder resin or a different resin, but if different resins are used, What is necessary is just to determine in consideration of the various characteristics determined by the compatibility.

マスターバッチペレット中に配合される赤外線反射性黒色顔料の量は、結合材樹脂１００重量部に対して１〜２００重量部、好ましくは１〜１５０重量部、より好ましくは１〜１００重量部である。１重量部未満の場合には、混練時の溶融粘度が不足し、赤外線反射性黒色顔料の良好な分散混合が困難である。２００重量部を超える場合には、赤外線反射性黒色顔料に対する結合材樹脂が少ないため、赤外線反射性黒色顔料の良好な分散混合が難しく、また、マスターバッチペレットの添加量のわずかな変化によって樹脂組成物中に配合される赤外線反射性黒色顔料の含有量が大きく変化するため所望の含有量に調製することが困難となり好ましくない。また、機械摩耗が激しく適当ではない。   The amount of the infrared reflective black pigment blended in the master batch pellet is 1 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the binder resin. . When the amount is less than 1 part by weight, the melt viscosity at the time of kneading is insufficient, and it is difficult to achieve good dispersion and mixing of the infrared reflective black pigment. When the amount exceeds 200 parts by weight, since there is little binder resin for the infrared reflective black pigment, good dispersion and mixing of the infrared reflective black pigment is difficult, and the resin composition can be changed by a slight change in the addition amount of the master batch pellet. Since the content of the infrared-reflective black pigment blended in the product greatly changes, it is difficult to prepare the desired content, which is not preferable. Also, mechanical wear is severe and not suitable.

＜作用＞
本発明において最も重要な点は、本発明に係る赤外線反射性黒色顔料は、有害元素を含有することなく、高い赤外線反射性を有し、赤外線領域波長１５００ｎｍにおいても高い反射率を有するという事実である。 <Action>
The most important point in the present invention is the fact that the infrared reflective black pigment according to the present invention does not contain harmful elements, has high infrared reflectivity, and has high reflectivity even in the infrared region wavelength of 1500 nm. is there.

本発明に係る赤外線反射性黒色顔料が高い赤外線反射性を有する理由は、未だ明らかではないが、後出する実施例及び比較例から明らかなとおり、実質的にＣｒを含有せず、少なくともＣｏ、Ｍｇ、Ｆｅ、Ａｌ及びＣｕを含有する複合酸化物からなり、Ｃｕ／（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）をモル比で１０〜９０％、平均粒子径を０．０２〜２．０μｍとすることで、赤外線領域波長１５００ｎｍの反射率も含め赤外線反射率を向上させることができたものである。   The reason why the infrared-reflective black pigment according to the present invention has high infrared reflectivity is not yet clear, but as is apparent from Examples and Comparative Examples described later, substantially does not contain Cr, at least Co, It consists of a complex oxide containing Mg, Fe, Al and Cu, Cu / (Co + Mg + Fe + Al + Cu) is 10 to 90% in molar ratio, and the average particle diameter is 0.02 to 2.0 μm, so that the infrared region wavelength is 1500 nm. It was possible to improve the infrared reflectance including the reflectance.

また、本発明に係る赤外線反射性黒色顔料は、Ｃｒ６＋などの有害金属元素を含有しておらず、安全な顔料である。 Further, the infrared reflective black pigment according to the present invention does not contain a harmful metal element such as Cr 6+ and is a safe pigment.

本発明の代表的な実施例は、次の通りである。   A typical embodiment of the present invention is as follows.

粒子の平均粒子径は電子顕微鏡写真に示される粒子３５０個の粒子径をそれぞれ測定し、その平均値で示した。   The average particle size of the particles was measured by measuring the particle size of 350 particles shown in the electron micrograph, and the average value was shown.

比表面積値は、ＢＥＴ法により測定した値で示した。   The specific surface area value was indicated by a value measured by the BET method.

赤外線反射性黒色顔料の金属元素の含有量は、「蛍光Ｘ線分析装置３０６３Ｍ型」（理学電機工業株式会社製）を使用し、ＪＩＳ Ｋ０１１９の「けい光Ｘ線分析通則」に従って測定した。   The content of the metal element in the infrared reflective black pigment was measured using a “fluorescence X-ray analyzer 3063M type” (manufactured by Rigaku Denki Kogyo Co., Ltd.) in accordance with “General X-ray fluorescence analysis rules” of JIS K0119.

Ｃｒ６＋の測定方法は、「ＩＣＰ発光分光分析装置」（エスエスアイ・ナノテクノロジー（株）社製）を使用し、ＪＩＳ Ｋ０１０２ ６５．２．４の「ＩＣＰ 発光分光分析法」に従って測定した。   The measuring method of Cr6 + was measured according to “ICP emission spectroscopic method” of JIS K0102 652.4 using “ICP emission spectroscopic analyzer” (manufactured by SSI Nanotechnology Co., Ltd.).

真比重（密度）の測定方法は、ＪＩＳ Ｋ５１０１の「顔料試験方法」に従って測定した。   The true specific gravity (density) was measured according to “pigment test method” of JIS K5101.

赤外線反射性黒色顔料の色相（Ｌ＊値、ａ＊値、ｂ＊値）は、試料０．５ｇとヒマシ油０．５ｍｌとをフーバー式マーラーで練ってペースト状とし、このペーストにクリアラッカー４．５ｇを加え、混練、塗料化してキャストコート紙上に１５０μｍ（６ｍｉｌ）のアプリケーターを用いて塗布した塗布片（塗膜厚み：約３０μｍ）を作製した塗膜片について、「多光源分光測色計ＭＳＣ−ＩＳ−２Ｄ」（スガ試験機株式会社製）を用いて測定を行い、ＪＩＳ Ｚ ８７２９に定めるところに従って表色指数（Ｌ＊値、ａ＊値、ｂ＊値）で示した。 The hue (L * value, a * value, b * value) of the infrared reflective black pigment was prepared by mixing 0.5 g of a sample and 0.5 ml of castor oil with a Hoover type Mahler to form a paste. .5 g, kneaded and coated to form a coating piece (coating thickness: about 30 μm) coated on cast-coated paper using a 150 μm (6 mil) applicator. Measurement was performed using “MSC-IS-2D” (manufactured by Suga Test Instruments Co., Ltd.), and the color index (L * value, a * value, b * value) was indicated according to JIS Z 8729.

赤外線反射性黒色顔料の可視光領域及び赤外線領域での波長の反射性は、上記の色相を測定するために作製した塗膜片について、「分光光度計 ＵＶ−３１００ＰＣ」（株式会社島津製作所）を用いて測定を行い、３００〜２１００ｎｍの波長における平均反射率（％）及び１０００ｎｍ、１５００ｎｍの波長における反射率（％）で示した。   The reflectance of the wavelength in the visible light region and the infrared region of the infrared reflective black pigment is determined by using “spectrophotometer UV-3100PC” (Shimadzu Corporation) for the coating film piece prepared for measuring the above hue. The measurement was performed using the average reflectance (%) at a wavelength of 300 to 2100 nm and the reflectance (%) at a wavelength of 1000 nm and 1500 nm.

赤外線反射性黒色顔料の耐酸性の評価は、ＪＩＳ Ｋ５１０１−８の「顔料試験方法 第８部：耐薬品性」に従い、試験管に顔料２ｇを２％の硫酸を２０ｍｌ加え、密封して５分振り混ぜ、常温に静置させた後、ろ過分離後の溶液をＩＣＰでＣｕ量を測定し、溶解Ｃｕを分析した。   The acid resistance of the infrared reflective black pigment was evaluated in accordance with JIS K5101-8 “Pigment Test Method Part 8: Chemical Resistance”. Add 2 g of 2% sulfuric acid to the test tube and add 20 ml of 2% sulfuric acid, and seal it for 5 minutes. After shaking and allowing to stand at room temperature, the Cu amount of the solution after filtration and separation was measured by ICP, and dissolved Cu was analyzed.

赤外線反射性黒色顔料を含有する塗料の評価は、次の要領で行なった。
塗料の評価方法は、マヨネーズビン（内容積１４０ｍｌ)中に、ガラスビーズ９０ｇ、黒色顔料１０ｇ、アミノアルキッド樹脂（クリヤー）１６．０ｇ、溶剤６．０ｇ配合し、ペイントコンデイショナーで４０分間分散後、更にアルミアルキッド樹脂（クリヤー）５０ｇ追加後、ペイントコンデイショナーで５分分散し、ガラスビーズと分離した。静置５時間後の塗料について、安定性は目視で分離状態を判定した。 The paint containing the infrared reflective black pigment was evaluated in the following manner.
The paint was evaluated by mixing 90 g of glass beads, 10 g of black pigment, 16.0 g of amino alkyd resin (clear), and 6.0 g of solvent in mayonnaise bin (internal volume 140 ml), and dispersing for 40 minutes with a paint conditioner. Further, after adding 50 g of aluminum alkyd resin (clear), it was dispersed with a paint conditioner for 5 minutes and separated from glass beads. The stability of the paint after standing for 5 hours was determined by visual observation of the separated state.

実施例１
ＣｏＯ、Ａｌ２Ｏ３、ＭｇＯ、Ｆｅ２Ｏ３及びＣｕＯを、組成式（ＣｏＯ）ｘ・（ＭｇＯ）１−ｘ・（Ｆｅ２Ｏ３）ｙ・（Ａｌ２Ｏ３）１−ｙ・（ＭＯ）ｚ・（ＣｕＯ）ｎにおいて、ｘ＝０．５、ｙ＝０．５、ｚ＝０、ｎ＝０．３５となるように計量、混合し電気炉で９７０℃で２時間焼成した。組成式中Ｍは金属元素である。焼成品を粉砕し平均粒子径０．６μｍ、ＢＥＴ比表面積８．５ｍ２／ｇの黒色顔料を得た。 Example 1
CoO, Al 2 O 3 , MgO, Fe 2 O 3 and CuO are converted into a composition formula (CoO) x · (MgO) 1-x · (Fe 2 O 3 ) y · (Al 2 O 3 ) 1-y · ( MO) z · (CuO) n was weighed and mixed so that x = 0.5, y = 0.5, z = 0, n = 0.35, and calcined in an electric furnace at 970 ° C. for 2 hours. In the composition formula, M is a metal element. The fired product was pulverized to obtain a black pigment having an average particle size of 0.6 μm and a BET specific surface area of 8.5 m 2 / g.

得られた黒色顔料は、可視光領域から赤外線領域波長３００〜２１００ｎｍにおける平均反射率（日射反射率）が３０％、赤外線領域波長１０００ｎｍにおける反射率が７５％、赤外線領域波長１５００ｎｍにおける反射率が２４％であった。また、耐酸性を評価した結果、溶液中のＣｕの濃度は１００ｐｐｍと非常に小さく、さらに塗料構成基材に対する分散性、分散安定性、塗料としての貯蔵安定性とも良好であった。   The obtained black pigment has an average reflectance (solar reflectance) of 30% from the visible light region to the infrared region wavelength of 300 to 2100 nm, a reflectance of 75% at the infrared region wavelength of 1000 nm, and a reflectance of 24 at the infrared region wavelength of 1500 nm. %Met. In addition, as a result of evaluating acid resistance, the concentration of Cu in the solution was as extremely low as 100 ppm, and the dispersibility, dispersion stability, and storage stability as a coating material were also good.

実施例２
湿式法で合成した後、８２０℃で２時間焼成した以外は前記実施例１と同様にして黒色顔料を得た。 Example 2
After synthesizing by a wet method, a black pigment was obtained in the same manner as in Example 1 except that it was calcined at 820 ° C. for 2 hours.

実施例３
前記実施例１と同様にして黒色顔料を得た。次いで、得られた黒色顔料を水中に湿式分散させ、７０℃に保温した黒色顔料のスラリーに対し水ガラス０．５ｗｔ％を滴下しながら塩酸及び水酸化ナトリウムでｐＨ７に調整し１時間維持した。その後、水洗・乾燥・粉砕処理した。耐酸性を評価した結果、溶液中のＣｕの濃度は６０ｐｐｍと非常に小さかった。 Example 3
A black pigment was obtained in the same manner as in Example 1. Next, the obtained black pigment was wet-dispersed in water, adjusted to pH 7 with hydrochloric acid and sodium hydroxide while dropping 0.5 wt% of water glass to a black pigment slurry kept at 70 ° C., and maintained for 1 hour. Then, it washed with water, dried and pulverized. As a result of evaluating acid resistance, the concentration of Cu in the solution was as extremely low as 60 ppm.

実施例４
焼成温度及び表面処理を変化させた以外は実施例３と同様にして黒色顔料を得た。 Example 4
A black pigment was obtained in the same manner as in Example 3 except that the firing temperature and the surface treatment were changed.

比較例１
原料組成を変化させた以外は、実施例１と同様にして黒色顔料を得た。 Comparative Example 1
A black pigment was obtained in the same manner as in Example 1 except that the raw material composition was changed.

比較例２
比較例１で得られたＣｕを含有しない黒色顔料１モルに対して３．１モルの粉末状の酸化第二銅（ＣｕＯ）を添加、自動乳鉢で３０分混合し、混合物からなる黒色顔料を得た。該黒色顔料を塗料構成基材に添加混合し該塗料を５時間静置させたところ、ＣｕＯが沈降分離した。 Comparative Example 2
3.1 mol of powdered cupric oxide (CuO) is added to 1 mol of the black pigment not containing Cu obtained in Comparative Example 1, and mixed for 30 minutes in an automatic mortar. Obtained. When the black pigment was added to and mixed with the paint constituting substrate and the paint was allowed to stand for 5 hours, CuO was precipitated and separated.

比較例３
平均粒子径０．５μｍの粉末状のＣｕＯである。塗料構成基材に添加混合し該塗料を５時間静置させたところＣｕＯが沈降分離した。さらに耐酸性を評価した結果、溶液中のＣｕの濃度は２５００ｐｐｍであった。 Comparative Example 3
It is a powdery CuO having an average particle diameter of 0.5 μm. When the paint was added to and mixed with the paint base material and the paint was allowed to stand for 5 hours, CuO settled and separated. Furthermore, as a result of evaluating acid resistance, the concentration of Cu in the solution was 2500 ppm.

実施例１〜実施例４、比較例１〜３の製造条件を表１に、得られた赤外線反射性黒色顔料の諸特性、塗膜の特性（反射率％）及び塗料の特性を表２及び表３に示した。なおＣｒ６＋の含有量が「５ｐｐｍ未満」とは、前記測定装置の検出限界以下であることを示す。 The production conditions of Examples 1 to 4 and Comparative Examples 1 to 3 are shown in Table 1, and the properties of the obtained infrared reflective black pigment, the properties of the coating film (reflectance%), and the properties of the paint are shown in Table 2. It is shown in Table 3. The Cr 6+ content “less than 5 ppm” indicates that the content is below the detection limit of the measuring device.

Figure 0005201405
Figure 0005201405

Figure 0005201405
Figure 0005201405

Figure 0005201405
Figure 0005201405

本発明に係る赤外線反射性黒色顔料は、赤外線反射性に優れ、赤外線領域波長１５００ｎｍにおいても高い反射率を有するので赤外線反射性黒色顔料として好適である。   The infrared-reflective black pigment according to the present invention is suitable as an infrared-reflective black pigment because it is excellent in infrared reflectivity and has a high reflectance even in the infrared region wavelength of 1500 nm.

Claims (7)

実質的にＣｒを含有せず、少なくともＣｏ、Ｍｇ、Ｆｅ、Ａｌ及びＣｕを含有する複合酸化物からなる黒色顔料であって、
Ｃｕ／（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）がモル比で１０〜９０％であり、該黒色顔料の平均粒子径が０．０２〜２．０μｍであることを特徴とする赤外線反射性黒色顔料。 A black pigment which is substantially free of Cr and is composed of a composite oxide containing at least Co, Mg, Fe, Al and Cu,
An infrared-reflective black pigment, wherein Cu / (Co + Mg + Fe + Al + Cu) is 10 to 90% in molar ratio, and the average particle size of the black pigment is 0.02 to 2.0 μm. 請求項１記載の赤外線反射性黒色顔料の（Ｃｏ＋Ｍｇ＋Ｆｅ＋Ａｌ＋Ｃｕ）／全金属元素がモル比で５０〜１００％であることを特徴とする赤外線反射性黒色顔料。   2. The infrared reflective black pigment according to claim 1, wherein (Co + Mg + Fe + Al + Cu) / total metal elements of the infrared reflective black pigment according to claim 1 are in a molar ratio of 50 to 100%. 請求項１又は２記載の赤外線反射性黒色顔料の明度（Ｌ＊）が３０以下であることを特徴とする赤外線反射性黒色顔料。 An infrared reflective black pigment characterized in that the lightness (L * ) of the infrared reflective black pigment according to claim 1 or 2 is 30 or less. 請求項１乃至３のいずれか１項に記載の赤外線反射性黒色顔料の日射反射率が２５％以上であり、かつ赤外線領域波長１５００ｎｍの反射率が２３％以上であることを特徴とする赤外線反射性黒色顔料。   The infrared reflectance of the infrared reflective black pigment according to any one of claims 1 to 3, wherein the solar reflectance is 25% or more, and the reflectance at an infrared region wavelength of 1500 nm is 23% or more. Black pigment. 請求項１乃至４のいずれか１項に記載の赤外線反射性黒色顔料の表面がＳｉ、Ａｌ、Ｚｒ、Ｔｉから選ばれる一種以上の化合物で被覆されていることを特徴とする赤外線反射性黒色顔料。   The infrared reflective black pigment, wherein the surface of the infrared reflective black pigment according to any one of claims 1 to 4 is coated with one or more compounds selected from Si, Al, Zr, and Ti. . 請求項１乃至５のいずれか１項に記載の赤外線反射性黒色顔料を塗料構成基材中に配合したことを特徴とする塗料。   6. A paint comprising the paint-constituting substrate formulated with the infrared-reflective black pigment according to any one of claims 1 to 5. 請求項１乃至５のいずれか１項に記載の赤外線反射性黒色顔料を用いて着色したことを特徴とする樹脂組成物。   A resin composition, characterized by being colored using the infrared reflective black pigment according to any one of claims 1 to 5.
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