WO2020184694A1 - Pigment réfléchissant les infrarouges - Google Patents

Pigment réfléchissant les infrarouges Download PDF

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Publication number
WO2020184694A1
WO2020184694A1 PCT/JP2020/010973 JP2020010973W WO2020184694A1 WO 2020184694 A1 WO2020184694 A1 WO 2020184694A1 JP 2020010973 W JP2020010973 W JP 2020010973W WO 2020184694 A1 WO2020184694 A1 WO 2020184694A1
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WO
WIPO (PCT)
Prior art keywords
metal thin
thin film
infrared reflective
reflective pigment
film layer
Prior art date
Application number
PCT/JP2020/010973
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English (en)
Japanese (ja)
Inventor
長谷川　洋
利明 菅原
泉 佐々木
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デクセリアルズ株式会社
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Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Publication of WO2020184694A1 publication Critical patent/WO2020184694A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/62—Metallic pigments or fillers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/66—Copper alloys, e.g. bronze
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds

Definitions

  • the present invention relates to infrared reflective pigments.
  • the infrared reflective pigment is, for example, a scaly laminate having at least one metal thin film layer and at least two transparent dielectric layers (see, for example, Patent Document 1).
  • Such infrared reflective pigments often use silver for the metal thin film layer.
  • an infrared reflective pigment using silver for the metal thin film layer may be inferior in heat resistance.
  • An object of the present invention is to solve the above-mentioned problems in the past and to achieve the following objects. That is, an object of the present invention is to provide an infrared reflective pigment having excellent heat resistance and good reflectance.
  • the means for solving the above-mentioned problems are as follows. That is, ⁇ 1> It has a metal thin film layer and dielectric layers arranged on both sides of the metal thin film layer.
  • the metal thin film layer contains at least one of an AgCu alloy and an AgBiNd alloy.
  • the dielectric layer contains titanium oxide. It is an infrared reflective pigment characterized by this.
  • ⁇ 4> The infrared reflective pigment according to any one of ⁇ 2> to ⁇ 3>, wherein the Cu content in the AgCu alloy is 5 at% or more and 20 at% or less with respect to Ag.
  • ⁇ 5> The infrared reflective pigment according to any one of ⁇ 1> to ⁇ 4>, wherein the titanium oxide contains at least one of Ti 4 O 7 and Ti 3 O 5 .
  • ⁇ 6> The infrared reflective pigment according to any one of ⁇ 1> to ⁇ 5>, wherein the titanium oxide contains Ti 4 O 7 .
  • ⁇ 7> The infrared reflective pigment according to any one of ⁇ 1> to ⁇ 6>, wherein the metal thin film layer has an average thickness of 10 nm to 30 nm.
  • ⁇ 8> The infrared reflective pigment according to any one of ⁇ 1> to ⁇ 7>, wherein the metal thin film layer has an average thickness of 15 nm to 25 nm.
  • ⁇ 9> The infrared reflective pigment according to any one of ⁇ 1> to ⁇ 8>, wherein the dielectric layer has an average thickness of 20 nm to 50 nm.
  • ⁇ 10> The infrared reflective pigment according to any one of ⁇ 1> to ⁇ 9>, wherein the dielectric layer has an average thickness of 25 nm to 35 nm.
  • an infrared reflective pigment which can solve the above-mentioned problems in the past, achieve the above object, have excellent heat resistance, and have good reflectance.
  • FIG. 1 is a result of measuring the reflectance of the AgCu alloy layer.
  • FIG. 2 shows the reflectance measurement results of the AgSn alloy layer.
  • FIG. 3 shows the reflectance measurement results of the AgZn alloy layer.
  • FIG. 4 shows the reflectance measurement results of the AgBiNd alloy layer.
  • FIG. 5 shows the transmittance measurement result of the AgCu alloy layer or the Ag layer.
  • FIG. 6 shows the measurement result of the transmission loss of the titanium oxide layer.
  • FIG. 7 shows the spectral characteristics of the suitable structure of the infrared reflective pigment.
  • FIG. 8 shows the spectral characteristics of an example of an infrared reflective pigment.
  • FIG. 9 is a schematic cross-sectional view showing an example of the layer structure of the infrared reflective pigment.
  • FIG. 10 is a schematic cross-sectional view showing another example of the layer structure of the infrared reflective pigment.
  • the infrared reflective pigment of the present invention has a metal thin film layer and a dielectric layer.
  • the dielectric layer is arranged on both sides of the metal thin film layer.
  • the metal thin film layer has a function of reflecting infrared rays. Since silver has excellent reflectance, it is preferable as a material for the metal thin film layer, but it is inferior in heat resistance.
  • the metal thin film layer containing at least one of the AgCu alloy and the AgBiNd alloy has high reflectance and excellent heat resistance.
  • the metal thin film layer preferably contains at least one of an AgCu alloy and an AgBiNd alloy.
  • a metal thin film layer using an AgCu alloy is most preferable.
  • the reflectances of the AgCu alloy, AgSn alloy, AgZn alloy, and AgBiNd alloy were measured.
  • the composition of the alloy used is as follows. -AgCu alloy; 2 at% of Cu with respect to Ag -AgSn alloy; 2 at% of Sn with respect to Ag -AgZn alloy; 2at% of Zn with respect to Ag -AgBiNd alloy; 2 at% each of Bi and Nd with respect to Ag
  • each alloy was used to form a metal thin film layer having a thickness of 30 nm on a glass substrate by a vapor deposition method.
  • a metal thin film layer having a thickness of 30 nm was formed on a glass substrate by a sputtering method.
  • the reflectance of the formed metal thin film layer was measured at the initial stage of formation and after storage at 150 ° C. for 2 hours. The reflectance was measured in the range of 350 nm to 850 nm using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Table 1. Further, FIGS. 1 to 4 show the reflectance of each metal thin film layer.
  • the metal thin film layer using the AgCu alloy or the AgBiNd alloy has both excellent reflectance and excellent heat resistance.
  • the Cu content in the AgCu alloy is preferably more than 0 at% and 30 at% or less, more preferably 0.1 at% or more and 30 at% or less, still more preferably 2 at% or more and 25 at% or less, and 5 at% with respect to Ag. More than 20 at% or less is particularly preferable.
  • the Cu content is low, the heat resistance tends to decrease and the transmittance after the heat resistance test tends to decrease significantly, and when the Cu content is high, the color tends to be colored. From the viewpoint of obtaining excellent heat resistance while preventing coloring, 5 at% or more and 20 at% or less is particularly preferable.
  • the heat resistance test (2 hours at 200 ° C.) of the metal thin film layer (AgCu alloy layer or Ag layer) was performed by changing the Cu content, and the transmittance was confirmed.
  • the test piece was prepared by forming a metal thin film layer (AgCu alloy layer or Ag layer) having a thickness of 30 nm on a glass substrate by a thin film deposition method.
  • the transmittance was measured in the range of 400 nm to 850 nm using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd.). The results are shown in FIG.
  • the reference numerals in FIG. 5 are as shown in Table 2 below.
  • the average thickness of the metal thin film layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it may be 5 nm to 50 nm, 10 nm to 30 nm, or 15 nm to. It may be 25 nm.
  • the average thickness is an arithmetic mean value when any 10 points are measured using a transmission electron microscope.
  • the dielectric layer is arranged on both sides of the metal thin film layer.
  • the dielectric layer is, for example, transparent and functions as an antireflection layer in the visible light peripheral region of the metal thin film layer. That is, the dielectric layer has a function of improving the transmittance of incident light in the visible light peripheral region.
  • the dielectric layer preferably contains titanium oxide, more preferably at least one of TiO 2 , Ti 4 O 7 , and Ti 3 O 5 , and Ti 4 O 7 and Ti 3 O 5. It is even more preferable to contain at least one of the above, and it is particularly preferable to contain Ti 4 O 7 .
  • the dielectric layer is formed, for example, by vapor deposition. At that time, in order for the vapor deposition source to be uniformly dissolved, it is preferable that the vapor deposition source has conductivity. If the vapor deposition source is not uniformly dissolved during vapor deposition, punctate film defects may occur in the formed dielectric layer.
  • TiO 2 is not conductive, but Ti 4 O 7 , Ti 3 O 5 , and TiO are conductive. On the other hand, Ti 4 O 7 , Ti 3 O 5 , and Ti O may have lower transparency than TiO 2 . Therefore, the transparency (permeation loss) of Ti 4 O 7 , Ti 3 O 5 , TiO, and TiO 2 was examined.
  • the test piece was produced by forming a dielectric layer (titanium oxide layer) having a thickness of 50 nm on a glass substrate by a thin-film deposition method.
  • the transmission loss was measured in the range of 400 nm to 700 nm using a spectrophotometer (manufactured by JASCO Corporation). The results are shown in FIG. From FIG. 6, it was confirmed that Ti 4 O 7 and Ti 3 O 5 are preferable, and Ti 4 O 7 is more preferable in terms of low transmission loss.
  • the average thickness of each layer of the dielectric layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it may be 10 nm to 100 nm, 20 nm to 50 nm, or the like. It may be 25 nm to 35 nm.
  • the average thickness is an arithmetic mean value when any 10 points are measured using a transmission electron microscope.
  • the suitable structure of the infrared reflective pigment is shown below.
  • the metal thin film layer contains AgCu.
  • the average thickness of the metal thin film layer is 15 nm to 25 nm.
  • the dielectric layer contains Ti 4 O 7 .
  • the average thickness of the dielectric layer is 25 nm to 35 nm.
  • the structure is such that the dielectric layer, the metal thin film layer, and the dielectric layer are laminated in this order.
  • the spectral characteristics of the infrared reflective pigment satisfying the above (1) to (5) are shown in FIG.
  • the spectral characteristics in FIG. 7 are the results of measurement in the range of 400 nm to 700 nm using a spectrophotometer (manufactured by JASCO Corporation).
  • the layer structure of the test piece is a three-layer structure of a dielectric layer (Ti 4 O 7 , 30 nm) / a metal thin film layer (AgCu, 20 nm) / a dielectric layer (Ti 4 O 7 , 30 nm).
  • the spectral characteristics of the infrared reflective pigment having a five-layer structure ( 2 , 35 nm) were measured by the same method. The results are shown in FIG. Comparing FIGS. 7 and 8, the infrared reflective pigments satisfying the above (1) to (5) were excellent in the balance between the transmittance and the reflectance. Further, in the infrared reflective pigment satisfying the above (1) to (5), almost no visual tint was observed.
  • the method for producing the infrared reflective pigment is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the infrared reflective pigment is produced after forming a laminate having a metal thin film layer and a dielectric layer on a support.
  • the infrared reflective pigment is produced. Examples thereof include a method of peeling the laminate from the support and crushing the laminate.
  • the method for forming the metal thin film layer and the dielectric layer on the support is not particularly limited and may be appropriately selected depending on the intended purpose.
  • CVD chemical vapor deposition
  • sputtering method electron.
  • EB beam vapor deposition method
  • ion plating method an ion plating method.
  • FIG. 9 is a schematic cross-sectional view showing an example of the layer structure of the infrared reflective pigment.
  • the infrared reflective pigment 10 of FIG. 9 has a dielectric layer 2A, a metal thin film layer 1, and a dielectric layer 2B in this order.
  • FIG. 10 is a schematic cross-sectional view showing another example of the layer structure of the infrared reflective pigment.
  • the infrared reflective pigment 10 of FIG. 10 has a dielectric layer 2A, a metal thin film layer 1A, a dielectric layer 2B, a metal thin film layer 1B, and a dielectric layer 2C in this order.
  • the infrared reflective pigment of the present invention has excellent heat resistance and good reflectance, it can be suitably used as a heat shield pigment to be blended in a paint.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

L'invention concerne un pigment réfléchissant les infrarouges comprenant une couche de film mince métallique et une couche diélectrique disposée des deux côtés de la couche de film mince métallique. La couche de film mince métallique contient au moins un allliage parmi un alliage d'AgCu et un alliage d'AgBiNd. La couche diélectrique contient de l'oxyde de titane.
PCT/JP2020/010973 2019-03-13 2020-03-12 Pigment réfléchissant les infrarouges WO2020184694A1 (fr)

Applications Claiming Priority (2)

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JP2019-045546 2019-03-13
JP2019045546A JP2020147661A (ja) 2019-03-13 2019-03-13 赤外線反射顔料

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WO2020184694A1 true WO2020184694A1 (fr) 2020-09-17

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021206062A1 (fr) * 2020-04-09 2021-10-14 日本ペイントホールディングス株式会社 Pigment réfléchissant les infrarouges, composition de peinture, film de peinture et article

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022064710A (ja) * 2020-10-14 2022-04-26 尾池工業株式会社 鱗片状顔料、分散液、塗料、及び塗膜

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002141694A (ja) * 2000-10-31 2002-05-17 Furuya Kinzoku:Kk 電磁波遮蔽膜及びこれを用いた電磁波遮蔽積層体
JP2009051713A (ja) * 2007-08-29 2009-03-12 Bridgestone Corp 熱線遮蔽性合わせガラス
JP2011520000A (ja) * 2008-05-09 2011-07-14 ビーエーエスエフ ソシエタス・ヨーロピア 金属酸化物／水酸化物層およびアクリルコポリマーで塗布された真珠箔顔料
WO2016006664A1 (fr) * 2014-07-10 2016-01-14 日本ペイントホールディングス株式会社 Pigment et composition de revêtement réfléchissant l'infrarouge
JP2017030348A (ja) * 2015-08-04 2017-02-09 株式会社神戸製鋼所 積層膜及び熱線反射材
JP2019085482A (ja) * 2017-11-06 2019-06-06 トヨタ自動車株式会社 赤外線反射顔料の粉末を製造する方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002141694A (ja) * 2000-10-31 2002-05-17 Furuya Kinzoku:Kk 電磁波遮蔽膜及びこれを用いた電磁波遮蔽積層体
JP2009051713A (ja) * 2007-08-29 2009-03-12 Bridgestone Corp 熱線遮蔽性合わせガラス
JP2011520000A (ja) * 2008-05-09 2011-07-14 ビーエーエスエフ ソシエタス・ヨーロピア 金属酸化物／水酸化物層およびアクリルコポリマーで塗布された真珠箔顔料
WO2016006664A1 (fr) * 2014-07-10 2016-01-14 日本ペイントホールディングス株式会社 Pigment et composition de revêtement réfléchissant l'infrarouge
JP2017030348A (ja) * 2015-08-04 2017-02-09 株式会社神戸製鋼所 積層膜及び熱線反射材
JP2019085482A (ja) * 2017-11-06 2019-06-06 トヨタ自動車株式会社 赤外線反射顔料の粉末を製造する方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021206062A1 (fr) * 2020-04-09 2021-10-14 日本ペイントホールディングス株式会社 Pigment réfléchissant les infrarouges, composition de peinture, film de peinture et article

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