JP2006008874A - Coating material - Google Patents
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Abstract
Description
本発明は塗料に関し、特に白色顔料と非白色顔料を調色する際に非白色顔料の使用量を相対的に抑制可能であると共に高い日射反射率を有する塗料に関する。 The present invention relates to a paint, and more particularly to a paint having a high solar reflectance while being able to relatively reduce the amount of non-white pigment used when toning white and non-white pigments.
日射反射率を高めたいわゆる遮熱性塗料が近年注目を集めており、本出願人が提案した特許文献１の塗料は従来にみられない係れた日射反射能をもつものである。この塗料の典型例は、ＪＩＳ Ａ ５７５９に定義される日射反射率が１５％以上であって、かつＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間におけるＬ＊値が２４以下の顔料と白色顔料とからなるものである。 In recent years, a so-called heat-shielding paint having an increased solar reflectance has attracted attention, and the paint of Patent Document 1 proposed by the present applicant has a related solar reflectance that is not seen in the past. A typical example of this coating, there is solar reflectance as defined in JIS A 5759 15% or more, and CIE1976L * a * b * which L * value in the color space is composed of the 24 following pigment and a white pigment It is.
白色顔料としては種々の顔料が知られており、ルチル型酸化チタンもこの一つである。一般に塗料用に用いられているルチル型酸化チタンは重量分布による平均粒子経（粒子径分布のピークも同様）が０．３μｍ以下のものである。 Various pigments are known as white pigments, and rutile type titanium oxide is one of them. In general, rutile titanium oxide used for coating materials has an average particle size (as well as a peak of particle size distribution) by weight distribution of 0.3 μm or less.
人間が白色として物体を認識するためには０．３５μｍ〜０．７８μｍの可視光線領域が高いレベルで反射される必要があり、ここで可視光線領域０．３５μｍ〜０．７８μｍを反射せしめるためには、この波長のほぼ半分の粒子径を持つ上記のルチル型酸化チタンを白色塗料の願料として使用することは利にかなっているといえる。しかし上記のルチル型酸化チタンは、白色の着色力が強いために、白色以外に塗料を調色する場合には、多量の着色顔料を混合する必要があった。 In order for a human to recognize an object as white, the visible light region of 0.35 μm to 0.78 μm needs to be reflected at a high level, and here the visible light region of 0.35 μm to 0.78 μm is reflected. Therefore, it can be said that it is advantageous to use the rutile-type titanium oxide having a particle size almost half of this wavelength as a white paint application. However, since the above rutile titanium oxide has a strong white coloring power, it is necessary to mix a large amount of coloring pigments when toning the paint other than white.
ＪＩＳ Ａ ５７５９に定義される３５０ｎｍ〜２，１００ｎｍの波長域における日射反射率の算出式に基づいて、上記のルチル型酸化チタンを用いた着色塗料の日射反射率を測定すると、白色では高い日射反射率を示すものの、明度が低い例えばＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間に於けるＬ＊値が８０以下に調色した場合には、規定のＬ＊値を発現するためには相当量の黒色顔料を混合する必要があるため、該黒色顔料が日射を吸収してしまい、塗膜全体としての日射反射率を高く出来ない問題があった。また、塗料の調色において、白色以外の顔料を混合する場合に、該顔料の混合比が増えることは塗料全体のコストアップの原因にもなっていた。 When the solar reflectance of the colored paint using the rutile titanium oxide is measured based on the formula for calculating the solar reflectance in the wavelength range of 350 nm to 2,100 nm defined in JIS A 5759, the white solar reflectance is high. For example, when the L * value in the CIE 1976 L * a * b * color space is adjusted to 80 or less, a considerable amount of black pigment is required to express the specified L * value. Therefore, there is a problem that the black pigment absorbs solar radiation and the solar reflectance of the entire coating film cannot be increased. Further, when a pigment other than white is mixed in the toning of the paint, an increase in the mixing ratio of the pigment also causes an increase in the cost of the entire paint.
本発明の目的は上記した従来技術の問題点を解決することにあり、特に白色以外の着色顔料を相対的に少量含有させるだけで要求される色相に発色せしめ、また高い日射反射率を有する塗料を提供することにある。 An object of the present invention is to solve the above-described problems of the prior art, and in particular, a paint that develops a required hue only by containing a relatively small amount of a color pigment other than white and has a high solar reflectance. Is to provide.
本発明は、第１に、非白色顔料と白色顔料を必須成分として含有する塗料において、白色顔料として平均粒子経が０．５〜１．４μｍのルチル型酸化チタンを用いることを特徴とする塗料である。 A first aspect of the present invention is a paint containing a non-white pigment and a white pigment as essential components, wherein the rutile titanium oxide having an average particle size of 0.5 to 1.4 μm is used as the white pigment. It is.
本発明は、第２に、非白色顔料がＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間に於けるＬ＊値が３０以下の着色顔料からなる上記の塗料である。 The present invention, in the second, in the L * value in a non-white pigment is CIE1976L * a * b * color space is the above described coating material consisting of 30 or less color pigment.
本発明は、第３に、非白色顔料がＪＩＳ Ａ ５７５９に定義される３５０ｎｍ〜２，１００ｎｍの波長域における日射反射率が１５％以上の着色顔料からなる上記の塗料である。 The third aspect of the present invention is the above-described coating material, wherein the non-white pigment is a color pigment having a solar reflectance of 15% or more in a wavelength range of 350 nm to 2,100 nm as defined in JIS A 5759.
本発明は、第４に、無機微細粒子および／または無機中空微細粒子を存在させてなる上記の塗料である。 Fourthly, the present invention is the above-described coating material in which inorganic fine particles and / or inorganic hollow fine particles are present.
本発明により、白色以外の着色顔料の含有量を相対的に低下させても要求される色相に発色させることができ経済性に係れると共に、より高い日射反射率を達成することが可能となる。 According to the present invention, even if the content of a color pigment other than white is relatively reduced, the required hue can be developed, and it is possible to achieve higher solar reflectance while being economical. .
本発明で用いる白色顔料は平均粒子経（重量分布による）が０．５〜１．４μｍのルチル型酸化チタンであり、これは従来塗料に一般的に用いられていた粒子経が０．３μｍ以下のルチル型酸化チタンとは明瞭に区別される。本発明で用いるルチル型酸化チタンは５０重量％以上、より好ましくは７０重量％以上が上記の０．５〜１．４μｍの粒子径内にあるものが好ましい。 The white pigment used in the present invention is a rutile type titanium oxide having an average particle size (by weight distribution) of 0.5 to 1.4 μm, which has a particle size of 0.3 μm or less that has been generally used in conventional paints. It is clearly distinguished from rutile titanium oxide. The rutile type titanium oxide used in the present invention preferably has 50% by weight or more, more preferably 70% by weight or more within the particle diameter of 0.5 to 1.4 μm.
本発明の塗料において上記のルチル型酸化チタンと組合せる非白色顔料即ち着色顔料としては、黒色や茶色を典型例とする混色系顔料が好ましく、特にＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間に於けるＬ＊値が３０以下の混色系顔料、特にそれらのうちでもＪＩＳ Ａ ５７５９に定義される３５０ｎｍ〜２，１００ｎｍの波長域における日射反射率が１５％以上である混色系顔料が好ましい。前者の要件のみを満足する顔料の例としてはカーボンブラックや鉄黒等があり、これらの場合、白色顔料として上記の限定されたルチル型酸化チタンを用いることによって、従来のルチル型酸化チタンを用いた場合に比し、着色顔料の量を相対的に低下させることができる。 As the non-white pigment, that is, the colored pigment combined with the rutile-type titanium oxide in the paint of the present invention, a mixed color pigment such as black or brown is preferable, and in particular, L in the CIE 1976 L * a * b * color space. * A mixed color pigment having a value of 30 or less, particularly a mixed color pigment having a solar reflectance of 15% or more in a wavelength range of 350 nm to 2,100 nm as defined in JIS A 5759 is preferable. Examples of pigments that satisfy only the former requirement include carbon black and iron black. In these cases, conventional rutile titanium oxide is used by using the limited rutile titanium oxide as a white pigment. The amount of the color pigment can be relatively reduced as compared with the case where the color pigment is present.
上記の両要件を満足する混色系顔料の例としては、アゾメチアゾ系顔料（商品名もクロモファインブラックＡ−１１０３（大日精化工業（株）製）、モノアゾ系エロー（商品名ホスターパームエローＨ３Ｇ：ヘキスト（株）製）等の黄色系顔料、酸化鉄（商品名トダカラー１２０ＥＤ：戸田工業（株）製）、キナクリドンレッド（Ｈｏｓｔａｐｅｒｍ Ｒｅｄ Ｅ２Ｂ７０：ヘキスト（株）製）等の赤色系顔料、フタロシアニンブルー（商品名シヤニンブルーＳＰＧ−８：大日本インキ（株）製）等の青色系顔料、フタロシヤニングリーン（商品名シヤニングリーン５３１０：大日精化工業（株）製）等の緑色系顔料等が挙げられる。 Examples of mixed color pigments that satisfy both of the above requirements include azomethiazo pigments (trade name also Chromofine Black A-1103 (manufactured by Dainichi Seika Kogyo Co., Ltd.)), monoazo yellow (trade name Hoster Palm Yellow H3G: Yellow pigments such as Hoechst), red oxides such as iron oxide (trade name Toda Color 120ED: Toda Kogyo Co., Ltd.), quinacridone red (Hostaperm Red E2B70: Hoechst Co., Ltd.), phthalocyanine blue ( Blue pigments such as trade name “Syanin Blue SPG-8: manufactured by Dainippon Ink Co., Ltd.” and the like, and green pigments such as phthalocyanine green (trade name “Syanin Green 5310” manufactured by Dainichi Seika Kogyo Co., Ltd.) It is done.
塗料を構成するバインダとしては塗料用として知られた適宜の樹脂を用いることができる。具体例としては、アクリル樹脂、アルキド樹脂、ポリエステル樹脂、シリコーン変性ポリエステル樹脂、シリコーン変性アクリル樹脂、エポキシ樹脂、ポリカーボネート樹脂、シリケート樹脂、フッ素樹脂、塩素系樹脂、尿素系樹脂、メラミン樹脂、ビニルエステル樹脂、不飽和ポリエステル（メタ）アクリレート樹脂、エポキシ（メタ）アクリレート樹脂、ウレタン（メタ）アクリレート樹脂、メチル（メタ）アクリレート樹脂等が挙げられる。通常これらの樹脂は、溶剤溶液型、非水系分散型及び水溶性型等として用途に応じて用いられる。 As the binder constituting the paint, an appropriate resin known for paint can be used. Specific examples include acrylic resins, alkyd resins, polyester resins, silicone-modified polyester resins, silicone-modified acrylic resins, epoxy resins, polycarbonate resins, silicate resins, fluorine resins, chlorine resins, urea resins, melamine resins, and vinyl ester resins. , Unsaturated polyester (meth) acrylate resin, epoxy (meth) acrylate resin, urethane (meth) acrylate resin, methyl (meth) acrylate resin, and the like. Usually, these resins are used as a solvent solution type, a non-aqueous dispersion type, a water-soluble type, and the like according to applications.
本発明の塗料中の各成分の割合は特に制限されないが、塗料全体の重量当り平均粒子経０．５〜１．４μｍのルチル型酸化チタンを１０〜１５重量％存在させることが好ましい。非白色顔料は意図する色相に応じてその使用量を変化させうるが、通常白色顔料１００重量部に対して５〜１５０重量部、特に１０〜８０重量部が好ましい。 The ratio of each component in the coating material of the present invention is not particularly limited, but it is preferable that 10 to 15% by weight of rutile titanium oxide having an average particle size of 0.5 to 1.4 μm per weight of the entire coating material is present. The amount of the non-white pigment used can be changed according to the intended hue, but is usually 5 to 150 parts by weight, particularly 10 to 80 parts by weight based on 100 parts by weight of the white pigment.
本発明の塗料には必要に応じ体質顔料その他の従来知られた添加剤を加えることができるが、特に無機微細粒子、無機中空微細粒子を加えることは好ましい。これらの粒子径は５〜１５０μｍが好ましく、特に透明ないし半透明のセラミック中空微細粒子が好ましい。これらは塗料中に１〜２０重量％程度配合しうる。 If necessary, extender pigments and other conventionally known additives can be added to the paint of the present invention, but it is particularly preferable to add inorganic fine particles and inorganic hollow fine particles. These particle diameters are preferably 5 to 150 μm, particularly transparent or translucent ceramic hollow fine particles. These can be blended in the paint in an amount of about 1 to 20% by weight.
尚、本発明では白色顔料として従来のルチル型酸化チタンを併用することもできる。次に本発明を実施例に基づいて説明する。 In the present invention, a conventional rutile type titanium oxide can be used in combination as a white pigment. Next, this invention is demonstrated based on an Example.
例１：
平均粒子経が０．２２μｍ（０．１〜０．４μｍの粒子の含有量が８９重量％）のルチル型酸化チタン（酸化チタンＡと称する）と平均粒子径が１μｍ（０．５〜１．５μｍの粒子の含有量が８６重量％）のルチル型酸化チタン（酸化チタンＢと称する）を単独でまた混合して白色塗料を試作し、その塗料を用いて乾燥膜厚が３００μｍとなるようにアルミ金属板に塗装したものをＪＩＳ Ａ ５７５９に定義される３５０ｎｍ〜２，１００ｎｍの波長域における日射反射率を測定した。結果を表１に示す。
Example 1:
Rutile-type titanium oxide (referred to as titanium oxide A) having an average particle size of 0.22 μm (the content of 0.1-0.4 μm particles is 89% by weight) and an average particle size of 1 μm (0.5-1. A rutile-type titanium oxide (referred to as titanium oxide B) having a content of 5 μm particles of 86% by weight is singly and mixed to produce a white paint, and the dry film thickness is 300 μm using the paint. The solar reflectance in the wavelength range of 350 nm to 2,100 nm defined in JIS A 5759 was measured for the coated aluminum metal plate. The results are shown in Table 1.
波長と分光反射率の関係を図１に示す。 The relationship between wavelength and spectral reflectance is shown in FIG.
図１から、波長域が１，３００ｎｍ近辺より長い波長の反射率を見ると、酸化チタンＢの配合量を増やせば増やすほど反射率が高くなっているのが分かる。このことから、１，３００ｎｍ以上の波長に対しては酸化チタンＢが日射反射率の向上に役立つことが分かる。 From FIG. 1, it can be seen that the reflectance increases as the blending amount of titanium oxide B increases when the reflectance of a wavelength longer than 1,300 nm is observed. From this, it is understood that titanium oxide B is useful for improving the solar reflectance for wavelengths of 1,300 nm or more.
次に、太陽光線に含まれる電磁波エネルギーの波長毎の照射強度を図２に示す。
図２から明らかなように、太陽光線の内約１，３００ｎｍより長い波長に含まれる太陽エネルギーの量は極端に少ない。従って、酸化チタンＢを用いた塗料を日射が直接当たる屋外に使用する場合には、約１，３００ｎｍより長い波長の反射率は高いものの、太陽エネルギーの多くが含まれる約１，３００ｎｍより短い波長に対する反射率が低いために、太陽光を反射する能力が少ない。しかし、１，３００ｎｍ以上の波長を多く含む白熱灯などの光を反射せしめる塗料に使用することに対しては有用である。
Next, the irradiation intensity | strength for every wavelength of the electromagnetic wave energy contained in a solar ray is shown in FIG.
As is clear from FIG. 2, the amount of solar energy contained in a wavelength longer than about 1,300 nm among the solar rays is extremely small. Therefore, when the paint using titanium oxide B is used outdoors where the solar radiation directly hits, although the reflectance at a wavelength longer than about 1,300 nm is high, the wavelength shorter than about 1,300 nm including a lot of solar energy. Because of its low reflectivity, the ability to reflect sunlight is low. However, it is useful for use in paints that reflect light such as incandescent lamps that contain many wavelengths of 1,300 nm or more.
例２：
次に、酸化チタンＡと酸化チタンＢの着色力に関する実験を行った。
酸化チタンＡとＢをそれぞれ用い、カーボンブラックＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間に於けるＬ＊値が３０となるように調色した場合の重量配合比を比較すると表３のとおりとなった。ここで使用した樹脂はアクリル樹脂である。
Example 2:
Next, an experiment on the coloring power of titanium oxide A and titanium oxide B was performed.
Table 3 shows a comparison of the weight blending ratios when the titanium oxides A and B were used and the colors were adjusted so that the L * value in the carbon black CIE 1976 L * a * b * color space was 30. The resin used here is an acrylic resin.
上記から、酸化チタンＢを用いた方が、着色顔料の混合を少なくできることが分かる。 From the above, it can be seen that the use of titanium oxide B can reduce the mixing of the color pigments.
着色顔料の配合量を少なくできるから、着色顔料が高価な場合には塗料製造に必要な原材料全体のコスト低減を図ることができることになる。 Since the blending amount of the color pigment can be reduced, when the color pigment is expensive, it is possible to reduce the cost of the entire raw material necessary for manufacturing the paint.
例３：
次に、可視波長域で吸収を示し赤外線波長領域では反射または透過する特性を示す顔料で、ＪＩＳ Ａ ５７５９に定義される３５０ｎｍ〜２，１００ｎｍの波長域における日射反射率が１０％以上好ましくは１５％以上の顔料と、酸化チタンＡおよび酸化チタンＢをアクリル樹脂中に混入させて、ＣＩＥ１９７６Ｌ＊ａ＊ｂ＊色空間に於けるＬ＊値が３０となる塗料を試作し、乾燥膜厚が２００ｎｍとなるような塗板を作成し、各日射反射率を測定した。結果を表３に示す。
Example 3:
Next, it is a pigment that exhibits absorption in the visible wavelength range and reflects or transmits in the infrared wavelength range, and has a solar reflectance of 10% or more, preferably 15 in the wavelength range of 350 nm to 2,100 nm as defined in JIS A 5759. % or more of a pigment, and titanium oxide a and titanium oxide B was mixed in an acrylic resin, CIE1976L * a * b * in the L * value in the color space is a prototype coating of 30, a dry film thickness of 200nm A coated plate was prepared, and each solar reflectance was measured. The results are shown in Table 3.
この結果から、酸化チタンＢを使用した塗料では、黒色顔料の含有量を少なくできることから、太陽光に含まれる近赤外線領域の反射率を向上せしめ、ＪＩＳ Ａ ５７５９に定義される３５０ｎｍ〜２，１００ｎｍの波長領域における日射反射率を高くすることが明らかとなった。 From this result, since the content of the black pigment can be reduced in the paint using titanium oxide B, the reflectance in the near-infrared region contained in sunlight is improved, and 350 nm to 2,100 nm as defined in JIS A 5759. It has been clarified that the solar reflectance in the wavelength region is increased.
ここで、日射反射率の違いが塗膜表面温度の上昇に及ぼす影響を考察する。日射による表面温度上昇は一般的に下記の式で表される。（特許第３３７５６０３号参照）
Ｔ＝Ｗｘ（１−日射反射率）／αｏ
ここで、
Ｔ： 日射による上昇温度（℃）
Ｗ： 日射量
αｏ：外表面熱伝達率
Ｗ＝８００、αｏ＝２０と仮定し、表３における２−１および２−２の配合による上昇温度を計算すると表４のとおりとなる。
Here, the effect of the difference in solar reflectance on the increase in the coating surface temperature is considered. The surface temperature rise due to solar radiation is generally expressed by the following formula. (See Japanese Patent No. 3375603)
T = Wx (1-sun reflectance) / αo
here,
T: Temperature rise due to solar radiation (℃)
W: Solar radiation amount αo: External surface heat transfer coefficient Assuming that W = 800 and αo = 20, calculated temperature rises due to the combination of 2-1 and 2-2 in Table 3 are as shown in Table 4.
このように、本発明の選択されたルチル型酸化チタンを用いることによって従来型のルチル型酸化チタンを用いた場合より日射による温度上昇を抑制できることが明らかとなった。 Thus, it became clear that the use of the selected rutile type titanium oxide of the present invention can suppress the temperature rise due to solar radiation as compared with the case of using the conventional type rutile type titanium oxide.
Claims (4)
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| JP2004189088A JP2006008874A (en) | 2004-06-28 | 2004-06-28 | Coating material |
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| JP2009167662A (en) * | 2008-01-15 | 2009-07-30 | Chugai Shoko Kk | Paving material, its manufacturing method, and pavement body |
| JP2009167661A (en) * | 2008-01-15 | 2009-07-30 | Chugai Shoko Kk | Paving material, its manufacturing method, and pavement body |
| WO2010037071A1 (en) * | 2008-09-29 | 2010-04-01 | E. I. Du Pont De Nemours And Company | Polymer-based products having improved solar reflectivity and uv protection |
| CN102762669A (en) * | 2010-02-17 | 2012-10-31 | 钛白粉欧洲有限公司 | Solar reflectance |
| CN102762670A (en) * | 2010-02-17 | 2012-10-31 | 钛白粉欧洲有限公司 | Titanium dioxide |
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| JP2009167662A (en) * | 2008-01-15 | 2009-07-30 | Chugai Shoko Kk | Paving material, its manufacturing method, and pavement body |
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| CN102762669A (en) * | 2010-02-17 | 2012-10-31 | 钛白粉欧洲有限公司 | Solar reflectance |
| CN102762670A (en) * | 2010-02-17 | 2012-10-31 | 钛白粉欧洲有限公司 | Titanium dioxide |
| KR101881728B1 (en) | 2010-02-17 | 2018-07-27 | 훈츠만 피앤에이 유케이 리미티드 | Solar reflectance |
| JP2013023624A (en) * | 2011-07-22 | 2013-02-04 | Kikusui Chemical Industries Co Ltd | Film composition |
| US10174213B2 (en) | 2011-09-16 | 2019-01-08 | Basf Se | Coating system |
| JP2013147571A (en) * | 2012-01-19 | 2013-08-01 | Kikusui Chemical Industries Co Ltd | Heat-shielding coating |
| JP2018028015A (en) * | 2016-08-17 | 2018-02-22 | 旭化成ホームズ株式会社 | Heat-shielding coating material, heat-shielding laminated coating film, and coated product |
| US11808833B2 (en) | 2016-10-28 | 2023-11-07 | Ppg Industries Ohio, Inc. | Coatings for increasing near-infrared detection distances |
| US11977154B2 (en) | 2016-10-28 | 2024-05-07 | Ppg Industries Ohio, Inc. | Coatings for increasing near-infrared detection distances |
| KR20180066326A (en) * | 2016-12-07 | 2018-06-19 | 주식회사 라온테크 | Appatus and method for attaching wet tissues cover |
| KR20190034061A (en) * | 2018-05-30 | 2019-04-01 | (주)두온에너지원 | High durable thermally shielding paint composition with high infrared reflection |
| KR101970633B1 (en) | 2018-05-30 | 2019-04-22 | (주)두온에너지원 | High durable thermally shielding paint composition with high infrared reflection |
| US11809933B2 (en) | 2018-11-13 | 2023-11-07 | Ppg Industries Ohio, Inc. | Method of detecting a concealed pattern |
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