WO2021206062A1 - Pigment réfléchissant les infrarouges, composition de peinture, film de peinture et article - Google Patents

Pigment réfléchissant les infrarouges, composition de peinture, film de peinture et article Download PDF

Info

Publication number
WO2021206062A1
WO2021206062A1 PCT/JP2021/014518 JP2021014518W WO2021206062A1 WO 2021206062 A1 WO2021206062 A1 WO 2021206062A1 JP 2021014518 W JP2021014518 W JP 2021014518W WO 2021206062 A1 WO2021206062 A1 WO 2021206062A1
Authority
WO
WIPO (PCT)
Prior art keywords
less
mol
infrared reflective
layer
laminate
Prior art date
Application number
PCT/JP2021/014518
Other languages
English (en)
Japanese (ja)
Inventor
翔大 佐々木
聖也 太田
藤田　健
裕司 川島
卓也 木下
芳樹 岡田
Original Assignee
日本ペイントホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本ペイントホールディングス株式会社 filed Critical 日本ペイントホールディングス株式会社
Publication of WO2021206062A1 publication Critical patent/WO2021206062A1/fr

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

  • the present invention relates to infrared reflective pigments, coating compositions, coatings and articles.
  • the surface of the laminated body of the infrared reflective pigment is coated with a surface treatment layer, so that when the infrared reflective pigment is blended in the coating film, the resin is laminated. It is disclosed that it suppresses deterioration due to direct contact with the dielectric layer and the metal thin film layer inside.
  • Example 1 (paragraph [0085]) of Patent Document 1
  • an infrared reflective pigment on which a surface-treated layer of aluminum oxide is formed is obtained by a neutralization hydrolysis method using sodium aluminate and sulfuric acid. ing.
  • Example 5 of Patent Document 1 an infrared reflective pigment on which a surface-treated layer of silica is formed is obtained (Patent Document 1, Table 1).
  • the present invention has improved durability of infrared reflection performance and visible light transmission performance even when a surface layer composed of a compound of oxygen and silicon is used, and suppresses adhesion between infrared reflective pigments. It is an object of the present invention to provide an infrared reflective pigment.
  • Another object of the present invention is to provide a coating composition containing such an infrared reflective pigment.
  • Another object of the present invention is to provide a coating film having improved durability of infrared reflection performance and visible light transmission performance and a small haze value.
  • Another object of the present invention is to provide an article having improved durability of infrared reflection performance and visible light transmission performance and a small haze value.
  • the infrared reflective pigment is Laminated body and A surface layer composed of a compound of oxygen and silicon, Including
  • the laminate is composed of a metal layer and a dielectric layer.
  • the laminates are, in order, The first dielectric layer and With a metal layer
  • the surface layer composed of the oxygen and silicon compound covers at least the exposed metal layer on the side surface of the laminate, and the thickness of the surface layer composed of the oxygen and silicon compound covering the coating is 20 to 200 nm.
  • the metal layer is a silver layer or a silver alloy layer.
  • the coating composition according to the present invention is a coating composition containing any of the above infrared reflective pigments. As a result, it is possible to form a coating film having improved durability of infrared reflection performance and visible light transmission performance and a small haze value.
  • the coating film according to the present invention is a coating film using the above coating composition.
  • the coating film has improved durability of infrared reflection performance and visible light transmission performance, and has a small haze value.
  • the article according to the present invention is an article having the above coating film.
  • the article has improved durability of infrared reflection performance and visible light transmission performance, and has a small haze value.
  • the present invention even when a surface layer composed of a compound of oxygen and silicon is used, it has improved durability of infrared reflection performance and visible light transmission performance, and suppresses adhesion between infrared reflective pigments.
  • Infrared reflective pigments can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the infrared reflective pigment of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the infrared reflective pigment of the present invention.
  • FIG. 3 is a schematic cross-sectional view showing another example of the configuration of the infrared reflective pigment of the present invention.
  • FIG. 4 is a schematic cross-sectional view showing another example of the configuration of the infrared reflective pigment of the present invention.
  • film thickness the thickness of the coating film and various layers is referred to as "film thickness”.
  • film thickness and “dry film thickness” other than “optical film thickness” mean physical film thickness unless otherwise specified.
  • visible light refers to an electromagnetic wave having a wavelength in the range of 380 to 780 nm.
  • the visible light peripheral region refers to a wavelength of 180 to 980 nm.
  • the wavelength range of infrared light refers to the range of 780 to 2,500 nm, and the wavelength range of radio waves refers to the range of 0.1 mm to 10 km.
  • 380 to 780 nm means 380 nm or more and 780 nm or less.
  • the paint and the paint composition can be used interchangeably.
  • first, second, and third are used herein to describe the various layers, but these layers are not limited by these terms. These terms are used only to distinguish one layer from another.
  • the third dielectric layer may be located outside the laminate than the second dielectric layer, or may be located outside the first dielectric layer. May be located on the outside of the laminate.
  • the infrared reflective pigment according to the present invention is a flat plate-shaped infrared reflective pigment.
  • the infrared reflective pigment is Laminated body and A surface layer composed of a compound of oxygen and silicon, Including
  • the laminate is composed of a metal layer and a dielectric layer.
  • the laminates are, in order, The first dielectric layer and With a metal layer
  • the surface layer composed of the oxygen and silicon compound covers at least the exposed metal layer on the side surface of the laminate, and the thickness of the surface layer composed of the oxygen and silicon compound covering the coating is 20 to 200 nm.
  • the "surface layer composed of a compound of oxygen and silicon” may be simply referred to as a "surface layer”.
  • the “surface tension adjusting layer” described later is not a "surface layer”.
  • FIG. 1 is a schematic cross-sectional view showing an example of the configuration of the infrared reflective pigment of the present invention.
  • the infrared reflective pigment 1 of the example of FIG. 1 is composed of a laminate 10 and a surface layer 11 composed of a compound of oxygen and silicon.
  • the laminate 10 is composed of two dielectric layers 12 and one metal layer 13.
  • the surface layer 11 covers the entire surface including the side surface of the laminated body 10.
  • the film thickness of the surface layer 11 is 20 to 200 nm.
  • the dielectric layer 12, the metal layer 13, and the dielectric layer 12 are laminated adjacent to each other in this order. Further, in the laminated body 10 of the example of FIG. 1, the two dielectric layers 12 have the same film thickness.
  • FIG. 2 is a schematic cross-sectional view showing another example of the configuration of the infrared reflective pigment of the present invention.
  • the surface layer 11 covers all the exposed side surfaces of the metal layer 13 of the laminate 10 and a part of the exposed side surfaces of the dielectric layer 12, but the infrared reflective pigment 1 The upper and lower surfaces of the are not covered.
  • the film thickness of the surface layer 11 is 20 to 200 nm.
  • FIG. 3 is a schematic cross-sectional view showing another example of the configuration of the infrared reflective pigment of the present invention.
  • the surface layer 11 covers all the side surfaces of the laminate 10, but does not cover the upper surface and the lower surface of the infrared reflective pigment 1.
  • the film thickness of the surface layer 11 is 20 to 200 nm.
  • FIG. 4 is a schematic cross-sectional view showing another example of the configuration of the infrared reflective pigment of the present invention.
  • the laminated body 10 is composed of a three-layer dielectric layer 12 and a two-layer metal layer 13.
  • the film thickness of the surface layer 11 is 20 to 200 nm.
  • the laminated body containing the infrared reflective pigment of the present invention comprises a metal layer and a dielectric layer. Then, the laminate includes, in order, a first dielectric layer, a metal layer, and a second dielectric layer. With this laminated structure, infrared reflectivity by the metal layer, protection of the metal layer by the dielectric layer, and visible light transmission can be ensured.
  • the laminate may include at least three layers of a first dielectric layer, a metal layer, and a second dielectric layer in order, and may further include a dielectric layer and a metal layer.
  • the first dielectric layer / metal layer / second dielectric layer As an example of the layer structure of the laminate, the first dielectric layer / metal layer / second dielectric layer; the first dielectric layer / metal layer (first metal layer) / second dielectric layer / Second metal layer / third dielectric layer; first dielectric layer / metal layer (first metal layer) / second dielectric layer / second metal layer / third dielectric layer / Third metal layer / Fourth dielectric layer and the like.
  • the metal layer is sandwiched between the two dielectric layers, and the outermost two layers in the stacking direction of the laminated body are the dielectric layers.
  • the laminate has a number of layers selected from the group consisting of 3 layers, 5 layers, 7 layers and 9 layers. In another embodiment, the laminate has a number of layers selected from the group consisting of three layers, five layers and seven layers. Two or more laminated bodies having different numbers of layers may be used in combination.
  • the thickness of the laminated body may be appropriately adjusted in consideration of infrared reflectance and visible light transmission due to the dielectric layer and the metal layer described later.
  • the average thickness of the laminate can be 30 to 200 nm.
  • the average thickness of the laminate is 50-100 nm, in another embodiment the laminate has three layers and the average thickness of the laminate is 30-150 nm, yet another.
  • the laminated body has five layers, and the average thickness of the laminated body is 50 to 200 nm.
  • the average thickness of the laminate can be obtained by a method for measuring the average thickness of the infrared reflective pigment, which will be described later.
  • the dielectric layer functions as an antireflection layer in the visible light peripheral region of the metal 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 imparts excellent visible light transmission to the coating film containing the infrared reflective pigment. Further, since the metal layer is usually thin, the first and second dielectric layers sandwich the metal layer to reinforce and protect the metal layer.
  • the material of the dielectric layer a conventionally known material of the dielectric layer can be used.
  • the material of the dielectric layer include titanium dioxide (TIO 2 ), titanium oxide (TIO), trititanium pentoxide (Ti 3 O 5 ), tetratitanium heptaoxide (Ti 4 O 7 ), and dititanium trioxide (Titanium trioxide).
  • Ti 2 O 3 zinc oxide (ZnO), zinc oxide (ZnS), niobium oxide (Nb 2 O 5 ), cerium oxide (CeO 2 ), tantalum oxide (Ta 2 O 5 ), aluminum oxide (Al 2 O 3) ), Zinc oxide (ZrO 2 ), silicon dioxide (SiO 2 ), tin dioxide (SnO 2 ), lanthanum titanate (La 2 Ti 2 O 7 ), tin-doped indium oxide (ITO), cerium-doped indium oxide (ICO). , Gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), indium oxide-zinc oxide (IZO) and antimony-doped tin oxide (ATO).
  • the above-mentioned materials can be used alone or in combination of two or more.
  • the material of the dielectric layer is at least selected from the group consisting of tin-doped indium oxide (ITO), zinc oxide (ZnO), titanium dioxide (TiO 2 ) and tin oxide (IV) (SnO 2). It is one kind. In another embodiment, the material of the dielectric layer is different from the material of the surface layer composed of a compound of oxygen and silicon.
  • the thickness of the dielectric layer may be appropriately set in consideration of the refractive indexes of the dielectric layer and the metal layer within a range in which the transmission of visible light can be enhanced by utilizing the light interference action.
  • the thickness of the dielectric layer is an integer of ⁇ / 4n. It is preferably double ⁇ 10 nm. From the viewpoint of visible light transmittance, an integer of 1, 2, 3 or 4 is preferable as an integer that is an integral multiple of the above.
  • the refractive index n is determined by ellipsometry measurement. Specifically, HORIBA and J. A. The value is measured at a temperature of 25 ° C. using an ellipsometer manufactured by Woolam JAPAN.
  • the refractive index of the dielectric layer is, for example, 2.3 for titanium dioxide (TiO 2 ), 1.83 for zinc oxide (ZnO), and 1.9 for tin-doped indium oxide (ITO).
  • the refractive index of the dielectric layer in the laminate is higher than the refractive index of the metal layer.
  • the film thickness of the dielectric layer is 10 nm or more, 15 nm or more, 18 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 70 nm. As mentioned above, it is 80 nm or more, 90 nm or more, 100 nm or more, or 110 nm or more.
  • the film thickness of the dielectric layer is 120 nm or less, 110 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 55 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, It is 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, or 10 nm or less.
  • the dielectric layer has a film thickness of 25-100 nm.
  • each dielectric layer there are at least two dielectric layers.
  • the material and film thickness of each dielectric layer may be the same or different.
  • the metal layer has a function of reflecting infrared light.
  • the metal layer imparts excellent infrared light reflectivity to the coating film containing the infrared reflective pigment.
  • the material of the metal layer a conventionally known material of a metal layer or an infrared reflective layer can be used.
  • the material of the metal layer include silver, silver alloy, aluminum, copper, gold, gold alloy, palladium, zinc, titanium, chromium and silicon.
  • the above-mentioned materials can be used alone or in combination of two or more.
  • the silver alloy refers to a silver alloy containing silver as a main component (for example, 50% by mass or more of the composition).
  • a silver-indium alloy, a silver-gold alloy, a silver-palladium-copper alloy, a silver-palladium-gold alloy and the like can be used.
  • the gold alloy refers to a gold alloy containing gold as a main component (for example, 50% by mass or more of the composition).
  • a gold-silver alloy, a gold-silver-copper alloy, a gold-silver-palladium-copper alloy, a gold-silicon alloy, a gold-antimon alloy, a gold-indium alloy and the like can be used. can.
  • the material of the metal layer is at least one selected from the group consisting of silver, silver alloy, aluminum, zinc and titanium. In another embodiment, the material of the metal layer is at least one selected from the group consisting of silver, silver alloys, aluminum, gold, gold alloys, zinc and titanium. In another embodiment, the metal layer is a silver layer or a silver alloy layer.
  • the film thickness of the metal layer may be appropriately set in consideration of the refractive indexes of the dielectric layer and the metal layer within a range in which the infrared light reflectivity can be enhanced. For example, it is 5 to 20 nm. In one embodiment, the film thickness of the metal layer is 5 nm or more, 8 nm or more, 10 nm or more, 15 nm or more, or 20 nm. In another embodiment, the film thickness of the metal layer is 30 nm or less, 25 nm or less, 20 nm or less, 15 nm or less, 10 nm or less, 8 nm or less, or 5 nm. In yet another embodiment, the thickness of the metal layer is 10 to 20 nm. When the film thickness of the metal layer is 20 nm or less, the visible light transmittance of the coating film is further enhanced. When the film thickness of the metal layer is 5 nm or more, the infrared light reflectivity of the coating film is further enhanced.
  • each metal layer When there are two or more metal layers, the material and film thickness of each metal layer may be the same or different.
  • the infrared reflective pigment of the present invention has a surface layer that covers at least the exposed metal layer on the side surface of the laminate.
  • the surface layer has a function of suppressing deterioration of the metal layer, that is, deterioration of infrared reflectivity and visible light transmission of the infrared reflective pigment.
  • the surface layer may cover at least the exposed metal layer on the side surface of the laminate.
  • the surface layer may, for example, cover the entire surface of the laminate as shown in FIG. 1; it may cover the metal layer on the side surface of the laminate as shown in FIG. 2, plus one of the dielectric layers.
  • the portion may be covered; the entire side surface of the laminate may be covered as shown in FIG.
  • the present inventors further examined the infrared reflective pigment having the silica surface treatment layer of Example 5 of Patent Document 1, the surface layer (with oxygen) covering the exposed silver layer on the side surface of the laminate was examined.
  • the film thickness of the surface layer made of a silicon compound By setting the film thickness of the surface layer made of a silicon compound to a certain level or higher, the durability of the infrared reflectivity and visible light transmission of the infrared reflective pigment can be further improved even under severe conditions such as acidic conditions. I found it.
  • the adhesion of the infrared reflective pigment having the surface treatment layer of silica is caused through the surface treatment layer, and the film thickness of the surface treatment layer has a constant thickness.
  • the amount of adhesion between pigments increases, and by reducing the thickness of the surface layer (surface layer composed of a compound of oxygen and silicon) to a certain level or less, the adhesion between pigments is suppressed and the haze of the coating film is haze. We found that the value could be reduced.
  • the film thickness of the surface layer is 20 to 200 nm.
  • the film thickness of the surface layer covering the exposed metal layer is 20 nm or more, the durability of infrared reflectance and visible light transmission is improved, and when it is 200 nm or less, the pigments are fixed to each other. It can be suppressed and the haze value of the coating film can be reduced.
  • the film thickness of the surface layer composed of a compound of oxygen and silicon is 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 55 nm or more, 60 nm or more, 65 nm or more, 70 nm.
  • nm or more 75 nm or more, 80 nm or more, 85 nm or more, 90 nm or more, 95 nm or more, 100 nm or more, 110 nm or more, 120 nm or more, 130 nm or more, 140 nm or more, 150 nm or more, 160 nm or more, 170 nm or more, 180 nm or more, 190 nm or more or 200 nm. ..
  • the film thickness of the surface layer composed of a compound of oxygen and silicon is 200 nm or less, 190 nm or less, 180 nm or less, 170 nm or less, 160 nm or less, 150 nm or less, 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, At 100 nm or less, 95 nm or less, 90 nm or less, 85 nm or less, 80 nm or less, 75 nm or less, 70 nm or less, 65 nm or less, 60 nm or less, 55 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less or 20 nm. be.
  • the film thickness of the surface layer composed of a compound of oxygen and silicon is 20 to 150 nm.
  • the surface layer composed of a compound of oxygen and silicon contains silicon dioxide. In another embodiment, the surface layer made of a compound of oxygen and silicon is made of silicon dioxide.
  • the surface layer composed of a compound of oxygen and silicon contains silicone. In another embodiment, the surface layer made of a compound of oxygen and silicon is made of silicone.
  • the surface layer composed of a compound of oxygen and silicon is in M (R 3 SiO 1/2 ) units, D (R 2 SiO 2/2 ) units, T (RSiO 3/2 ) units and Q (SiO) units. 4/2 ) Silicone containing at least one selected from the group consisting of units.
  • the surface layer composed of a compound of oxygen and silicon is a silicone composed of at least one selected from the group consisting of M units, D units, T units and Q units.
  • the surface layer composed of a compound of oxygen and silicon is a silicone composed of at least one selected from the group consisting of D units, T units and Q units.
  • the surface layer composed of a compound of oxygen and silicon is a silicone composed of at least one selected from the group consisting of T units and Q units. In yet another embodiment, the surface layer composed of a compound of oxygen and silicon is a silicone composed of Q units.
  • the surface layer composed of a compound of oxygen and silicon contains silicon dioxide and silicone. In another embodiment, the surface layer made of a compound of oxygen and silicon is made of silicon dioxide and silicone.
  • the surface layer consisting of a compound of oxygen and silicon is silicon dioxide and M (R 3 SiO 1/2 ) units, D (R 2 SiO 2/2 ) units, T (RSiO 3/2 ) units and Contains silicone containing at least one selected from the group consisting of Q (SiO 4/2) units.
  • the surface layer composed of a compound of oxygen and silicon is silicon dioxide and M (R 3 SiO 1/2 ) units, D (R 2 SiO 2/2 ) units, T (RSiO 3/2 ) units. And consists of silicone containing at least one selected from the group consisting of Q (SiO 4/2) units.
  • the surface of the infrared reflective pigment may be optionally coated with a surface tension adjusting layer.
  • the surface tension adjusting layer has a function of promoting the movement of the infrared reflective pigment to the coating film surface when the infrared reflective pigment is blended in the coating film.
  • the flat plate surface of the infrared reflective pigment is likely to be oriented parallel to the surface of the coating film, and excellent infrared light reflection and visible light transmission of the coating film can be obtained.
  • the surface tension adjusting layer may be provided on at least a part of the surface of the infrared reflective pigment, and may be provided on the entire surface of the infrared reflective pigment.
  • the material of the surface tension adjusting layer can be appropriately selected from known materials in consideration of its function. Examples include stearic acid, oleic acid, phosphonic acid and phosphoric acid esters. As the material of the surface tension adjusting layer, the above-mentioned materials can be used alone or in combination of two or more.
  • the blending amount of the material of the surface tension adjusting layer may be appropriately adjusted in consideration of its function.
  • the blending amount of the surface tension adjusting layer can be 0.01 to 10 parts by mass with respect to 100 parts by mass of the infrared reflective pigment. Preferably, it is 0.1 to 3 parts by mass.
  • the thickness of the surface tension adjusting layer may be appropriately adjusted in consideration of its function.
  • the thickness of the surface tension adjusting layer can be 0.1 to 10 nm. It is preferably 0.1 to 5 nm, more preferably 0.1 to 2 nm.
  • the dimensions of the infrared reflective pigment may be adjusted as appropriate.
  • the average maximum diameter of the infrared reflective pigment is 1,000 nm or more, 5,000 nm or more, 10,000 nm or more, 15,000 nm or more, 20,000 nm or more, 25,000 nm or more, 30,000 nm. As mentioned above, it is 35,000 nm or more, 40,000 nm or more, 45,000 nm or more, or 50,000 nm or more.
  • the average maximum diameter of the infrared reflective pigment is 50,000 nm or less, 45,000 nm or less, 40,000 nm or less, 35,000 nm or less, 30,000 nm or less, 25,000 nm or less, 20, It is 000 nm or less, 15,000 nm or less, 10,000 nm or less, 5,000 nm or less, or 1,000 nm or less. In yet another embodiment, the average maximum diameter of the infrared reflective pigment is 10,000-30,000 nm.
  • the maximum diameter of the infrared reflective pigment means the maximum length (major axis) of the infrared reflective pigment.
  • an infrared reflective pigment dispersion liquid added to butyl acetate so that the maximum diameter of the infrared reflective pigment is 0.1% by weight of the infrared reflective pigment is prepared, and a flow type particle image is obtained. Measurement is performed using an analyzer FPIA-3000S (manufactured by Sysmex).
  • the average of the maximum diameters of the infrared reflective pigments means the number average of the measurement results of the maximum diameters of 10,000 pigments in the infrared reflective pigment dispersion liquid.
  • the thickness of the infrared reflective pigment is 30 nm or more, 50 nm or more, 100 nm or more, 150 nm or more, 200 nm or more, 250 nm or more, 300 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more or 540 nm or more. Is.
  • the thickness of the infrared reflective pigment is 540 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 300 nm or less, 250 nm or less, 200 nm or less, 150 nm or less, 100 nm or less or 50 nm or less. .. In yet another embodiment, the thickness of the infrared reflective pigment is 50-300 nm.
  • the thickness of the infrared reflective pigment means the length of the infrared reflective pigment in the direction perpendicular to the plane where the maximum diameter of the infrared reflective pigment exists.
  • the thickness of the infrared reflective pigment was determined by scanning an infrared reflective pigment dispersion liquid added to butyl acetate so that the infrared reflective pigment was 0.1% by weight of the scanning electron microscope JSM-6060A (manufactured by JEOL Ltd.).
  • Infrared reflectivity arbitrarily selected from infrared reflective pigments that are dropped on a sample table, dried at room temperature, gold-deposited, observed by SEM, and fixed in a state where the thickness can be measured on the sample table. It is calculated from the number average of the thicknesses of 20 pigments.
  • the method for producing an infrared reflective pigment of the present invention is, for example, (1) a step of producing a laminate composed of a metal layer and a dielectric layer, and then (2) desired. This includes a step of crushing the laminate to the size shown in (3), and then (3) coating an exposed metal layer on at least the side surface of the pulverized laminate with a surface layer composed of a compound of oxygen and silicon.
  • the above three steps may be referred to as (1) step, (2) step and (3) step, respectively.
  • the steps (1) and (2) may include other steps such as a step of separating the laminate from the support.
  • other steps such as a step of classifying the crushed laminate may be included between the steps (2) and (3).
  • a step of providing the surface tension adjusting layer described in Patent Document 1 may be optionally included.
  • the steps (1) and (2) are not particularly limited, and conventionally known production methods such as pigment laminates and pulverization methods can be used.
  • the crushing step of the first production method described in Patent Document 1 or International Publication No. 2018/034261 may be performed, or the crushing of the second production method described in Patent Document 1 or International Publication No. 2018/034261 may be performed. You may go to the process.
  • step (3) the exposed metal layer on at least the side surface of the laminate is coated with the surface layer by the sol-gel method having a specific material concentration.
  • the sol-gel method itself is a known method, the present inventors have performed the sol-gel method at a specific concentration rather than a general concentration to expose the side surface of the laminate of infrared reflective pigments and to have fine particles. It has been found that the metal layer can be coated with a constant film thickness.
  • the step includes, for example, the following steps: (I) A step of preparing a laminate slurry by adding a laminate crushed to a desired size to one or more solvents selected from the group consisting of alcohols, ester solvents, ketone solvents and aromatic solvents. ; (Ii) A step of adding 5.6 mol or more of water and 5.9 mol or more of bases to 100 g of the laminate to prepare a laminate dispersion liquid; and (iii) laminate. A step of adding 0.48 mol or more of alkoxysilane to 100 g of the laminate to the body dispersion liquid.
  • the above three steps may be referred to as (i) step, (ii) step and (iii) step, respectively.
  • Step (i) a laminate crushed to a desired size is added to one or more solvents selected from the group consisting of alcohols, ester solvents, ketone solvents and aromatic solvents. Prepare a laminate slurry.
  • the alcohol is not particularly limited and can be appropriately selected.
  • examples of the alcohol in the step (i) include methanol, ethanol, propanol, butanol and the like.
  • the alcohol in step (i) is at least one selected from methanol, ethanol, propanol and butanol.
  • the alcohol in step (i) is ethanol.
  • the ester solvent is not particularly limited and can be appropriately selected.
  • the ester solvent include ethyl acetate, butyl acetate, isobutyl acetate and the like.
  • the ester solvent is at least one selected from ethyl acetate, butyl acetate and isobutyl acetate.
  • the ester solvent is butyl acetate.
  • the ketone solvent is not particularly limited and can be appropriately selected.
  • the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like.
  • the ketone solvent is at least one selected from acetone, methyl ethyl ketone and methyl isobutyl ketone.
  • the ketone solvent is acetone.
  • the aromatic solvent is not particularly limited and can be appropriately selected.
  • the aromatic solvent include benzene, toluene, xylene and the like.
  • the aromatic solvent is at least one selected from benzene, toluene and xylene.
  • the aromatic solvent is xylene.
  • the concentration of the laminate in the laminate slurry may be adjusted as appropriate.
  • the concentration of the laminate in the laminate slurry is, for example, 0.01 to 5% by mass.
  • the concentration of the laminate is 0.01% by mass or more, 0.05% by mass or more, 0.10% by mass or more, 0.30% by mass or more, 0.50% by mass or more, 1.00. Mass% or more, 1.50 mass% or more, 2.00 mass% or more, 2.50 mass% or more, 3.00 mass% or more, 3.50 mass% or more, 4.00 mass% or more or 4.50 mass % Or more.
  • the concentration of the laminate is 5.00% by mass or less, 4.50% by mass or less, 4.00% by mass or less, 3.50% by mass or less, 3.00% by mass or less, 2. It is 50% by mass or less, 2.00% by mass or less, 1.50% by mass or less, 1.00% by mass or less, 0.50% by mass or less, or 0.30% by mass or less.
  • the concentration of the laminate is 0.10 to 0.50% by mass.
  • Step (ii) In the step (ii), 5.6 mol or more of water and 5.9 mol or more of bases are added to 100 grams of the laminate to prepare a laminate dispersion liquid. ..
  • the water added in the step (ii) examples include tap water, distilled water, and deionized water.
  • the water added in step (ii) is at least one selected from the group consisting of distilled water and deionized water.
  • the water added in step (ii) is distilled water.
  • the amount of water added in the step (ii) is, for example, 5.6 mol or more with respect to 100 grams of the laminate.
  • the amount of water added in the step (ii) is, for example, 560 mol or less with respect to 100 grams of the laminate.
  • the amount of water added in step (ii) is 5.6 mol or more, 10 mol or more, 50 mol or more, 100 mol or more, 150 mol or more, 160 mol or more with respect to 100 grams of the laminate.
  • step (ii) is 560 mol or less, 550 mol or less, 500 mol or less, 450 mol or less, 400 mol or less, 350 mol or less, based on 100 grams of the laminate.
  • step (ii) is 56-290 mol per 100 grams of laminate.
  • Examples of the base added in the step (ii) include ammonia, ammonium hydroxide, diethanolamine, triethylamine and the like.
  • Ammonia may be used as ammonia water.
  • Commercially available aqueous ammonia usually has a concentration of about 28%.
  • the base may be used alone or in combination of two or more.
  • the amount of the base added in the step (ii) is, for example, 5.9 mol or more with respect to 100 grams of the laminate.
  • the amount of the base added in the step (ii) is, for example, 176 mol or less with respect to 100 grams of the laminate.
  • the amount of base added in step (ii) is 5.9 mol or more, 10 mol or more, 20 mol or more, 29 mol or more, 30 mol or more, 40 mol or more with respect to 100 grams of the laminate. , 50 mol or more, 60 mol or more, 70 mol or more, 80 mol or more, 90 mol or more, 100 mol or more or 150 mol or more.
  • the amount of base added in step (ii) is 176 mol or less, 170 mol or less, 150 mol or less, 120 mol or less, 118 mol or less, 100 mol or less, based on 100 grams of the laminate. 90 mol or less, 80 mol or less, 70 mol or less, 60 mol or less, 50 mol or less, 40 mol or less, 30 mol or less, 20 mol or less or 10 mol or less. In yet another embodiment, the amount of base added in step (ii) is 29-118 mol per 100 grams of laminate.
  • Step (iii) In the step (iii), 0.48 mol or more of alkoxysilane is added to the laminate dispersion liquid with respect to 100 grams of the laminate.
  • alkoxysilane added in the step (iii) examples include tetraalkoxysilane, trialkoxysilane, and dialkoxysilane. In addition, monoalkoxysilane may be used.
  • alkoxy group of the alkoxysilane examples include a methoxy group, an ethoxy group, a propoxy group, a tert-butoxy group and the like.
  • the alkoxysilane added in the step (iii) is at least one selected from the group consisting of tetraalkoxysilane, trialkoxysilane and dialkoxysilane. In another embodiment, the alkoxysilane added in step (iii) is at least one selected from the group consisting of tetraalkoxysilanes and trialkoxysilanes. In yet another embodiment, the alkoxysilane added in step (iii) is tetraalkoxysilane.
  • the alkoxysilanes added in step (iii) are tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetratert-butoxysilane; trimethoxysilane, triethoxysilane, tripropoxysilane, tritert-butoxylane.
  • Silane at least one selected from the group consisting of dimethoxysilane, diethoxysilane, dipropoxysilane and ditert-butoxysilane.
  • the alkoxysilane added in step (iii) is at least one selected from the group consisting of tetraethoxysilane, triethoxysilane and diethoxysilane. In yet another embodiment, the alkoxysilane added in step (iii) is at least one selected from the group consisting of tetraethoxysilane and triethoxysilane. In yet another embodiment, the alkoxysilane added in step (iii) is tetraethoxysilane.
  • the amount of alkoxysilane added in the step (iii) is, for example, 0.48 mol or more with respect to 100 grams of the laminate.
  • the amount of alkoxysilane added in the step (iii) is, for example, 6.90 mol or less with respect to 100 grams of the laminate.
  • the amount of alkoxysilane added in step (iii) is 0.48 mol or more, 0.50 mol or more, 0.64 mol or more, 0.75 mol or more, based on 100 grams of the laminate. 0.96 mol or more, 1.00 mol or more, 1.10 mol or more, 1.20 mol or more, 1.30 mol or more, 1.40 mol or more, 1.50 mol or more, 1.60 mol or more 1.
  • the amount of alkoxysilane added in step (iii) is 6.75 mol or less, 6.70 mol or less, 6.50 mol or less, 6.00 mol or less, 5.50 mol or less, 5 .00 mol or less, 4.50 mol or less, 4.00 mol or less, 3.50 mol or less, 3.40 mol or less, 3.25 mol or less, 3.00 mol or less, 2.50 mol or less, 2.00 mol Mol or less 1.90 mol or less, 1.80 mol or less, 1.70 mol or less, 1.60 mol or less, 1.50 mol or less, 1.40 mol or less, 1.30 mol or less, 1.20 mol or less , 1.10 mol or less, 1.00 mol or less, 0.75 mol or less, or 0.50 mol or less.
  • the amount of alkoxysilane added in step (iii) is 0.96 to 1.7 mol per 100 grams of laminate.
  • the alkoxysilane added in the step (iii) may be added as an alcohol solution of the alkoxysilane.
  • the alcohol solvent include those similar to the alcohol in step (i).
  • the alcohol solvent of this alkoxysilane and the alcohol in step (i) may be the same or different.
  • the concentration of alkoxysilane may be adjusted as appropriate.
  • the concentration of alkoxysilane in the alcohol solution is, for example, 1 to 10% by mass, preferably 2 to 5% by mass.
  • the reaction temperature in the step (iii) may be adjusted as appropriate.
  • the reaction temperature of the step (iii) is, for example, 0 to 80 ° C, preferably 15 to 35 ° C.
  • the reaction time of the (iii) step may be adjusted as appropriate.
  • the reaction time of the step (iii) is, for example, 30 to 300 minutes, preferably 60 to 240 minutes.
  • steps such as filtration, recovery, and cleaning of the precipitated product, that is, the laminate coated with the surface layer may be performed.
  • the amount of water added in step (ii) is 100 to 10 with respect to 100 parts by mass of the laminate. 000 parts by mass; the amount of ammonia added in step (ii) is 100 to 3,000 parts by mass with respect to 100 parts by mass of the laminate; the amount of tetraethoxysilane added in step (iii). Is 100 to 1410 parts by mass with respect to 100 parts by mass of the laminated body.
  • the amount of water added in step (ii) is 1, with respect to 100 parts by mass of the laminate. 000 to 5,220 parts by mass; the amount of ammonia added in step (ii) is 490 to 2,010 parts by mass with respect to 100 parts by mass of the laminate; tetraethoxy added in step (iii).
  • the amount of silane is 100 to 710 parts by mass or 200 to 355 parts by mass with respect to 100 parts by mass of the laminate.
  • the coating composition according to the present invention is a coating composition containing any of the above infrared reflective pigments. As a result, deterioration of infrared reflection performance and visible light transmission performance can be suppressed, and a coating film having a small haze value can be formed.
  • the infrared reflective pigment of the present invention may be used alone or in combination of different materials, dimensions, layer configurations and the like.
  • the amount of the infrared reflective pigment of the present invention in the coating composition may be appropriately adjusted.
  • the amount of the infrared reflective pigment in the coating composition is, for example, 0.15 to 20%, preferably 1 to 10%, based on the total solid content.
  • the coating composition according to the present invention includes a resin component, a solvent, an anti-sagging agent, a viscosity modifier, an anti-settling agent, a cross-linking accelerator, a curing agent, a leveling agent, a surface adjusting agent, and an erasing agent. It may contain other ingredients such as foaming agents, plasticizers, preservatives, fungicides, and UV stabilizers.
  • the resin component has a function as a coating film forming element.
  • a resin component of a conventionally known coating composition can be used.
  • the resin component include acrylic resin, polyester resin, alkyd resin, fluororesin, epoxy resin, polyurethane resin, melamine resin, and polyether resin described in Patent Document 1.
  • the resin component may have an unsaturated double bond in the side chain of the resin.
  • a polymer compound containing an inorganic component or composed of an inorganic component, such as a silicone resin or an alkoxysilane condensate can also be used.
  • the resin component may be used alone or in combination of two or more.
  • the above resin components include a curing type and a lacquer type, and these may be used alone or in combination.
  • the curable type it is used by mixing with a cross-linking agent such as an amino resin, a (block) polyisocyanate compound, an amine-based, a polyamide-based, or a polyvalent carboxylic acid.
  • a reaction with an acrylate compound and a polymerization initiator is also used.
  • the curing type resin component can proceed with the curing reaction by heating or UV irradiation, or at room temperature.
  • a solvent of a conventionally known coating composition can be appropriately selected and used.
  • alcohols such as methanol, ethanol, 2-propanol and 1-butanol; ethyl acetate, butyl acetate, isobutyl acetate, ethyl propionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like.
  • Ethers such as diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, tetrahydrofuran (THF); ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3- Glycols such as butylene glycol, pentamethylene glycol, 1,3-octylene glycol; formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP) Amidos such as: acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isobutyl ketone, acetyl acetone, cyclohexanone and other ketones; toluene, xylene, mesityrene, dodecylbenzene
  • the method for preparing a coating composition is not particularly limited, and the above-mentioned infrared reflective pigment and resin component and other components which are optional components are mixed and prepared by a conventionally known method. be able to.
  • the coating film according to the present invention is a coating film using the above coating composition. As a result, the coating film has improved durability of infrared reflection performance and visible light transmission performance, and has a small haze value.
  • the film thickness of the coating film is not particularly limited and may be adjusted as appropriate.
  • the film thickness of the coating film is 1 to 100 ⁇ m (1,000 to 100,000 nm).
  • a method for producing a coating film As a method for producing a coating film, a conventionally known coating method can be used. For example, it can be painted using an applicator, a bar coater, a brush, a spray, a roller, or the like.
  • the drying temperature after applying the coating composition may be appropriately adjusted according to the solvent and the like. For example, when drying in a short time such as 10 seconds to 30 minutes is required, the temperature can be 60 to 200 ° C, preferably 80 to 160 ° C. If it is not necessary to dry in a short time, it may be dried at room temperature, for example.
  • the article according to the present invention is an article having the above coating film. As a result, the article has improved durability of infrared reflection performance and visible light transmission performance, and has a small haze value.
  • Articles having a coating are not particularly limited, and vehicles such as automobiles, trains, buses, and taxis; vehicle tires; ships; aircraft such as airplanes and helicopters; detached houses, apartment buildings such as condominiums, office buildings, and public Buildings or structures such as facilities, commercial facilities, research facilities, military facilities, tunnels, floors, ceilings, roofs, pillars, signs, electronic signage (digital signage), doors, gates, windows; vehicles and buildings Glass such as; bridges; vending machines; road signs; signals; street lights; lightning bulletin boards such as LED, liquid crystal, and light bulbs; work machines, construction machines; stone monuments; tombstones; clothing; footwear such as shoes; umbrellas, kappa Rain gear such as rain gear; packaging materials; lenses such as glasses; mirrors; fan; toys; fishing gear such as lures and fishing rods; cases made of glass, acrylic, polycarbonate, etc., containers, resin plates, transparent materials such as films, etc. Can be mentioned.
  • the coating film of the article may be only one type or two or more types.
  • the article according to the present invention may or may not have other coating film layers such as an undercoat layer and a topcoat layer in addition to the coating film of the present invention.
  • Example 1 titanium dioxide and silver are used as materials for the dielectric layer and the metal layer, respectively, in accordance with the manufacturing method of Example 5 of Patent Document 1, and the first shown in Table 2 is used. A five-layered laminate of the dielectric layer, the first metal layer, the second dielectric layer, the second metal layer, and the third dielectric layer was obtained. The maximum diameter of the laminate was 20 ⁇ m.
  • Example 1 The obtained laminate was added to ethanol to prepare a laminate slurry having a concentration of 0.30% by mass. Next, while stirring the laminate slurry, 3744 g (208 mol) of distilled water and an amount of ammonia water (concentration 28%) so as to have 935 g (55 mol) of ammonia were added to 100 g of the laminate. To prepare a laminate dispersion. On the other hand, tetraethoxysilane (TEOS) was added to ethanol to prepare a TEOS solution having a concentration of 3.5% by mass.
  • TEOS tetraethoxysilane
  • Example 1 The ethanol solution of the infrared reflective pigment obtained in Example 1 was dropped onto a TEM grit of a field emission transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.), vacuum dried at room temperature, and then observed by TEM. By TEM observation, it was confirmed that the side surface of the laminate was covered with a surface layer composed of a compound of oxygen and silicon as shown in FIG.
  • Example 2 In Example 1, a silver-palladium-copper alloy (APC; containing Ag as a main component, 0.91 at% of Pd and 1.69 at% of Cu) was used as the material of the metal layer instead of silver. Except for the above, the laminate was formed and the surface layer was coated in the same manner as in Example 1 to obtain an infrared reflective pigment.
  • APC silver-palladium-copper alloy
  • Examples 3 to 8 and Comparative Examples 1 to 3 In the treatment of Example 1, the surface layer was coated in the same manner as in Example 1 except that the amount of TEOS was changed as shown in Table 1, to obtain an infrared reflective pigment.
  • Example 9 In the first embodiment, except that gold was used instead of silver as the material of the metal layer, the laminate was formed and the surface layer was coated in the same manner as in Example 1, and the infrared reflective pigment was used.
  • Example 10 In Example 1, instead of the five-layered laminate, titanium dioxide and silver are used as the materials for the dielectric layer and the metal layer, respectively, and the first dielectric layer / first metal shown in Table 3 is used. The surface layer was coated in the same manner as in Example 1 except that a three-layered laminate of a layer / a second dielectric layer was used to obtain an infrared reflective pigment.
  • Example 11 An infrared reflective pigment was obtained by forming the laminate and coating the surface layer in the same manner as in Example 1 except that the maximum diameter of the laminate was set to 10 ⁇ m in Example 1.
  • Example 12 An infrared reflective pigment was obtained by forming the laminate and coating the surface layer in the same manner as in Example 1 except that the maximum diameter of the laminate was set to 30 ⁇ m in Example 1.
  • Example 13 An infrared reflective pigment was obtained in Example 1 by forming a laminate and coating the surface layer in the same manner as in Example 1 except that butyl acetate was used instead of ethanol.
  • Example 4 A surface layer was formed on the release layer in advance by an electron beam method using a vacuum vapor deposition apparatus (model number: EX-200) manufactured by ULVAC, and a first dielectric layer (titanium dioxide) was sequentially formed on the surface layer. / After forming the first metal layer (silver) / second dielectric layer (titanium dioxide) / second metal layer (silver) / third dielectric layer (titanium dioxide), the third dielectric An infrared reflective pigment was obtained in accordance with the production method of Example 5 of Patent Document 1 except that a surface layer was formed on the layer by an electron beam method. That is, in the laminated body of Comparative Example 4, the exposed metal layer on the side surface of the laminated body was not covered with the surface layer.
  • An infrared reflective pigment dispersion was prepared by adding the infrared reflective pigment to butyl acetate so as to have a content of 0.1% by weight. Next, using the dispersion, the amount of the infrared reflective pigment fixed was evaluated from the particle image of 10,000 pigments using the flow type particle image analyzer FPIA-3000S (manufactured by Sysmex) according to the following evaluation criteria. .. Scores 3 to 5 pass and scores 1 and 2 fail. The results are shown in Tables 2 and 3. Evaluation Criteria 5: No adhesion between pigments 4: There is less than 5% of adhered pigments. 3: The adhered pigment is present in an amount of 5% or more and less than 10%. 2: The adhered pigment is present in an amount of 10% or more and less than 20%. 1: 20% or more of the fixed pigment is present.
  • nax multi-eco 1,000% by mass of nax multi-eco (3: 1) 20LX clear (manufactured by Nippon Paint) and 340% by mass of nax ultra hardener (manufactured by Nippon Paint) with respect to the butyl acetate dispersion of the infrared reflective pigment. In addition, it was stirred with a spatula. Further, butyl acetate was added to adjust the non-volatile content (NV) to 40%. A glass plate (10 mm ⁇ 10 mm) was coated with an applicator (3 mill) and dried at 65 ° C. for 30 minutes to obtain a test plate having a coating film on the glass plate.
  • Haze evaluation The haze value of the test plates of each Example and Comparative Example was measured using a haze meter (NDH2000 / manufactured by Nippon Denshoku Kogyo Co., Ltd.). The evaluation criteria are as follows. Scores 2 and 3 pass and score 1 fails. The results are shown in Tables 2 and 3. Evaluation Criteria 3: Haze value is 1 or less 2: Haze value is greater than 1 and less than 3 1: Haze value is 3 or more
  • the infrared reflectance of the portion of the test plate in contact with the aqueous hydrochloric acid solution was measured in accordance with JIS-R3106: 1998 "Test method for transmittance, reflectance, emissivity, and solar radiation acquisition rate of plate glass".
  • a spectrophotometer U-4100 manufactured by Hitachi, Ltd. was used for the measurement.
  • the suppression of deterioration of infrared reflectivity was evaluated by the following evaluation criteria. Scores 3 to 5 pass and scores 1 and 2 fail. The results are shown in Tables 2 and 3.
  • Evaluation Criteria 5 The infrared reflectance after the test does not change compared to the infrared reflectance before the test 4: The infrared reflectance after the test is 90% or more and less than 100% with respect to the infrared reflectance before the test.
  • Yes 3 The post-test infrared reflectance with respect to the pre-test infrared reflectance is 70% or more and less than 90% 2: The post-test infrared reflectance with respect to the pre-test infrared reflectance is 50% or more and 70%. Less than 1: The post-test infrared reflectance is less than 50% of the pre-test infrared reflectance.
  • a polyethylene cylinder having an inner diameter of 38 mm and a height of 15 mm was crimped onto the obtained test plate via a circular packing made of silicon rubber. Subsequently, an aqueous hydrochloric acid solution adjusted to 0.05% by weight was dropped from the opening at the top of the cylinder, and the opening was closed with a water resistant tape. The test piece was placed in an oven at 80 ° C. and heated for 8 hours. After the heating was completed, the cylinder and packing were removed, and the hydrochloric acid aqueous solution adhering to the test plate was removed with running water.
  • the visible light transmittance of the portion of the test plate in contact with the hydrochloric acid aqueous solution was measured in accordance with JIS-R3106: 1998 "Test method for transmittance, reflectance, emissivity, and solar radiation acquisition rate of plate glass".
  • a spectrophotometer U-4100 manufactured by Hitachi, Ltd. was used for the measurement.
  • the suppression of deterioration of visible light transmission was evaluated according to the following evaluation criteria. Scores 3 to 5 pass and scores 1 and 2 fail. The results are shown in Tables 2 and 3.
  • Evaluation Criteria 5 The visible light transmittance after the test does not change compared to the infrared reflectance before the test 4: The visible light transmittance after the test with respect to the infrared reflectance before the test is 95% or more and less than 100%.
  • Yes 3 The visible light transmittance after the test with respect to the infrared reflectance before the test is 90% or more and less than 95% 2: The visible light transmittance after the test with respect to the infrared reflectance before the test is 80% or more and 90% Less than 1: The visible light transmittance after the test is less than 80% with respect to the infrared reflectance before the test.
  • the present invention even when a surface layer composed of a compound of oxygen and silicon is used, it has improved durability of infrared reflection performance and visible light transmission performance, and suppresses adhesion between infrared reflective pigments. It was possible to provide an infrared reflective pigment. According to the present invention, it has been possible to provide a coating film and an article having improved durability of infrared reflection performance and visible light transmission performance and a small haze value.
  • Infrared reflective pigment 10 Laminated body 11: Surface layer composed of a compound of oxygen and silicon 12: Dielectric layer 13: Metal layer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un pigment réfléchissant les infrarouges qui, même lorsqu'une couche de surface comprenant un composé d'oxygène et de silicium est utilisée, présente en outre une durabilité améliorée des performances de réflexion des infrarouges et des performances de transmission de la lumière visible et qui supprime l'adhérence des pigments réfléchissant les infrarouges les uns aux autres. Le pigment réfléchissant les infrarouges en forme de plaque plate selon l'invention comprend un corps stratifié et une couche de surface qui est formée à partir d'un composé d'oxygène et de silicium ; le corps stratifié comprend une couche métallique et des couches diélectriques. Le corps stratifié comprend, dans l'ordre, une première couche diélectrique, une couche métallique et une seconde couche diélectrique. La couche de surface recouvre la couche métallique, qui est exposée au moins sur le côté du corps stratifié, et l'épaisseur de film de la couche de surface appliquée en recouvrement est de 20 à 200 nm.
PCT/JP2021/014518 2020-04-09 2021-04-05 Pigment réfléchissant les infrarouges, composition de peinture, film de peinture et article WO2021206062A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020070570 2020-04-09
JP2020-070570 2020-04-09

Publications (1)

Publication Number Publication Date
WO2021206062A1 true WO2021206062A1 (fr) 2021-10-14

Family

ID=78023281

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/014518 WO2021206062A1 (fr) 2020-04-09 2021-04-05 Pigment réfléchissant les infrarouges, composition de peinture, film de peinture et article

Country Status (1)

Country Link
WO (1) WO2021206062A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008291109A (ja) * 2007-05-24 2008-12-04 Sumitomo Metal Mining Co Ltd 赤外線遮蔽微粒子およびその製造方法、赤外線遮蔽微粒子分散体、赤外線遮蔽体、ならびに赤外線遮蔽基材
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
WO2017122733A1 (fr) * 2016-01-13 2017-07-20 日本ペイントホールディングス株式会社 Composition de revêtement réfléchissant les infrarouges
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
WO2020184694A1 (fr) * 2019-03-13 2020-09-17 デクセリアルズ株式会社 Pigment réfléchissant les infrarouges

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008291109A (ja) * 2007-05-24 2008-12-04 Sumitomo Metal Mining Co Ltd 赤外線遮蔽微粒子およびその製造方法、赤外線遮蔽微粒子分散体、赤外線遮蔽体、ならびに赤外線遮蔽基材
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
WO2017122733A1 (fr) * 2016-01-13 2017-07-20 日本ペイントホールディングス株式会社 Composition de revêtement réfléchissant les infrarouges
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
WO2020184694A1 (fr) * 2019-03-13 2020-09-17 デクセリアルズ株式会社 Pigment réfléchissant les infrarouges

Similar Documents

Publication Publication Date Title
US9127171B2 (en) Anti-reflection film and method for manufacturing the same
KR101044113B1 (ko) 반사방지 코팅 조성물 및 이것을 이용하여 제조된 반사방지필름
KR101074948B1 (ko) 반사 방지 필름, 전자파 실드성 광 투과창재, 가스 방전형발광 패널, 플랫 디스플레이 패널, 진열창재 및 태양 전지모듈
CN104797641B (zh) 具有增强的耐久性的纳米二氧化硅涂层组件
EP2557130B1 (fr) Composition de revêtement antireflet, film antireflet, et procédé de préparation associé
US10131802B2 (en) Nanosilica based compositions, structures and apparatus incorporating same and related methods
TW201314249A (zh) 防止反射膜及防止反射板
WO2011027827A1 (fr) Article ayant un film à faible réflexion sur une surface de matériau de base
CN104769023B (zh) 用于阻碍露珠形成的纳米二氧化硅涂层
WO2009064128A2 (fr) Composition de revetement antireflet, film antireflet et procede de preparation associe
WO2013065801A1 (fr) Procédé de production d'un objet doté d'un film à faible réflexion
WO2005085913A1 (fr) Couche antireflet et processus pour fabriquer celle-ci
JP6956089B2 (ja) 塗膜および物品
AU2007337365A1 (en) Composite particle and uses thereof
CN102119198A (zh) 涂料组合物及形成有涂膜的物品
US20090216492A1 (en) Solar radiation shielding member and solar radiation shielding member forming fluid dispersion
WO2021206062A1 (fr) Pigment réfléchissant les infrarouges, composition de peinture, film de peinture et article
CN209368167U (zh) 一种低反射率窗膜
JP6736049B2 (ja) ガラス複合体、それを備えた透明スクリーン、およびそれを備えた映像投影システム
KR20090049519A (ko) 반사방지 코팅 조성물 및 이것을 이용하여 제조된 반사방지필름
JP2019028313A (ja) 低反射板
JP2016118632A (ja) 光学制御フィルムの製造方法
WO2023058454A1 (fr) Stratifié antireflet
JP5742671B2 (ja) 赤外遮蔽フィルム、赤外遮蔽フィルムの製造方法、および赤外遮蔽体
JP2022040749A (ja) 透明部材および物品

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21783696

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21783696

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP