JP6100665B2 - Thermal barrier pigment composition, article, and infrared shielding composition - Google Patents

Description

  The present invention relates to a heat-shielding pigment composition for coloring having excellent near-infrared absorption characteristics, which simultaneously imparts transparency and a neutral gray hue to an article, etc., an article obtained by using this heat-shielding pigment composition, and infrared shielding The present invention relates to a composition for use and synthetic leather.

  In recent years, materials that can reflect or shield infrared rays (infrared cut materials) have been actively studied from the viewpoint of protecting the global environment and saving energy. Applications of infrared cut materials are being considered for windows in houses, buildings, and vehicles, and attempts have been made to suppress temperature rise in rooms and cars by blocking the light in the infrared region of the incident light. Has been made.

  Among infrared cut materials, tin-doped indium oxide (ITO) and antimony-doped tin oxide (ATO) are known as colorless and transparent materials. These materials are transparent without absorbing light in the visible light region, but absorb light in the infrared region. However, these materials have a problem that the absorptivity in the infrared region is insufficient unless the addition amount, coating amount, or film thickness is increased. There is also a problem that light absorption in the near infrared region is not so strong.

  In addition, metal compounds such as tungsten oxide and lanthanum hexaboride, which have transparency in the wavelength range of visible light and also have transparency, are known. These metal compounds have effective absorption performance in the infrared region. However, since tungsten oxide has a bluish color and lanthanum hexaboride has a yellowish color, there is a problem in using these metal compounds alone for color preparation. When these metal compounds are simply combined with other colorants, the infrared absorption performance may be lowered.

  By the way, considering the coloring of the window glass and the window of the vehicle, it is common to color with black from the viewpoint of suppressing the temperature rise, and carbon black is usually used. Carbon black is black in dark color, but when made into a thin film, it becomes yellowish and has a brownish hue. For this reason, in order to adjust this hue, the carbon black is used after being subjected to a blue tint or the like. Organic black pigments include perylene black and azomethine azo black. However, these organic black pigments transmit light in the infrared region without absorbing it. Further, it is known that the light resistance is inferior to that of inorganic pigments.

  Taking advantage of transparency, which is one of the characteristics of fine particle pigments, by applying fine particle pigments directly to glass or film, or by attaching an adhesive layer colored with fine particle pigments to glass or film, etc. It is known to color window glass and vehicle windows. In particular, for coloring liquid crystal displays (LCDs), plasma display panels (PDPs), organic EL panels, etc., a clear neutral gray clear bluish color different from dark black or bluish color is preferable. .

  However, as described above, the most frequently used carbon black, when made into a thin film, has a yellowish dull color and a brownish hue. For this reason, it cannot be said that the clear neutral gray has a vivid blue hue. Further, since perylene black exhibits a reddish purple hue when it is formed into a thin film, it cannot be said that it exhibits a clear neutral gray clear bluish color. And azomethine azo black has a preferable hue, but does not absorb light in the infrared region. Moreover, even with inorganic pigments, there are currently few materials that have excellent light transmission, a clear neutral gray, vivid blue, and excellent infrared absorption performance.

  The pigment used as described above is required to have light resistance. For this reason, the expectation with respect to the inorganic pigment excellent in light resistance compared with an organic pigment is increasing. For example, a copper (Cu) -manganese (Mn) -iron (Fe) -based composite oxide black pigment having a high tinting strength and a bluish hue, which is prepared by a wet method, is known (Patent Documents 1 to 3). 3). Moreover, the complex oxide which exhibits black and has an absorptivity in the wavelength range from visible region to infrared region is known (patent documents 4 to 6). Furthermore, it is known that carbon black is used for an optical film for display aimed at a neutral gray color tone (Patent Documents 7 and 8). Also known is a dispersion in which fine particles of infrared shielding material containing tungsten as a constituent element are dispersed in a medium (Patent Document 9).

Japanese Patent No. 3212065 JP 2002-309123 A Japanese Patent No. 3347934 Japanese Patent No. 4348872 JP 2001-99497 A JP 2007-230848 A JP 2004-69931 A JP 2000-265133 A JP 2012-72402 A

  However, even the pigments described in Patent Documents 1 to 6 can obtain a clear neutral gray clear blue color suitable for coloring LCDs, PDPs, and organic EL panels. It wasn't. In addition, the optical films and the like described in Patent Documents 7 and 8 have a color tone adjusted to neutral gray using a color pigment other than carbon black together with carbon black. For this reason, the clear, neutral gray and vivid bluish color of the intended use was not obtained. Furthermore, since the dispersion described in Patent Document 9 uses tungsten as a constituent material of the infrared shielding material fine particles, blue becomes an emphasized color. Therefore, it is difficult to obtain a neutral blue gray that maintains transparency. In any of the patent documents, the evaluation of the absorption characteristics in the wavelength region of 800 to 1400 nm and the method for maximizing the absorption in the wavelength region have not been studied.

  The present invention has been made in view of such problems of the prior art, and the problem is that it is possible to obtain a clear neutral gray with a clear bluish color. An object of the present invention is to provide a heat-shielding pigment composition that maximizes absorption of red exterior and has excellent absorption characteristics in the near infrared region. Further, the subject of the present invention is that a clear neutral gray clear blue color is imparted, and as an unprecedented near-infrared absorption characteristic, a better article, an infrared shielding composition And providing synthetic leather.

That is, according to the present invention, the following heat shielding pigment composition is provided.
[1] A heat-shielding pigment for coloring containing a composite oxide black pigment (A) comprising an oxide of a main component metal containing copper, manganese and iron, and metal compound particles (B) having heat-shielding performance The composite oxide black pigment (A) has a manganese / iron molar ratio of 3/1 to 30/1 and a copper / (manganese + iron) molar ratio of 1/2 to The composite oxide black pigment (A) and the metal compound particles (B) both have a maximum wavelength of 400 to 700 nm at which the transmittance is maximum in the wavelength range of 400 to 1400 nm. And a metal pigment particle (B) is at least one of tungsten oxide particles and lanthanum hexaboride particles, and gives a neutral gray color tone.
[2] The composite oxide black pigment (A) has a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ and has a BET specific surface area of 30 m ² / g or more [1] The heat-shielding pigment composition described in 1 .
[3 ] The [1] or [ 1], wherein the composite oxide black pigment (A) is obtained by introducing 2 to 10 mol% of a divalent metal of at least one of calcium and magnesium with respect to the copper . 2] The heat-shielding pigment composition described in 2] .

Moreover, according to this invention, the article | item shown below is provided.
[ 4 ] A transparent base material, and the heat-shielding pigment composition according to any one of [1] to [ 3 ] arranged in a dispersed state on at least one of the surface and the inside of the transparent base material. Articles with a neutral gray color with a clear blue tint.
[ 5 ] The article according to [ 4 ], wherein the a value is -4 to 0 and the b value is -8 to 0 in the CIE LAB (L ^* a ^* b ^* ) color system.

Furthermore, according to the present invention, the following infrared shielding composition is provided.
[ 6 ] An infrared shielding composition comprising a resin material and the thermal barrier pigment composition according to any one of [1] to [ 3 ].
[ 7 ] The above further containing at least one infrared shielding material selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, tin-doped zinc oxide, and silicon-doped zinc oxide. [ 6 ] The infrared shielding composition according to [ 6 ].
[ 8 ] The infrared shielding composition according to [ 6 ] or [ 7 ], which is a coating agent or an adhesive.

Moreover, according to this invention, the synthetic leather shown below is provided.
[ 9 ] A synthetic leather comprising a skin layer made of the infrared shielding composition according to any one of [ 6 ] to [ 8 ].

  The heat-shielding pigment composition for coloring according to the present invention can obtain a clear and clear bluish neutral gray color and is excellent in absorption characteristics in the near infrared region and heat ray shielding. For this reason, if the heat-shielding pigment composition for color of the present invention is used, a clear neutral gray with a clear blue color is imparted, and the near-infrared absorption characteristics are unprecedented and the temperature rises. An article to which a suppression effect is imparted can be obtained.

It is a schematic diagram which shows the outline of the test apparatus used for the confirmation test of the temperature rise inhibitory effect. It is a mimetic diagram showing one embodiment of the synthetic leather of the present invention.

  Hereinafter, the preferred embodiment will be described as an example, and the details of the thermal insulation pigment composition for coloring of the present invention will be described. The heat-shielding pigment composition of the present invention contains a composite oxide black pigment (A) composed of oxides of main component metals including copper, manganese, and iron, and metal compound particles (B) having heat-shielding performance. It is a pigment composition for coloring, and has a characteristic of absorbing visible light and near infrared light. The composite oxide black pigment and the metal compound particles both have a maximum wavelength at which the transmittance reaches a maximum in the wavelength range of 400 to 1400 nm when the transmittance in the wavelength range from visible light to infrared is measured. It has a wavelength range of ˜700 nm. The composite oxide black pigment preferably has a maximum wavelength in which the transmittance is maximum in the wavelength range of 400 to 1400 nm in the wavelength range of 400 to 500 nm. The composite oxide black pigment preferably has a minimum wavelength in the wavelength range of 600 to 800 nm in which the transmittance is minimum in the wavelength range of 400 to 1400 nm.

  Since the heat-shielding pigment composition of the present invention has the optical properties as described above, it has excellent heat ray shielding performance simultaneously with the clear blue color of transparent neutral gray. In addition, the composite oxide black pigment is soft and excellent in dispersibility despite being extremely fine particles. Furthermore, even if it does not contain an element such as chromium (Cr), it is possible to obtain a clear transparent neutral gray color with a clear bluish color, which is excellent in safety and has high utility value.

  In addition, the transmittance | permeability in the predetermined wavelength range of the heat-shielding pigment composition of this invention, the composite oxide black pigment used for it, and a metal compound particle is a spectrophotometer (brand name "U-4100", the Hitachi Ltd. make, for example). ) To measure the transmittance in the wavelength region of 300 to 2500 nm. Compared with carbon black, which is widely used as a black pigment, the composite oxide black pigment used in the thermal barrier pigment composition of the present invention has a low transmittance in the wavelength range of 500 to 1400 nm from visible light to infrared light. It shows stronger absorbency. Moreover, the metal compound particle used for the thermal-insulation pigment composition of this invention has the characteristics in the transmittance | permeability and reflectance in a 500-1400 nm wavelength range from visible light to infrared rays. By providing such a composite oxide black pigment and metal compound particles, the thermal barrier pigment composition of the present invention having not only a property of absorbing infrared rays more strongly but also a property of reflecting infrared rays is provided. Can do.

Furthermore, the present inventors have found that a black pigment having a spinel structure composed of oxides of main component metals including copper, manganese, and iron is useful among the composite oxides. In particular, in a Cu—Mn—Fe-based composite oxide black pigment having a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ , the composition of manganese (Mn) / iron (Fe) (molar ratio) It was found that the absorption characteristics in the near infrared region can be remarkably improved by adjusting (). For example, when the composition has a large manganese / iron molar ratio (many manganese and little iron), the absorption in the near infrared region increases. However, a composition having a too large molar ratio of manganese / iron not only does not increase the absorption in the near infrared region, but also tends to decrease the coloring power. For this reason, in order to achieve efficient infrared shielding while maintaining the coloring power, the molar ratio of manganese / iron is set to 3/1 to 30/1, preferably 4/1 to 10/1. . By setting the manganese / iron molar ratio within the above range, the transmittance in the near-infrared region (800 to 1400 nm) can be reduced, and a clearer blue color can be obtained.

  If the molar ratio of manganese / iron is less than 3/1 (the ratio of iron increases), the hue becomes yellowish and shows a transmittance curve that approximates carbon black. For this reason, when it mixes with the metal compound particle | grains which have heat ray shielding performance, the high absorptivity in a near-infrared area | region cannot be obtained. On the other hand, when the molar ratio of manganese / iron exceeds 30/1 (the ratio of iron decreases), not only does the hue bluish not strengthen, but also the coloring power decreases. When the hue is yellowish, it tends to be difficult to absorb light in the near-infrared region when mixed with metal compound particles having heat ray shielding performance. On the other hand, the absorptivity in the near-infrared region tends to increase as the hue bluish increases. That is, the coloring heat-shielding pigment composition of the present invention exhibits a clear neutral gray hue and excellent light absorption in the near-infrared region depending on the characteristics of the mixed composite oxide black pigment. Shows the effect of heavy.

Moreover, the coloring power and particle diameter of the composite oxide black pigment vary depending on the increase or decrease of the copper content. For this reason, it is preferable to appropriately control the copper content. Specifically, the composite oxide black pigment preferably has a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ . The molar ratio of copper / (manganese + iron) is 1/2 to 1.2 / 2, preferably 1/2 to 1.1 / 2. When the molar ratio of copper / (manganese + iron) is less than ½ (the ratio of copper decreases), the hue becomes dull and the coloring power decreases. On the other hand, when the molar ratio of copper / (manganese + iron) exceeds 1.2 / 2 (the proportion of copper increases), the pigment particle size tends to increase, so that the pigment has a small BET specific surface area. End up.

  Furthermore, in addition to copper, manganese, and iron, introduction of a divalent metal of at least one of calcium (Ca) and magnesium (Mg) is extremely effective in adjusting the color tone and coloring power. By introducing the divalent metal, a more vivid and neutral gray bluish black pigment can be obtained. However, if the amount of divalent metal introduced is too small, the sharpness tends to be insufficient. On the other hand, if the amount of divalent metal introduced is excessive, there will be no significant change in hue and no further effect will be expected. For this reason, it is preferable to set it as 2-10 mol% in the ratio with respect to copper, and, as for the introduction amount of a bivalent metal, it is more preferable to set it as 4-8 mol%. These divalent metals can be used alone or in combination of two or more.

The BET specific surface area of the composite oxide black pigment is preferably 30 m ² / g or more, and more preferably 40 m ² / g or more. When the BET specific surface area is 30 m ² / g or more, the haze can be lowered to 10% or less. Furthermore, the thing of 40 m < ² > / g or more can make haze 3% or less especially, and a more excellent thing with high transparency is obtained. The BET specific surface area of the composite oxide black pigment was measured by a nitrogen adsorption method in accordance with Japanese Industrial Standard JIS Z8830-1990 using a BET specific surface area measuring device (trade name “NOVA-2000”, manufactured by Quantachrome). can do.

  The heat-shielding pigment composition of the present invention contains a composite oxide black pigment and metal compound particles having heat-ray shielding performance, so that it has a coloring performance that gives a neutral gray color tone and has excellent heat-ray shielding performance. Also have. As described above, when the transmittance of the wavelength range from visible light to near infrared is measured, the metal compound particles have a maximum wavelength at which the transmittance is maximum in the wavelength range of 400 to 1400 nm. Have. The metal compound particles preferably have a reduced transmittance in the wavelength range of 800 to 1400 nm. By using the metal compound particles having such optical characteristics, the infrared absorption ability and the heat shielding performance of the composite oxide black pigment can be further utilized.

  As the metal compound particles, tungsten oxide particles such as tungsten oxide and tungsten composite oxide; lanthanum hexaboride particles and the like can be suitably used. These metal compound particles can be used singly or in combination of two or more. Further, a cesium / tungsten composite oxide or a metal surface that has been subjected to hydrothermal treatment or oxide coating treatment for the purpose of improving weather resistance can also be used.

  As the metal compound particles, it is preferable to use particles having characteristics of permeability or absorptivity in a wavelength range of 400 to 1400 nm. For example, the maximum wavelength of tungsten oxide in the wavelength region of 400 to 700 nm exists on the long wavelength side compared to the maximum wavelength of the composite oxide black pigment. In addition, the maximum wavelength of lanthanum hexaboride in the wavelength region of 400 to 700 nm exists on the longer wavelength side compared to the maximum wavelength of tungsten oxide. That is, tungsten oxide has a greenish blue hue, and lanthanum hexaboride has a yellowish green hue. Among them, lanthanum hexaboride known as a heat-shielding metal has a minimum wavelength in which the transmittance is minimized in the wavelength range of 800 to 1400 nm, and tungsten oxide has a low transmission sustained in the wavelength range of 800 to 1400 nm. Indicates the rate. The heat-shielding pigment composition of the present invention can impart a bluish neutral gray color that cannot be achieved with metal compound particles alone to articles or the like. Furthermore, it also has reflection and absorption characteristics in the near infrared region. Furthermore, in the solar radiation wavelength region, the wavelength region in which the weight coefficient (contribution to heat) defined in accordance with JIS R 3106 is greatly involved is the wavelength region of 800 nm to 1400 nm, and the transmission of solar radiation in this wavelength region The effect of reducing the amount indicates high industrial applicability.

  Since both the composite oxide black pigment and the metal compound particles have a maximum absorption wavelength in the visible light region, the article can be colored while maintaining transparency. The particle diameters of the composite oxide black pigment and the metal compound particles are preferably adjusted as appropriate according to the purpose. For example, when the particle size is more than 500 nm, the transparency is lowered, but the coloring property and the heat ray shielding property tend to be improved. Further, when the particle diameter is less than 10 nm, the transparency is improved, but the coloring property and the heat ray shielding property tend to be lowered. Although the influence of the particle size varies depending on the addition amount, the number average particle size of the composite oxide black pigment and the metal compound particles is preferably 200 nm or less, more preferably 100 nm or less, and 50 to 10 nm. It is particularly preferred.

  The mass ratio of the composite oxide black pigment (A) and the metal compound particles (B) contained in the heat-shielding pigment composition of the present invention is (A) :( B) = 3: 1 to 100: 1. Is preferable, and (A) :( B) = 6: 1 to 20: 1 is more preferable. When the content of the composite oxide black pigment is excessive, the infrared shielding effect tends to be insufficient. On the other hand, when the content of the metal compound particles is excessive, the infrared shielding effect is improved, but the color tends to deviate from the clear bluish color of neutral gray.

  When coloring by adding to the substrate without impairing the transparency of the substrate, the addition amount of the heat-shielding pigment composition of the present invention is preferably 0.001 to 10% by mass with respect to the substrate, More preferably, the content is 0.004 to 6% by mass. On the other hand, when it is not necessary to maintain the transparency of the substrate, it can be added within a range where the colorability and heat ray shielding properties are improved. Specifically, the addition amount of the heat shielding pigment composition is preferably 6 to 20% by mass with respect to the base material. It is preferable to use the heat-shielding pigment composition of this invention for a glass plate and a film, glass substitute resin, a thin film sheet, a coating agent, an adhesive agent, or an adhesive.

  If the heat-shielding pigment composition of the present invention is used, an article having a bluish neutral gray color can be produced. Such an article can be easily obtained by disposing the heat-shielding pigment composition in a dispersed state on the surface of or inside the transparent substrate according to a conventionally known method. Specific examples of the transparent substrate include glass, acrylic, PET, polyvinyl butyral, polyurethane, polyethylene, polypropylene, polycarbonate, polyimide, acrylic silicon, a plate made of fluororesin, a bottle, and a film. . Furthermore, it is also preferable to use it in combination with a conventionally known transparent material to the extent that the effects of the present invention are not impaired. For example, as a transparent infrared cut material, in order to compensate for the effects that cannot be obtained with colorless and transparent ITO (tin-doped indium oxide) or ATO (antimony-doped tin oxide), the heat-shielding pigment composition of the present invention is used in combination. Is also preferable.

As a method for expressing the color tone, there is a CIE L ^* a ^* b ^* color system (color space) which is expressed by the International Commission on Illumination (CIE) and expresses a visible color as a color space. In this CIE L ^* a ^* b ^* color system, a color is expressed by three coordinates, lightness is “L ^* ”, red (magenta) to green is “a ^* ” (positive is magenta, negative is green) , Yellow to blue correspond to “b ^* ” (positive is yellow, negative is blue), respectively. The neutral gray tone is ideally displayed when both the a and b values are close to zero. When the thermal pigment composition of the present invention is used, for example, an article having an a value of −4 to 0, preferably −2 to 0 and a b value of −8 to 0, preferably −8 to −3. Can be manufactured. Since the article having the above-mentioned color tone can be provided by the heat-shielding pigment composition of the present invention, there are many advantages in terms of quality stability, production / material cost, etc., and there is a high possibility of being effectively used. is there. Thus, the heat-shielding pigment composition of the present invention has two effects of heat-shielding properties and color (neutral gray) required from diversification of needs. At the same time, in view of the respective characteristics, the combination of the composite oxide black pigment and the metal compound particles, which are said to have a catalytic action, is a VOC-compatible composition (that is, an environmentally-friendly product) caused by decomposition of organic substances and the causative substances This material also suggests the possibility of

  The thermal barrier pigment composition of the present invention is excellent in dispersibility despite being fine particles. Therefore, the thermal barrier pigment composition of the present invention is useful as a resin coloring material (resin colorant). The type of resin to be colored is not particularly limited. For example, vinyl chloride, polycarbonate, fluorine resin, silicon resin, polyurethane resin, polyphenylene sulfide, polyethylene, polypropylene, polyvinyl butyral resin, polyimide resin, rosin ester resin , Acrylic resins, and cellulose resins. For example, about 0.2 parts by mass of the heat-shielding pigment composition is added to 100 parts by mass of these resins, and then kneaded using a roll, and then formed into various shapes such as sheets. As a result, there can be obtained a colored resin molded product having almost no pigment-biased particles and uniformly colored.

  If the thermal barrier pigment composition of the present invention is used, an infrared shielding composition can be obtained. That is, the infrared shielding composition of the present invention contains a resin material and the above-described coloring heat-shielding pigment composition. As described above, the thermal barrier pigment composition of the present invention is capable of obtaining a clear neutral gray and vivid blue color, and is excellent in absorption characteristics in the near infrared region. For this reason, if the infrared shielding composition of the present invention containing this thermal barrier pigment composition is used as a coating agent or adhesive, a clear neutral gray vivid blue color is imparted, and a near red color It is possible to produce a coating film, an adhesive film, and the like that are excellent in external absorption characteristics and have a temperature rise suppressing effect, and articles having such a coating film, an adhesive film, and the like.

  Resin materials include polyurethane resin, acrylic resin, silicon resin, fluorine resin, alkyd resin, vinyl chloride-vinyl acetate copolymer, alkoxysilane resin, phenol resin, polyvinyl butyral resin, polyimide resin Examples include resins, rosin ester resins, and cellulose resins. These resin materials can be used individually by 1 type or in combination of 2 or more types. The infrared shielding composition may contain various solvents such as water, a water-soluble organic solvent, and a water-insoluble organic solvent. The infrared shielding composition may be either an aqueous composition or a solvent composition.

  Moreover, it is preferable that the infrared shielding composition further contains an infrared shielding material. By including a combination of an infrared shielding material and the above-described heat-shielding pigment composition, it has a coating film, an adhesive film, and the like that have a further improved temperature rise suppression effect, and such a coating film, an adhesive film, and the like. Articles can be manufactured. A conventionally well-known thing can be used as an infrared rays shielding material. In particular, by using an infrared shielding material with high whiteness and excellent transparency, the effect of temperature rise can be further suppressed without impairing the clear blue color of the transparent neutral gray of the thermal pigment composition. Can be improved. Specific examples of such infrared shielding materials include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), aluminum-doped zinc oxide, indium-doped zinc oxide, tin-doped zinc oxide, and silicon-doped zinc oxide. be able to. These infrared shielding materials can be used alone or in combination of two or more.

  Infrared shielding materials such as ITO, ATO, aluminum-doped zinc oxide, indium-doped zinc oxide, tin-doped zinc oxide, and silicon-doped zinc oxide are almost colorless but slightly yellowish. In the display, a neutral gray hue is required so as not to impair the balance of R (red), G (green), and B (blue). Black organic pigments have no absorption in the infrared region. Carbon black (CB) has a slightly yellow hue. For this reason, it cannot be said that a black organic pigment or CB is preferable as a black coloring pigment for a display. Some CBs are bluish. However, the particle size of such a bluish CB is relatively large, does not have a neutral gray hue, and is inferior in transparency. On the other hand, the heat-shielding pigment composition of the present invention can obtain a preferable hue without inhibiting the absorption in the infrared region, and can increase the absorption in the near infrared region.

  The colorless infrared shielding material does not absorb visible light and has the property of absorbing infrared light, but does not absorb much light in the near infrared region up to about 1500 nm. Moreover, almost no organic pigment having absorption in the infrared region is found. Furthermore, there are almost no inorganic pigments having excellent transparency and absorption in the infrared region. On the other hand, the thermal barrier pigment composition of the present invention can be adjusted for absorption and reflection in the near infrared region. Therefore, by combining the heat-shielding pigment composition of the present invention with a colorless infrared shielding material that does not absorb much light in the near-infrared region, the two absorption wavelengths are complemented, and light in a wider infrared region is obtained. Can be absorbed and reflected.

  If said infrared shielding composition is used, synthetic leather can be manufactured. That is, the synthetic leather of the present invention includes a skin layer made of the aforementioned infrared shielding composition. The synthetic leather of the present invention uses an infrared shielding composition containing a heat shielding pigment composition as a coating agent, and has a skin layer formed by this coating agent. For this reason, the synthetic leather of the present invention exhibits a clear neutral gray clear bluish color, is excellent in absorption characteristics in the near-infrared region, and is imparted with a temperature rise suppressing effect. Therefore, the synthetic leather of the present invention is useful, for example, as an interior material for vehicles. Hereinafter, the synthetic leather of the present invention will be described with an example of the production method.

  FIG. 2 is a schematic view showing one embodiment of the synthetic leather of the present invention. In order to obtain the synthetic leather 20 of this embodiment, first, the infrared shielding composition as the coating agent described above is applied onto the surface of the release paper 11 so as to have an appropriate film thickness, and a coating film is formed. Form. Although the kind of resin material contained in a coating agent is not specifically limited, For example, a polycarbonate type non-yellowing polyurethane resin etc. can be used suitably. The skin layer 12 can be formed on one surface of the release paper 11 by drying the formed coating film while heating as necessary.

  The adhesive layer 13 can be formed on the surface of the skin layer 12 by applying an adhesive on the surface of the skin layer 12 so as to have an appropriate film thickness, and then drying while heating as necessary. it can. The adhesive usually contains a resin, a solvent such as toluene, methyl ethyl ketone, and dimethylformamide, and a component such as a crosslinking agent. Although the kind of resin used for an adhesive agent is not specifically limited, For example, the same kind as the resin material contained in a coating agent is preferable. The formed adhesive layer 13 is placed on the surface of a base material such as a woven fabric to form a laminate, and then pressed and heated as necessary, and then the release paper 11 is peeled off. 20 can be obtained.

  In addition, the white adhesive layer 13 with which light reflectivity was provided can also be formed by using the adhesive agent mix | blended with the white pigment. That is, it is possible to produce a synthetic leather having a double structure provided with a skin layer having excellent absorption characteristics in the near infrared region and exhibiting a temperature rise suppressing effect and an adhesive layer exhibiting light reflectivity. Synthetic leather having such a double structure is particularly useful as an interior material for vehicles such as automobiles.

  The heat-shielding pigment composition of the present invention can be prepared by mixing the composite oxide black pigment and the metal compound particles together with other components blended as necessary according to a conventional method. Commercially available metal compound particles can be used. The metal compound particles can also be prepared by heat-treating the starting material in an inert gas or reducing gas atmosphere.

  Next, a method for producing the composite oxide black pigment will be described. In the case of synthesizing a Cu—Mn—Fe oxide-based composite oxide black pigment by a wet precipitation method, the present inventors have produced a spinel structure by a solid-phase reaction at the time of firing. Further investigation was performed on the assumption that a more prominent bluish complex oxide black pigment could be obtained by preventing trivalent ions from entering the position (hereinafter referred to as “A site”). As a result, the Cu-Mn-Fe oxide black pigment is selectively coordinated to the A site of the spinel structure after the copper in the main component metal has a stoichiometric composition or a slight excess. By adding a divalent metal, a composite oxide black pigment having a clear neutral gray and vivid blue hue can be obtained by suppressing the entry of trivalent ions into the A site of the spinel structure. I found. Furthermore, the inventors of the present invention provide salts of main component metals (copper, manganese, and iron) constituting the composite oxide black pigment, and salts of divalent metals (Ca and / or Mg) used as necessary. Can be mixed and precipitated as a metal hydroxide with an alkali agent, and the precipitate can be oxidized in the liquid phase at the same time as or after the precipitation, so that the subsequent firing temperature can be made extremely low. I found out that

  The method for producing a composite oxide black pigment is to add an alkaline agent to a mixed aqueous solution of a metal salt containing a main component metal to precipitate a coprecipitate, and oxidize with an oxidizing agent simultaneously with or after the precipitation of the coprecipitate. A step (1) of generating a pigment precursor and a step (2) of pulverizing the generated pigment precursor after firing. Hereinafter, the details of the method for producing the composite oxide black pigment will be described.

  In step (1), a metal salt containing the main component metal is dissolved to prepare a mixed aqueous solution. As the metal salt, salts used in the production of conventional composite oxide black pigments such as sulfates, nitrates, chlorides and acetates can be used. The concentration of the metal salt in the mixed aqueous solution is suitably about 5 to 50% by mass. This mixed aqueous solution is simultaneously dropped into a preliminarily prepared precipitation medium together with an alkaline aqueous solution such as caustic soda as a precipitant. The reaction concentration in terms of metal salt may not be particularly bad for the precipitation product (coprecipitate), but 0.05 to 0.2 mol / liter in consideration of workability and subsequent steps. It is preferable that If it is less than 0.05 mol / liter, the dried product tends to be very hard and the yield tends to be low. On the other hand, when it exceeds 0.2 mol / liter, the composite may be non-uniform.

  The temperature at which the coprecipitate is deposited (synthesis temperature) may be a normal temperature in the wet method. Specifically, it is preferable to deposit (synthesize) the coprecipitate at 0 to 100 ° C. However, as the synthesis temperature increases, the generated particles grow faster and the particle size tends to increase. For this reason, the coloring power of the resulting composite oxide black pigment tends to be impaired, and the aggregation also becomes strong, which may adversely affect the dispersibility. Therefore, the synthesis temperature is preferably 30 ° C. or lower.

  When precipitating a coprecipitate by adding an aqueous solution of an alkali agent as a precipitant excessively to a mixed aqueous solution of metal salts, considering the application to the application utilizing the transparency of the resulting composite oxide black pigment, It is preferable to increase the pH at which the coprecipitate precipitates, compared to the case of synthesizing a general black pigment. Specifically, the pH at which the coprecipitate precipitates is preferably in the range of 11 to 13.5. The higher the pH when the coprecipitate is precipitated, the easier it is to obtain a pigment with a smaller particle diameter, but when the pH exceeds 13.5, the dried product becomes very hard and easily coagulates. In some cases, the pigment has poor dispersibility. On the other hand, if the pH at which the coprecipitate precipitates is less than 11, the resulting composite oxide black pigment particles tend to be large.

  Excess alkaline agent is preferably added after precipitation of the coprecipitate. The excess amount of the alkali agent is preferably 1.1 to 1.5 times, more preferably about 1.1 times the number of moles of the alkali agent required for coprecipitation (precipitation). The coprecipitate is precipitated while stirring for 30 minutes to 1 hour in this manner, and then aged for about 5 to 20 minutes to complete the coprecipitation (precipitation) reaction.

  The precipitated coprecipitate is oxidized with an oxidizing agent to convert divalent metal ions into trivalent metal ions. The oxidation treatment may be performed simultaneously with the precipitation of the coprecipitate in the coprecipitation system, or may be performed in the coprecipitation system or in another liquid phase after completion of the coprecipitation reaction. In any case, aging the coprecipitate after the oxidation treatment is preferable because the uniformity of the coprecipitate is improved and the purity is increased. If the coprecipitate is not aged, the color developability may be impaired by the stored impurities. By aging the coprecipitate, it is possible to obtain a composite oxide black pigment that is more excellent in color developability, and finer and excellent in dispersibility.

  Specific examples of the oxidizing agent include known oxidizing agents such as hydrogen peroxide, sodium chlorate, ammonium sulfite, and air (oxygen). However, when the coprecipitate is precipitated under high pH conditions, if an oxidizing agent such as sodium chlorate is used, the coprecipitate will be strongly condensed and the dispersibility of the resulting composite oxide black pigment will be increased. May decrease. For this reason, it is preferable to use hydrogen peroxide or air (oxygen) as an oxidizing agent because a composite oxide black pigment having a softer and better dispersibility can be obtained. In addition, the amount of the oxidizing agent used may be an amount necessary for the divalent metal to be oxidized into the trivalent metal ion. The temperature for aging the coprecipitate is not particularly limited, but may be 50 to 90 ° C. After aging for about 1 hour, filtering and washing with water, and then drying at a temperature of 100 to 150 ° C., a pigment precursor that is a dried coprecipitate can be obtained.

  In step (2), the obtained pigment precursor is fired and then pulverized. Thereby, the target complex oxide black pigment can be obtained. The firing temperature is usually 500 to 700 ° C., preferably 550 to 600 ° C., and preferably fired in an oxidizing atmosphere. The firing time may be 30 minutes to 1 hour. By grinding after firing, a complex oxide black pigment having a desired BET specific surface area can be obtained. The pulverization may be performed according to a conventionally known method, and may be dry, wet, or a combination of dry and wet. In the pulverization treatment, for example, an attritor, a ball mill, a vibration mill, a jet mill, a bead mill, a spray dryer, or the like can be used.

  By analyzing the composite oxide black pigment obtained as described above by, for example, powder X-ray diffraction, it can be confirmed that it is a single compound having a spinel structure and having no heterogeneous phase. It can also be confirmed by X-ray fluorescence analysis that a divalent metal is introduced into the composite oxide black pigment.

  Hereinafter, the present invention will be described more specifically based on examples. In the following text, “parts” and “%” are based on mass unless otherwise specified.

[Example 1]
Water was added and completely dissolved in 120 parts of copper sulfate, 130 parts of manganese sulfate, and 53.4 parts of iron sulfate to prepare 1000 parts of a mixed salt aqueous solution. In addition, water was added to 120 parts of caustic soda and completely dissolved to prepare 1000 parts of an aqueous caustic soda solution. The prepared mixed salt aqueous solution and caustic soda aqueous solution were simultaneously added dropwise to 1600 parts of water as a precipitation medium to complete the precipitation reaction over 1 hour. The pH of the reaction solution was adjusted to a range of 12.0 to 13.0. Further, after the dropwise addition of the mixed salt aqueous solution was completed, the excess caustic soda aqueous solution was dropped as it was. After completion of the dropwise addition, a solution obtained by diluting 60 parts of hydrogen peroxide (hydrogen peroxide concentration: 35%) into 120 parts of water was added dropwise to oxidize.

After completion of the oxidation treatment, the liquid temperature was raised to 80 ° C. and aging was performed for 1 hour. After thoroughly washing with water to wash away residual salts, the product obtained by filtration was dried at 100 to 140 ° C. to obtain a dried product. The obtained dried product was baked at 580 ° C. for 1 hour to obtain a baked product. The obtained fired product was pulverized to obtain a composite oxide black pigment 1 (number average particle diameter of 50 nm) having a BET specific surface area of 51.2 m ² / g. The obtained composite oxide black pigment 1 was subjected to powder X-ray diffraction analysis, and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 1. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of the complex oxide black pigment 1 obtained using the spectrophotometer (brand name "U-4100", Hitachi Ltd. make) was measured, and the transmittance | permeability was maximum. It has been confirmed that the maximum wavelength to be in the wavelength range of 400 to 700 nm.

  The obtained composite oxide black pigment 1 and tungsten oxide having a number average particle diameter of 50 nm were uniformly mixed at 6: 1 (mass ratio) to prepare a pigment. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of tungsten oxide is measured using a spectrophotometer, the maximum wavelength in which a transmittance | permeability becomes maximum exists in the wavelength range of 400-700 nm, and 800-1400 nm. It was confirmed that there was a low transmittance region in the wavelength region. The prepared pigment and the melamine alkyd resin are placed in a paint shaker (manufactured by Red Devil) with a pigment content of 3 PHR (PHR = (pigment (g) / resin (g)) × 100), sufficiently dispersed to form a paint, A paint was obtained. The obtained paint was applied onto a PET film with a # 6 bar coater. After drying, the sample for measurement was obtained by baking at 120 ° C. for 20 minutes. The film thickness of the coating film formed on the obtained measurement sample was 3 to 4 μm.

Using a spectrophotometer (trade name “U-4100”, manufactured by Hitachi, Ltd.), the transmittance of the measurement sample in the wavelength range of 300 to 2500 nm was measured. As a result, in the wavelength range of 400 to 1000 nm, it was confirmed that the wavelength range of 400 to 500 nm has a maximum wavelength that maximizes the transmittance. Furthermore, it was confirmed that the transmittance decreased in the infrared wavelength region as compared with the composite oxide black pigment 1 alone. This measurement sample has a transmittance of about 40 to 50% in the visible part, and in the CIE LAB (L ^* a ^* b ^* ) color system, the a value is −4 to 0 and the b value is −8. ~ 0. It was also confirmed that the transmitted light had a neutral gray hue. Furthermore, in the visible light region, the transmittance at the minimum wavelength near 700 to 800 nm is the smallest, the transmittance gradually increases toward the long wavelength side, and the absorption in the near infrared region is large. It was.

[Example 2]
In the same manner as in Example 1, except that 120 parts of copper sulfate, 130 parts of manganese sulfate, and 53.4 parts of iron sulfate were used, and 3.6 parts of calcium chloride were dissolved in the precipitation medium (water). A composite oxide black pigment 2 (number average particle diameter of 50 nm) having a specific surface area of 54.8 m ² / g was obtained. The obtained composite oxide black pigment 2 was subjected to powder X-ray diffraction analysis and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 2. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of the complex oxide black pigment 2 obtained using the spectrophotometer is measured, and the maximum wavelength where the transmittance is maximum exists in the wavelength range of 400-700 nm. It was confirmed.

  The obtained composite oxide black pigment 2 and tungsten oxide having a number average particle diameter of 50 nm were uniformly mixed at 8: 1 (mass ratio) to prepare a pigment. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of tungsten oxide is measured using a spectrophotometer, the maximum wavelength in which a transmittance | permeability becomes maximum exists in the wavelength range of 400-700 nm, and 800-1400 nm. It was confirmed that there was a low transmittance region in the wavelength region. The prepared pigment and the melamine alkyd resin are placed in a paint shaker (manufactured by Red Devil) with a pigment content of 3 PHR (PHR = (pigment (g) / resin (g)) × 100), sufficiently dispersed to form a paint, A paint was obtained. The resulting paint was applied onto white art paper using a 6 mil applicator. After drying, the sample for measurement was obtained by baking at 120 ° C. for 20 minutes. The film thickness of the coating film formed on the obtained measurement sample was 23 μm.

The transmittance of the measurement sample obtained in the same manner as in Example 1 was measured. As a result, in the wavelength range of 400 to 1000 nm, it was confirmed that the wavelength range of 400 to 500 nm has a maximum wavelength that maximizes the transmittance. Furthermore, it was confirmed that the transmittance decreased in the infrared wavelength region as compared with the composite oxide black pigment 2 alone. This measurement sample has a transmittance of about 40 to 50% in the visible part, and in the CIE LAB (L ^* a ^* b ^* ) color system, the a value is −4 to 0 and the b value is −8. ~ 0. It was also confirmed that the transmitted light had a neutral gray hue.

[Example 3]
A composite oxide black pigment 3 having a BET specific surface area of 43.3 m ² / g was obtained in the same manner as in Example 2 except that 120 parts of copper sulfate, 152.1 parts of manganese sulfate and 16.7 parts of iron sulfate were used. A number average particle diameter of 60 nm) was obtained. The obtained composite oxide black pigment 3 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 3. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of the complex oxide black pigment 3 obtained using the spectrophotometer is measured, and the maximum wavelength where the transmittance becomes maximum exists in the wavelength range of 400-700 nm. It was confirmed.

  The obtained composite oxide black pigment 3 and lanthanum hexaboride having a number average particle diameter of 50 nm were uniformly mixed at 10: 1 (mass ratio) to prepare a pigment. In addition, the transmittance | permeability in the 400-1400 nm wavelength range of lanthanum hexaboride is measured using a spectrophotometer, the maximum wavelength where the transmittance is maximum exists in the wavelength range of 400-700 nm, and the minimum It has been confirmed that the minimum wavelength is in the wavelength range of 800 to 1400 nm. The prepared pigment and the melamine alkyd resin are placed in a paint shaker (manufactured by Red Devil) with a pigment content of 3 PHR (PHR = (pigment (g) / resin (g)) × 100), sufficiently dispersed to form a paint, A paint was obtained. The obtained paint was applied onto a PET film with a # 6 bar coater. After drying, the sample for measurement was obtained by baking at 120 ° C. for 20 minutes. The film thickness of the coating film formed on the obtained measurement sample was 3 to 4 μm.

The transmittance of the measurement sample obtained in the same manner as in Example 1 was measured. As a result, in the wavelength range of 400 to 1000 nm, it is confirmed that the wavelength has a maximum wavelength in which the transmittance is maximized in the wavelength range of 400 to 500 nm and the wavelength in the wavelength range of 800 to 1400 nm has a minimum wavelength that has the minimum transmittance. did. This measurement sample has a transmittance of about 40 to 50% in the visible part, and in the CIE LAB (L ^* a ^* b ^* ) color system, the a value is −4 to 0 and the b value is −8. ~ 0. It was also confirmed that the transmitted light had a neutral gray hue. This measurement sample was more bluish than the measurement sample obtained in Example 2, and the transmittance in the near-infrared region was also reduced.

[Example 4]
Example 2 except that 120 parts of copper sulfate, 144.4 parts of manganese sulfate and 29.7 parts of iron sulfate were used, and 5.0 parts of magnesium chloride was dissolved in the precipitation medium (water) together with calcium chloride. Similarly, composite oxide black pigment 4 (number average particle diameter 60 nm) having a BET specific surface area of 49.2 m ² / g was obtained. The obtained composite oxide black pigment 4 was subjected to powder X-ray diffraction analysis to confirm that it was a single compound having a spinel structure and having no heterogeneous phase. Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 4. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of the complex oxide black pigment 4 obtained using the spectrophotometer is measured, and the maximum wavelength where the transmittance is maximum exists in the wavelength range of 400-700 nm. It was confirmed.

  The resulting composite oxide black pigment 4, lanthanum hexaboride having a number average particle diameter of 50 nm, and tungsten oxide having a number average particle diameter of 100 nm are uniformly distributed at 8: 0.5: 0.5 (mass ratio). A pigment was prepared by mixing. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of lanthanum hexaboride and a tungsten oxide is measured using a spectrophotometer, respectively, and the maximum wavelength in which the transmittance | permeability becomes the maximum is a wavelength range of 400-700 nm. It was confirmed that there was a low transmittance region in the wavelength range of 800 to 1400 nm. The prepared pigment and the melamine alkyd resin are placed in a paint shaker (manufactured by Red Devil) with a pigment content of 3 PHR (PHR = (pigment (g) / resin (g)) × 100), sufficiently dispersed to form a paint, A paint was obtained. The obtained paint was applied onto a PET film with a # 6 bar coater. After drying, the sample for measurement was obtained by baking at 120 ° C. for 20 minutes. The film thickness of the coating film formed on the obtained measurement sample was 3 to 4 μm.

The transmittance of the measurement sample obtained in the same manner as in Example 1 was measured. As a result, in the wavelength range of 400 to 1000 nm, it is confirmed that the wavelength has a maximum wavelength in which the transmittance is maximized in the wavelength range of 400 to 500 nm and the wavelength in the wavelength range of 800 to 1400 nm has a minimum wavelength that has the minimum transmittance. did. Furthermore, it was confirmed that the transmittance decreased in the infrared wavelength region as compared with the composite oxide black pigment 4 alone. This measurement sample has a transmittance of about 40 to 50% in the visible part, and in the CIE LAB (L ^* a ^* b ^* ) color system, the a value is −4 to 0 and the b value is −8. ~ 0. It was also confirmed that the transmitted light had a neutral gray hue.

[Example 5]
A composite oxide black pigment 5 having a BET specific surface area of 40.6 m ² / g was obtained in the same manner as in Example 2 except that 120 parts of copper sulfate, 157 parts of manganese sulfate, and 8.6 parts of iron sulfate were used. . The obtained composite oxide black pigment 5 (number average particle diameter 70 nm) was subjected to powder X-ray diffraction analysis, and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 5. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of the complex oxide black pigment 5 obtained using the spectrophotometer is measured, and the maximum wavelength where the transmittance becomes maximum exists in the wavelength range of 400-700 nm. It was confirmed.

  The resulting composite oxide black pigment 4, lanthanum hexaboride having a number average particle diameter of 50 nm, and tungsten oxide having a number average particle diameter of 100 nm are uniformly distributed at 8: 0.5: 0.5 (mass ratio). A pigment was prepared by mixing. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of lanthanum hexaboride and a tungsten oxide is measured using a spectrophotometer, respectively, and the maximum wavelength in which the transmittance | permeability becomes the maximum is a wavelength range of 400-700 nm. It was confirmed that there was a low transmittance region in the wavelength range of 800 to 1400 nm. The prepared pigment and the melamine alkyd resin are placed in a paint shaker (manufactured by Red Devil) with a pigment content of 3 PHR (PHR = (pigment (g) / resin (g)) × 100), sufficiently dispersed to form a paint, A paint was obtained. The obtained paint was applied onto a PET film with a # 6 bar coater. After drying, the sample for measurement was obtained by baking at 120 ° C. for 20 minutes. The film thickness of the coating film formed on the obtained measurement sample was 3 to 4 μm.

The transmittance of the measurement sample obtained in the same manner as in Example 1 was measured. As a result, in the wavelength range of 400 to 1000 nm, it is confirmed that the wavelength has a maximum wavelength in which the transmittance is maximized in the wavelength range of 400 to 500 nm and the wavelength in the wavelength range of 800 to 1400 nm has a minimum wavelength that has the minimum transmittance. did. Furthermore, it was confirmed that the transmittance decreased in the infrared wavelength region as compared with the composite oxide black pigment 5 alone. This measurement sample has a transmittance of about 40 to 50% in the visible part, and in the CIE LAB (L ^* a ^* b ^* ) color system, the a value is −4 to 0 and the b value is −8. ~ 0. It was also confirmed that the transmitted light had a neutral gray hue.

[Comparative Example 1]
In the same manner as in Example 2 except that 120 parts of copper sulfate, 144.4 parts of manganese sulfate, and 29.7 parts of iron sulfate were used, composite oxide black pigment 6 having a BET specific surface area of 47.5 m ² / g ( A number average particle diameter of 60 nm) was obtained. The obtained composite oxide black pigment 6 was subjected to powder X-ray diffraction analysis and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. Table 1 shows the composition (molar ratio) of the metal constituting the obtained composite oxide black pigment 6. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of the complex oxide black pigment 6 obtained using the spectrophotometer is measured, and the maximum wavelength where the transmittance is maximum exists in the wavelength range of 400-700 nm. It was confirmed.

  The obtained composite oxide black pigment 6 and the melamine alkyd resin were put in a paint shaker (manufactured by Red Devil) with a pigment content of 3 PHR (PHR = (pigment (g) / resin (g)) × 100) A paint was obtained by dispersing. The obtained paint was applied onto a PET film with a # 6 bar coater. After drying, the sample for measurement was obtained by baking at 120 ° C. for 20 minutes. The film thickness of the coating film formed on the obtained measurement sample was 3 to 4 μm.

The transmittance of the measurement sample obtained in the same manner as in Example 1 was measured. As a result, in the wavelength range of 400 to 1000 nm, it was confirmed that the wavelength range of 400 to 500 nm has a maximum wavelength that maximizes the transmittance. This measurement sample has a transmittance of about 40 to 50% in the visible part, and in the CIE LAB (L ^* a ^* b ^* ) color system, the a value is −4 to 0 and the b value is −8. ~ 0. It was also confirmed that the transmitted light had a neutral gray hue. This measurement sample had a higher transmittance in the near infrared region than any of the samples obtained in each example.

[Comparative Example 2]
A composite oxide black pigment 7 having a BET specific surface area of 47.3 m ² / g was obtained in the same manner as in Example 2 except that 120 parts of copper sulfate, 121.7 parts of manganese sulfate and 66.7 parts of iron sulfate were used. A number average particle diameter of 60 nm) was obtained. The obtained composite oxide black pigment 7 was subjected to powder X-ray diffraction analysis and confirmed to be a single compound having a spinel structure and having no heterogeneous phase. Table 1 shows the composition (molar ratio) of the metals constituting the obtained composite oxide black pigment 7. In addition, the transmittance | permeability in the wavelength range of 400-1400 nm of the complex oxide black pigment 7 obtained using the spectrophotometer is measured, and the maximum wavelength where the transmittance becomes maximum exists in the wavelength range of 400-700 nm. It was confirmed.

  The obtained composite oxide black pigment 7 and lanthanum hexaboride having a number average particle diameter of 50 nm were uniformly mixed at 10: 1 (mass ratio) to prepare a pigment. In addition, the transmittance | permeability in the 400-1400 nm wavelength range of lanthanum hexaboride is measured using a spectrophotometer, the maximum wavelength where the transmittance is maximum exists in the wavelength range of 400-700 nm, and the minimum It has been confirmed that the minimum wavelength is in the wavelength range of 800 to 1400 nm. The prepared pigment and the melamine alkyd resin are placed in a paint shaker (manufactured by Red Devil) with a pigment content of 3 PHR (PHR = (pigment (g) / resin (g)) × 100), sufficiently dispersed to form a paint, A paint was obtained. The obtained paint was applied onto a PET film with a # 6 bar coater. After drying, the sample for measurement was obtained by baking at 120 ° C. for 20 minutes. The film thickness of the coating film formed on the obtained measurement sample was 3 to 4 μm.

The transmittance of the measurement sample obtained in the same manner as in Example 1 was measured. As a result, it was confirmed that the transmittance had a minimum wavelength in the wavelength range of 800 to 1400 nm. This measurement sample had an a value of −4 to 0 and a b value of −8 to 0 in the CIE LAB (L ^* a ^* b ^* ) color system. Further, the hue of this measurement sample was yellowish and the transmitted light did not have a neutral gray hue. However, the transmittance in the near-infrared region was as low as that of the measurement sample obtained in the above example.

  Table 2 shows the compounding amounts of the composite oxide black pigment and the metal compound particles in Examples and Comparative Examples.

[Confirmation test of temperature rise suppression effect]
The confirmation test of the temperature rise inhibitory effect was conducted using the apparatus shown in FIG. The apparatus shown in FIG. 1 is disposed in a foamed polystyrene container 4 with black paper 7 attached to the inner wall surface thereof, a thermocouple 6 inserted through a hole formed in the lower part of the container, and an opening of the container 4. The glass plate 3 that prevents inflow of outside air into the container 4, the standard light source lamp 1 disposed above the glass plate 3, and the light emitted from the standard light source lamp 1 are prevented from directly hitting the thermocouple 6. And 5 for the purpose. The measurement sample 2 was placed on the glass plate 3, and the standard light source lamp 1 was set at a height of 30 cm from the measurement sample 2. Light was irradiated from the standard light source lamp 1 and the temperature in the container 4 was measured over time to create a temperature rise curve. In addition, as the measurement sample 2, a PET film (Ref) on which nothing was applied for reference, and the measurement samples obtained in Examples and Comparative Examples were used.

  The confirmation test of the temperature rise inhibitory effect was done by said setting. When the PET film (Ref) was used, the temperature inside the container rose and reached 55 ° C. after 20 minutes. Further, the temperature in the container after 20 minutes was measured using the measurement samples obtained in each of the examples and comparative examples. In Comparative Example 1, it was found that the temperature in the container after 20 minutes was 48 ° C., and the temperature suppression effect was about 7 ° C. On the other hand, when the measurement samples obtained in Examples 1 to 5 and Comparative Example 2 were used, the temperature suppression effect after 20 minutes was about 13 as compared with the case where the PET film (Ref) was used. It was found to be ° C. From this, it can be seen that the heat-shielding pigment compositions of Examples 1 to 5 and Comparative Example 2 have higher heat ray shielding properties than the pigment of Comparative Example 1. The measurement sample obtained in Comparative Example 2 did not have a bluish neutral gray hue. From the above, it can be seen that the thermal barrier pigment composition of the present embodiment has a neutral gray hue and also has an excellent temperature rise suppressing effect.

  The heat-shielding pigment composition of the present invention is a colorant such as a film or a coating material used for window glass of buildings, general houses, vehicles such as trains and automobiles, ships, and airplanes; a colorant for bottles and bottles; It is useful as a colorant for coating materials for LCDs, PDPs, organic EL panels, solar cells, synthetic leather manufacturing materials, adhesive materials, and light wavelength adjustment lens materials.

1: Standard light source lamp 2: Measurement sample 3: Glass plate 4: Container 5: 庇 6: Thermocouple 7: Black paper 11: Release paper 12: Skin layer 13: Adhesive layer 14: Base material 20: Synthetic leather

Claims (9)

A heat-shielding pigment composition for coloring, comprising a composite oxide black pigment (A) composed of an oxide of a main component metal containing copper, manganese, and iron, and metal compound particles (B) having heat ray shielding performance There,
The composite oxide black pigment (A) has a manganese / iron molar ratio of 3/1 to 30/1 and a copper / (manganese + iron) molar ratio of 1/2 to 1.2 / 2. Yes,
Each of the composite oxide black pigment (A) and the metal compound particles (B) has a maximum wavelength in the wavelength range of 400 to 700 nm in the wavelength range of 400 to 1400 nm.
The metal compound particles (B) are at least one of tungsten oxide particles and lanthanum hexaboride particles;
Thermal barrier pigment composition that gives a neutral gray color tone. ^2. The barrier according to claim 1, wherein the composite oxide black pigment (A) has a spinel structure represented by a composition of Cu (Mn, Fe) ₂ O ₄ and has a BET specific surface area of 30 m ² / g or more. Thermal pigment composition. 3. The barrier according to claim 1, wherein the composite oxide black pigment (A) is obtained by introducing 2 to 10 mol% of a divalent metal of at least one of calcium and magnesium in a ratio to the copper. Thermal pigment composition. Transparent blue provided with a transparent base material and the thermal-insulation pigment composition as described in any one of Claims 1-3 arrange | positioned in the dispersed state on the surface of the said transparent base material, and at least any inside. Articles with a neutral gray color of taste. The article according to claim 4 , wherein in the CIE LAB (L ^* a ^* b ^* ) color system, the a value is -4 to 0 and the b value is -8 to 0. An infrared shielding composition comprising a resin material and the thermal barrier pigment composition according to any one of claims 1 to 3 . 7. The method according to claim 6 , further comprising at least one infrared shielding material selected from the group consisting of tin-doped indium oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, tin-doped zinc oxide, and silicon-doped zinc oxide. The composition for infrared rays shielding of description. Infrared shielding composition according to claim 6 or 7, which is a coating agent or adhesive. A synthetic leather comprising a skin layer comprising the infrared shielding composition according to any one of claims 6 to 8 .

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