HEAT-RAY SHIELDING PARTICLE DISPERSION AND METHOD FOR PRODUCING SAME

Abstract

Provided is a heat-ray shielding particle dispersion which contains: ITO particles having a heat-ray shielding capability; a solvent containing 60% by mass or more of water; and a dispersant. The ITO particles have a BET specific surface area of 20 m.sup.2/g or more, have a blue or dark blue tone represented by an L value of 50 or less and a<0 and b<0 in the Lab color system, and are contained in an amount of 1-90% by mass with respect to 100% by mass of the dispersion. The solvent is a component obtained by removing the heating residue from the heat-ray shielding particle dispersion, and is contained in an amount of 6.1-99.0% by mass with respect to 100% by mass of the dispersion. The dispersant is at least one kind among a phosphate ester-based dispersant, a polyglycerin-based dispersant, a polyvinylpyrrolidone-based dispersant, a polyoxyethylene-polyoxypropylene condensate-based dispersant, and a polyacrylate-based dispersant.

Claims

1. A heat-ray shielding particle dispersion comprising a heat-ray shielding particle dispersion which contains ITO particles having a heat-ray shielding capability, a solvent containing 60% by mass or more of water and a dispersant, the ITO particles have a BET specific surface area of 20 m.sup.2/g or more, have a blue or dark blue tone represented by an L value of 50 or less, a<0 and b<0 in an Lab color system, and are contained in an amount of 1-90% by mass with respect to 100% by mass of the dispersion, the solvent is a component obtained by removing the heating residue from the heat-ray shielding particle dispersion, and is contained in an amount of 6.1-99.0% by mass with respect to 100% by mass of the dispersion, the dispersant is one kind or two or more kinds of dispersants selected from the group consisting of a phosphate ester-based dispersant, a polyglycerin-based dispersant, a polyvinylpyrrolidone-based dispersant, a polyoxyethylene-polyoxypropylene condensate-based dispersant, and a polyacrylate-based dispersant, and a content of an active ingredient(s) of the dispersant is 0.05-80 parts by mass with respect to 100 parts by mass of the ITO particles.

2. The heat-ray shielding particle dispersion according to claim 1, wherein, when the heat-ray shielding particle dispersion having an ITO particle concentration of 0.3% by mass is placed in a glass cell having an optical path length of 1 mm and measured, a haze is 5% or less, a transmittance at a wavelength of 1,200 nm is 60% or less and a visible light transmittance is 85% or more.

3. A method for producing a heat-ray shielding particle dispersion by mixing ITO particles having a heat-ray shielding capability, a solvent containing 60% by mass or more of water and a dispersant, the ITO particles have a BET specific surface area of 20 m.sup.2/g or more, have a blue or dark blue tone represented by an L value of 50 or less, a<0 and b<0 in an Lab color system, the solvent is a component obtained by removing the heating residue of the dispersion from the heat-ray shielding particle dispersion, the dispersant is one kind or two or more kinds of dispersants selected from the group consisting of a phosphate ester-based dispersant, a polyglycerin-based dispersant, a polyvinylpyrrolidone-based dispersant, a polyoxyethylene-polyoxypropylene condensate-based dispersant, and a polyacrylate-based dispersant, and these are mixed so as to contain 1 to 90% by mass of the ITO particles and 6.1 to 99.0% by mass of the solvent with respect to 100% by mass of the dispersion, respectively, and 0.05 to 80 parts by mass of the dispersant as an active ingredient of the dispersant when the ITO particles are made 100 parts by mass.

4. A method for producing a coating material for heat-ray shielding using the heat-ray shielding particle dispersion according to claim 1.

5. A method for producing a coating material for heat-ray shielding using the heat-ray shielding particle dispersion according to claim 2.

6. A method for producing a coating material for heat-ray shielding using the heat-ray shielding particle dispersion produced by the method according to claim 3.

Description

EXAMPLES

[0028] Next, Examples of the present invention will be explained in detail with Comparative Examples.

[Nine Kinds of ITO Particles]

[0029] Nine kinds of ITO particles to be used in Examples 1 to 50 of the present invention and Comparative Examples 1 to 7 are shown in Table 1. In Table 1, ITO particles having a BET specific surface area of less than 20 to 40 m.sup.2/g, an L value in an Lab color system of 40 to 50, a<0 and b<0, and a color tone of which is dark blue are shown with No. M-1 to No. M-3, and ITO particles having a BET specific surface area of 40 m.sup.2/g or more, an L value in an Lab color system of 20 to 30, a<0 and b<0, and a color tone of which is dark blue are shown with No. S-1 to No. S-5. ITO particles having a BET specific surface area which is out of the range of the present invention of less than 20 m.sup.2/g, an L value in an Lab color system of 70, a is 3.0 and b is 5.0, and a color tone of which is light blue is shown with No. L.

TABLE-US-00001 TABLE 1 Content of ITO particles BET value Kind (m.sup.2/g) Color tone L value a b No. L 18.0 Light blue 70.0 3.0 5.0 No. M-1 21.0 Blue 49.8 4.0 10.1 No. M-2 30.0 Blue 47.3 3.6 11.9 No. M-3 39.0 Blue 46.2 3.5 10.9 No. S-1 41.2 Dark blue 28.3 2.5 15.6 No. S-2 46.2 Dark blue 25.7 3.2 6.7 No. S-3 49.9 Dark blue 29.1 1.7 14.5 No. S-4 55.8 Dark blue 26.6 3.9 7.4 No. S-5 71.0 Dark blue 29.1 2.1 12.0

[Eleven Kinds of Dispersants]

[0030] Eleven kinds of dispersants to be used in Examples 1 to 50 of the present invention and Comparative Examples 1 to 7 are shown in Table 2. As can be clearly seen from Table 2, as the phosphate ester-based dispersants, No. 1a: DISPARLONAQ-320 (manufactured by Kusumoto Chemicals, Ltd.), No. 1b: SOLSPERSE 41000 (manufactured by The Lubrisol Corporation), No. 1c: PLYSURF A212C (manufactured by DSK Co., Ltd.) and No. Id: ethyl phosphate (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) were used. As the polyglycerin-based dispersant, No. 2: SY-Glyster MCA-750 (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was used. As the polyvinylpyrrolidone-based dispersant, No. 3: PITZCOL K-30L (manufactured by DSK Co., Ltd.) was used. As the polyoxyethylene-polyoxypropylene condensate-based dispersants, No. 4a: ADEKA Pluronic L-64 (manufactured by ADEKA CORPORATION) and No. 4b: ADEKA Pluronic L-101 (manufactured by ADEKA CORPORATION) were used. As the polyacrylate-based dispersant, No. 5: DESPERBYK-2013 (manufactured by BYK-Chemie) was used. For comparison, as the dispersants which were not the dispersant of the present invention, No. 6: LOMAR PWA-40K (manufactured by SAN NOPCO LIMITED) which is a condensed naphthalene sulfonic acid ammonium salt-based dispersant and No. 7: Nuosperse 2006 (manufactured by ELEMENTIS) which is a sulfosuccinic acid sodium salt-based dispersant were used.

TABLE-US-00002 TABLE 2 Kind Content of dispersant No. 1a Phosphate ester-based dispersant DISPARLON AQ-330 No. 1b Phosphate ester-based dispersant SOLSPERSE 41000 No. 1c Phosphate ester-based dispersant PLYSURF A212C No. 1d Phosphate ester-based dispersant Ethyl phosphate No. 2 Polyglycerin-based dispersant SY-Glyster MCA-750 No. 3 Polyvinylpyrrolidone-based dispersant PITZCOL K-30L No. 4a Polyoxyethylene-polyoxypropylene ADEKA Pluronic L-64 condensate-based dispersant No. 4b Polyoxyethylene-polyoxypropylene ADEKA Pluronic condensate-based dispersant L-101 No. 5 Polyacrylate-based dispersant DESPERBYK-2013 No. 6 Condensed naphthalene sulfonic LOMAR PWA-40K acid ammonium salt-based dispersant No. 7 Sulfosuccinic acid sodium salt-based Nuosperse 2006 dispersant

Example 1

[0031] As the ITO particles, the ITO particles of No. S-3 was used, and as the dispersant, DISPARLON AQ-320 (manufactured by Kusumoto Chemicals, Ltd.) of No. 1a was used. This dispersant was mixed with ion exchange water of room temperature to prepare a dispersant aqueous solution, and the ITO particles of the above-mentioned No. S-3 was added to the dispersant aqueous solution and dispersed by a beads mill which is a stirring apparatus to obtain a heat-ray shielding particle dispersion. At this time, a contained ratio of the dispersant was 0.05 part by mass when the ITO particles were made 100 parts by mass, a contained ratio of the ITO particles to 100% by mass of the dispersion was 20% by mass, a contained ratio of water in the solvent was 100% by mass, and a contained ratio of the solvent was 79.99% by mass based on 100% by mass of the dispersion. The content of the heat-ray shielding particle dispersion is shown in Table 3.

Examples 2 to 50 and Comparative Examples 1 to 7

[0032] Among the ITO particles and the dispersants of the kinds shown in Table 1 and Table 2, as shown in the following Table 3 to Table 5, the ITO particles and the dispersants of Examples 2 to 50 and Comparative Examples 1 to 7 were selected, respectively. Also, by using the same stirring apparatus as used in Example 1, as shown in Table 3 to Table 5, when the ITO particles were made 100 parts by mass, a contained ratio of the dispersant, a contained ratio of the ITO particles based on 100% by mass of the dispersion, a contained ratio of water in the solvent and a contained ratio of the solvent based on 100% by mass of the dispersion were determined. In Example 29, 40% by mass of the solvent was made ethanol, and the remaining 60% by mass was made water. Also, in Example 50, as the dispersant, both of No. 2 and No. 3 were used. A mass ratio of the dispersant of No. 2:the dispersant of No. 3 was 2:1.

TABLE-US-00003 TABLE 3 Evaluation of Heat-ray shielding particle dispersion dispersion Disper- ITO Transmit- sant/ITO parti- tance at Visible Kind of parti- cles/ Solvent/ wave- light ITO Kind of cles disper- Water/ disper- length transmit- parti- disper- (parts sion solvent sion Haze of 1,200 tance cles sant by mass) (mass %) (mass %) (mass %) (%) nm (%) (%) Example 1 No. S-3 No. 1a 0.05 20 100 79.99 1.0 25.4 94.02 Example 2 No. S-3 No. 1a 0.5 20 100 79.9 0.7 26.2 94.3 Example 3 No. S-3 No. 1a 1 20 100 79.8 0.3 30.0 95.5 Example 4 No. S-3 No. 1a 5 20 100 79.0 0.3 29.9 95.4 Example 5 No. S-3 No. 1a 15 20 100 77.0 0.4 27.1 95.3 Example 6 No. S-3 No. 1a 30 20 100 74.0 0.7 25.6 94.3 Example 7 No. S-3 No. 1a 80 20 100 64.0 2.8 25.0 93.0 Example 8 No. S-3 No. 1a 10 30 100 67.0 0.4 27.0 95.0 Example 9 No. S-3 No. 1a 20 30 100 64.0 0.4 27.2 95.1 Example 10 No. S-3 No. 1a 30 30 100 61.0 0.6 26.5 94.5 Example 11 No. S-1 No. 1a 30 20 100 74.0 1.2 25.4 93.8 Example 12 No. S-2 No. 1a 30 20 100 74.0 0.8 25.9 93.8 Example 13 No. S-4 No. 1a 30 20 100 74.0 0.5 26.2 94.8 Example 14 No. S-5 No. 1a 30 20 100 74.0 1.2 25.5 93.72 Example 15 No. S-3 No. 1b 0.5 30 100 69.85 1.5 28.9 93.2 Example 16 No. S-3 No. 1b 5 30 100 68.5 0.3 28.0 95.5 Example 17 No. S-3 No. 1b 15 30 100 65.5 0.3 28.4 95.6 Example 18 No. S-3 No. 1b 20 30 100 64.0 0.4 29.2 95.4 Example 19 No. S-3 No. 1b 25 30 100 62.5 0.4 29.1 95.6 Example 20 No. S-3 No. 1b 30 30 100 61.0 0.4 29.2 95.1 Example 21 No. S-3 No. 1b 50 30 100 55.0 1.5 29.2 92.03 Example 22 No. S-3 No. 1b 60 30 100 52.0 4.6 29.4 90.65

TABLE-US-00004 TABLE 4 Evaluation of Heat-ray shielding particle dispersion dispersion Disper- ITO Transmit- sant/ITO parti- tance at Visible Kind of parti- cles/ Solvent/ wave- light ITO Kind of cles disper- Water/ disper- length transmit- parti- disper- (parts sion solvent sion Haze of 1,200 tance cles sant by mass) (mass %) (mass %) (mass %) (%) nm (%) (%) Example 23 No. S-3 No. 1b 80 5 100 91.0 1.3 28.8 93.5 Example 24 No. S-3 No. 1b 1 1 100 99.0 1.5 28.6 93.4 Example 25 No. S-3 No. 1b 10 3 100 96.7 1.6 28.4 93.6 Example 26 No. S-3 No. 1b 20 50 100 40.0 1.1 21.1 93.1 Example 27 No. S-3 No. 1b 20 60 100 28.0 0.9 21.6 93.6 Example 28 No. S-3 No. 1b 80 20 100 64.0 1.7 19.3 93.6 Example 29 No. S-3 No. 1b 20 30 60 64.0 0.5 28.7 95.6 Example 30 No. S-3 No. 1c 1 20 100 79.8 0.5 30.0 95.2 Example 31 No. S-3 No. 1d 5 20 100 79.0 0.6 32.5 94.5 Example 32 No. S-3 No. 2 1 20 100 79.0 0.6 32.1 95.2 Example 33 No. S-3 No. 3 0.5 20 100 79.0 0.6 32.1 95.0 Example 34 No. S-3 No. 4a 5 30 100 68.5 0.6 28.9 95.4 Example 35 No. S-3 No. 4b 5 30 100 68.5 1.0 25.0 94.0 Example 36 No. S-3 No. 5 10 30 100 67.0 0.8 27.5 94.3 Example 37 No. M-2 No. 1a 0.05 20 100 79.99 3.0 38.8 89.5 Example 38 No. M-1 No. 1a 40 20 100 72.0 2.4 59.0 93.5 Example 39 No. M-2 No. 1a 40 20 100 72.0 1.5 41.2 92.5 Example 40 No. M-3 No. 1a 40 20 100 72.0 1.0 50.8 95.2 Example 41 No. M-2 No. 1b 40 20 100 72.0 1.2 50.7 95.1 Example 42 No. M-2 No. 1c 10 20 100 78.0 1.3 50.1 94.9 Example 43 No. M-2 No. 1d 10 20 100 78.0 2.3 39.5 90.8

TABLE-US-00005 TABLE 5 Evaluation of Heat-ray shielding particle dispersion dispersion Disper- ITO Transmit- sant/ITO parti- tance at Visible Kind of parti- cles/ Solvent/ wave- light ITO Kind of cles disper- Water/ disper- length transmit- parti- disper- (parts sion solvent sion Haze of 1,200 tance cles sant by mass) (mass %) (mass %) (mass %) (%) nm (%) (%) Example 44 No. M-2 No. 2 10 20 100 78.0 2.1 38.2 92.8 Example 45 No. M-2 No. 3 0.5 20 100 79.9 2.5 50.7 95.1 Example 46 No. M-2 No. 4a 50 20 100 70.0 3.2 38.0 94.0 Example 47 No. M-2 No. 4a 80 20 100 64.0 4.9 35.0 85.1 Example 48 No. M-2 No. 4b 50 20 100 70.0 3.3 36.2 93.1 Example 49 No. M-2 No. 5 10 20 100 78.0 1.8 39.8 95.1 Example 50 No. S-2 No. 2 3 20 100 79.4 0.9 39.8 95.1 No. 3 Comparative No. L No. 1a 1 20 100 79.8 11.2 61.2 82.3 Example 1 Comparative No. S-2 No. 6 1 20 100 79.8 cannot be cannot be cannot be Example 2 measured measured measured Comparative No. S-2 No. 7 1 20 100 79.8 cannot be cannot be cannot be Example 3 measured measured measured Comparative No. S-2 No. 1a 0.001 30 100 69.99 5.8 27.5 84.5 Example 4 Comparative No. S-2 No. 1a 90 20 100 62.0 6.11 28.2 83.3 Example 5 Comparative No. S-2 No. 1a 20 0.5 100 99.4 cannot be cannot be cannot be Example 6 mea-sured measured measured Comparative No. S-2 No. 1a 1 93 100 6.07 cannot be cannot be cannot be Example 7 measured measured measured

<Comparative Tests and Evaluation>

[0033] The heat-ray shielding particle dispersions obtained in Examples 1 to 50 and Comparative Examples 1 to 7 were made samples, a haze, a transmittance at a wavelength of 1,200 nm and a visible light transmittance of the respective samples were measured by the following methods. These measurement results are shown in Table 3 to Table 5.

(1) Haze

[0034] The sample was diluted with ion exchange water so that the concentration of the ITO particles in each of the sample became 0.3% by mass, and the diluted dispersion was measured by a haze computer (HZ-2 manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS standard (JISK7136).

(2) Transmittance at Wavelength of 1,200 nm and Visible Light Transmittance

[0035] A dispersion in which the sample was diluted in the same manner as in the sample in which the haze has been measured was placed in a glass cell having an optical path length of 1 mm, a transmittance at a wavelength of 1, 200 nm and visible light transmittance were measured by using an integrating sphere type spectrophotometer (UH4150 manufactured by Hitachi High-Technologies Corporation) in accordance with JIS standard (JIS R 3106).

[0036] As clearly seen from Table 5, in Comparative Example 1, the ITO particles of No. L were used, and the BET value was small as 18.0 m.sup.2/g and the L value was large as 70.0, so that the haze was high as 11.2% and the visible light transmittance was also low as 82.3%, whereby sufficient transparency could not be obtained.

[0037] In Comparative Example 2 and Comparative Example 3, the dispersants of No. 6 and No. 7 which were the dispersants other than the dispersants of the present invention were used, the ITO particles did not disperse uniformly, and evaluation of the dispersion could not be done.

[0038] In Comparative Example 4, even when the dispersant of the present invention is used as a dispersant, the dispersant was too little as 0.001 part by mass based on the ITO particles, dispersion of the ITO particles did not proceed sufficiently, the haze was high as 5.8% and the visible light transmittance was low as 84.5%, whereby sufficient transparency could not be obtained.

[0039] In Comparative Example 5, even when the dispersant of the present invention was used as a dispersant, if the dispersant was too much as 90 parts by mass to the ITO particles, the dispersion became too high viscosity and dispersion of the ITO particles did not proceed whereby it did not become a good dispersion, the haze was high as 6.11% and the visible light transmittance was low as 83.3%, whereby sufficient transparency could not be obtained.

[0040] In Comparative Example 6, the ITO particles were too little as 0.5% by mass to the dispersion, and the ITO particles did not sufficiently disperse, whereby evaluation of the dispersion could not be done.

[0041] In Comparative Example 7, the ITO particles were too much as 93% by mass with respect to the dispersion, and the solvent was too little as 6.07% by mass so that it became high viscosity, whereby evaluation of the dispersion could not be done.

[0042] To the contrary, as clearly seen from Table 3 and Table 4, in Examples 1 to 50, dispersion is done by using the ITO particles, the solvent and the dispersant which satisfy the requirements defined in the first aspect and the third aspect, so that heat-ray shielding particle dispersions having high transparency and heat-ray shielding capability can be prepared. At this time, when the ITO particles are used with the kinds of No. S-1 to No. S-5, more excellent heat-ray shielding capability can be given.

UTILIZABILITY IN INDUSTRY

[0043] The heat-ray shielding particle dispersion of the present invention can be utilized for a coating material for heat-ray shielding to be coated onto a transparent portion of automobiles, building materials, etc.