JP2011012112A - Dispersion for forming heat ray shielding film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat ray shielding dispersion capable of forming a transparent film with low haze and having excellent heat ray shielding effect.SOLUTION: The dispersion includes a heat ray shielding material powder, a plasticizer, an alcohol, a dispersion protecting agent and a dispersion stabilizer, and the dispersion for forming the heat ray shielding film contains 0.05-10.0 mass% of water relative to the content of the heat ray shielding material powder. Preferably, in the dispersion for forming the heat ray shielding film, the heat ray shielding material power is a mixed powder of an ATO powder and an ITO powder, a mixed powder of an ATO powder or an ITO powder or an ITO powder and an AlOpowder, a mixed powder of an ITO powder and a ZnO powder, or a mixed powder of an ITO powder and a TiOpowder and an ITO powder and a SiOpowder, the visible light transmittance (%Tv) is 84% or higher, the solar radiation transmittance (%Ts) is 64% or lower, and the haze is 0.65% or lower.

Description

The present invention relates to a heat ray shielding dispersion liquid that has an excellent heat ray shielding effect and can form a transparent film having low haze. The heat ray shielding dispersion of the present invention is suitable as an interlayer film composition for laminated glass, such as window glass for various vehicles, window glass for building materials, window glass for various devices such as medical instruments, general packaging, showcase, etc. It can be widely applied to the transparent part.

Conventionally, it is known to use antimony tin oxide powder (ATO powder) and indium tin oxide powder (ITO powder) as a heat ray shielding material. ITO powder has the advantage that it is excellent in transparency and heat ray shielding properties and also has good weather resistance, but it is expensive and expensive. On the other hand, ATO powder is cheaper than ITO powder and can form a film having a low haze, but there is a problem that transparency, heat ray shielding and weather resistance are inferior to ITO powder (Patent Document 1). ).

Therefore, it is conceivable to mix the ATO powder and the ITO powder to utilize the advantages of both, but the isoelectric point of the ITO powder is about pH 8, whereas the isoelectric point of the ATO powder is about pH 3. Therefore, there is a problem that it is difficult to obtain a stable liquid uniformly dispersed even if these are simply mixed. For this reason, conventionally, even if it intends combined use of ATO powder and ITO powder, a desired effect is not acquired and the specific application example is not known. (Patent Documents 2 and 3)

In order to solve this problem, a composition in which ATO powder and ITO powder are dispersed in the presence of a protective agent made of an organic compound having a phosphate group or a sulfonate group has been proposed (Patent Document 4). This dispersion composition (dispersion) has excellent heat ray shielding effect and weather resistance because ATO powder and ITO powder are stably and uniformly dispersed.

Japanese Patent No. 3250125 JP-A-9-208775 JP-A-9-208918 JP 2007-154152 A

Generally, laminated glass is formed by sandwiching a resin film (intermediate film) to which a plasticizer is added between at least a pair of glasses. Laminated glass with such a structure is widely used as a window glass for vehicles such as automobiles, aircrafts, buildings, etc., because it is safe to prevent glass fragments from scattering even if damaged by external impact. Has been.

It is known to form a laminated glass having a heat ray shielding effect by dispersing a heat ray shielding material such as ITO powder in the intermediate film. As this heat ray shielding material, ATO powder and ITO powder can be used in combination, and the dispersion of ATO powder and ITO powder described in Patent Document 4 can be used. Specifically, since the interlayer film of the laminated glass is formed of a resin to which a plasticizer is added, a dispersion liquid in which a plasticizer is added together with ATO powder and ITO powder can be used.

On the other hand, the interlayer film of laminated glass is required to have as high transparency as possible and low haze from the viewpoint of its use. The present invention provides a dispersion in which ATO powder and ITO powder are mixed and dispersed, which has a high heat ray shielding effect and a low haze.

The present invention is not limited to the combination of ATO powder and ITO powder, but a dispersion using ATO powder and ITO powder alone, or a mixed dispersion of ITO powder and Al ₂ O ₃ powder, ITO powder and ZrO _2. Also in the mixed dispersion of powder, mixed dispersion of ITO powder and TiO ₂ powder, mixed dispersion of ITO powder and SnO ₂ powder, mixed dispersion of ITO powder and SiO ₂ powder, the heat ray shielding effect is high and haze Provides a low dispersion.

〔６〕分散保護剤が次式[２]〔式中、Ｒ₃は金属塩またはエーテルを含有した基、Ｒ₄はアルキル基またはアルキルアリル基〕によって表されるスルホン酸基含有化合物である上記[１]〜上記[４]の何れかに記載する熱線遮蔽膜形成用分散液。

〔７〕分散保護剤が、リン酸ポリエステル、フェノールスルホン酸ナトリウム、アルキルベンゼンスルホン酸カリウム、アルキルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム、ジアルキルスルホ琥珀酸ナトリウム塩、ポリオキシエチレンスルホ琥珀酸ラウリル二ナトリウム、ヤシ油脂肪酸メチルタウリンナトリウム、ポリオキシエチレンスチレンフェニルエーテル硫酸アンモニウム塩、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシアルキルデシルエーテル硫酸ナトリウム、スルホン基含有カップリング剤の１種または２種である上記[１]〜上記[６]の何れかに記載する熱線遮蔽膜形成用分散液。
〔８〕分散安定剤が、リン酸エステル、硫酸エステル、βジケトン類、脂肪族カルボン酸の１種または２種以上である上記[１]〜上記[７]の何れかに記載する熱線遮蔽膜形成用分散液。
〔９〕記[１]〜上記[８]の何れかの分散液を用いた合わせガラス用中間膜または合わせガラス。 The present invention relates to a dispersion for forming a heat ray shielding film that has solved the above problems by having the following configuration.
[1] In a dispersion containing a heat ray shielding material powder, a plasticizer, an alcohol, a dispersion protective agent, and a dispersion stabilizer, 0.05% by mass to 10.0% by mass of water with respect to the content of the heat ray shielding material powder [2] The visible light transmittance (% Tv) is 84% or more, the solar radiation transmittance (% Ts) is 64% or less, and the haze is 0.65%. The dispersion for forming a heat ray shielding film as described in [1] above.
[3] The dispersion for forming a heat ray shielding film according to the above [1] or [2], wherein the heat ray shielding material powder is a mixed powder of ATO powder and ITO powder, or ATO powder or ITO powder.
[4] The heat ray shielding powder is a mixed powder of ITO powder and Al ₂ O ₃ powder, a mixed powder of ITO powder and ZnO powder, a mixed powder of ITO powder and TiO ₂ powder, or a mixed powder of ITO powder and SnO ₂ powder. The dispersion for forming a heat ray shielding film according to the above [1] or [2], which is a powder or a mixed powder of ITO powder and SiO ₂ powder.
[5] The dispersion protective agent is represented by the following formula [1] [wherein R ₁ is an alkyl group or alkylallyl group, R ₂ is hydrogen or R ₁ (CH ₂ CH ₂ O) _n group, and n is the number of moles of ethylene oxide added] The dispersion for forming a heat ray shielding film according to any one of the above [1] to [4], which is a phosphoric acid polyester represented by:

[6] The dispersion protective agent is a sulfonic acid group-containing compound represented by the following formula [2] [wherein R ₃ is a group containing a metal salt or ether, and R ₄ is an alkyl group or an alkylallyl group] [1] The dispersion for forming a heat ray shielding film according to any one of [4] above.

[7] Dispersion protective agent is phosphoric acid polyester, sodium phenolsulfonate, potassium alkylbenzenesulfonate, sodium alkylbenzenesulfonate, sodium lauryl sulfate, sodium dialkylsulfosuccinate, disodium lauryl polyoxyethylene sulfosuccinate, coconut oil [1] to [1] above, which is one or two of fatty acid methyl taurine sodium, polyoxyethylene styrene phenyl ether ammonium sulfate, polyoxyethylene lauryl ether sodium sulfate, polyoxyalkyl decyl ether sodium sulfate, and sulfone group-containing coupling agent [6] The dispersion for forming a heat ray shielding film according to any one of [6].
[8] The heat ray shielding film according to any one of [1] to [7], wherein the dispersion stabilizer is one or more of phosphoric acid ester, sulfuric acid ester, β diketone, and aliphatic carboxylic acid. Forming dispersion.
[9] An interlayer film for laminated glass or a laminated glass using the dispersion liquid according to any one of [1] to [8].

In the dispersion liquid of the present invention, the heat ray shielding material is uniformly dispersed, this dispersion state is stable, it has excellent visible light transmittance and heat ray shielding effect, and haze is significantly low.

When the dispersion of the present invention is used by mixing ATO powder and ITO powder, these dispersion states are stable and uniform, and a dispersion having a significantly low haze can be obtained. Not only the combination of ITO powder, but also a dispersion using ATO powder and ITO powder individually, mixed powder of ITO powder and Al ₂ O ₃ powder, mixed powder of ITO powder and ZnO powder, or ITO powder and TiO ₂ Even in a dispersion using a mixed powder of powder, a mixed powder of ITO powder and SnO ₂ powder, or a mixed powder of ITO powder and SiO ₂ powder, a dispersion having a high heat ray shielding effect and low haze can be obtained. .

The dispersion of the present invention is used as a material for forming an interlayer film for laminated glass having a heat ray shielding effect because the dispersibility of ITO powder and ATO powder is good in a system including a plasticizer that forms an interlayer film of laminated glass. be able to.

Hereinafter, the present invention will be specifically described based on embodiments.
The dispersion of the present invention is a dispersion containing a heat ray shielding material powder, a plasticizer, an alcohol, a dispersant, and a dispersion stabilizer, and is 0.05% by mass to 10.0% by mass with respect to the content of the heat ray shielding material powder. % Of water, and preferably has a visible light transmittance (% Tv) of 84% or more and a solar transmittance (% Ts) of 64% or less. It is a dispersion for forming a heat ray shielding film having a haze of 0.65% or less.

In the dispersion liquid of the present invention, a mixed powder of ATO powder and ITO powder can be used as the heat ray shielding material powder. Further, in the dispersion of the present invention, as the heat ray-shielding material powder, ATO powder and can be used ITO powder alone, further, ITO powder and Al ₂ O ₃ powder mixed powder or ITO powder and Al ₂ O ₃ Use of mixed powder of powder, mixed powder of ITO powder and ZnO powder, mixed powder of ITO powder and TiO ₂ powder, mixed powder of ITO powder and SnO ₂ powder, mixed powder of ITO powder and SiO ₂ powder it can.

The ITO powder can be produced, for example, by reacting a mixed aqueous solution of an indium chloride aqueous solution (InCl ₃ aqueous solution) and a tin chloride aqueous solution (SnCl ₄ aqueous solution) with an alkali and baking the generated precipitate. When the ITO powder produced in this way is used as a heat ray shielding material powder, it is preferable to use a powder obtained by reducing the powder surface by heating the ITO powder in an inert atmosphere in the presence of alcohol. By this reduction treatment, the ITO powder changes from a slightly yellow color tone to a slightly blue color tone, so that the familiarity with the alcohol solvent is improved, the heat ray shielding property is improved, and the haze is reduced.

The primary average particle diameter of heat ray shielding material powder such as ITO powder and ATO powder used in the dispersion of the present invention is preferably 0.2 μm or less, more preferably 0.1 μm or less, and even more preferably 0.08 μm or less. When the primary average particle diameter of the heat ray shielding material powder exceeds 0.2 μm, haze may be deteriorated when a film (interlayer film of laminated glass) is formed, and white turbidity due to scattering of visible light may occur.

In the dispersion liquid of the present invention, the content of the heat ray shielding material powder is not particularly defined, but is preferably 0.1 to 60% by mass. When the content of the heat ray shielding material powder is less than this, a sufficient heat ray shielding effect cannot be obtained, and when the content is more than this, the stability of the dispersion is impaired, and the product yield is greatly reduced.

In the dispersion of the present invention, when a mixed powder of ITO powder and ATO powder is used as the heat ray shielding material powder, the amount ratio of ITO powder and ATO powder is 90 to 30% by mass of ITO powder and 10 to 10 of ATO powder. A range of 70% by weight is suitable. Visible light transmittance (% Tv) and solar radiation transmittance (% Ts) can be controlled by adjusting the amount ratio of ITO powder and ATO powder.

As heat ray shielding powder, mixed powder of ITO powder and Al ₂ O ₃ powder, mixed powder of ITO powder and ZnO powder, mixed powder of ITO powder and TiO ₂ powder, mixed powder of ITO powder and SnO ₂ powder, ITO powder When a mixed powder of SiO ₂ and SiO ₂ powder is used, if there are too many Al ₂ O ₃ powder, ZnO powder, TiO ₂ powder, SnO ₂ powder, and SiO ₂ powder, transparency of visible light transmittance can be obtained, Since the thermal performance is inferior, the range of Al ₂ O ₃ powder, ZnO powder, TiO ₂ powder, SnO ₂ powder, and SiO ₂ powder is preferably 30% by mass or less with respect to the ITO powder.

In general, a polyvinyl acetal resin such as a polyvinyl butyral resin is used as an intermediate film (coating) of laminated glass as a resin component. As the plasticizer contained in the dispersion of the present invention, a general plasticizer for a polyvinyl acetal resin or the like can be used. For example, organic ester plasticizers such as monobasic acid esters and polybasic acid esters, or phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid can be used.

Specific examples of the organic ester plasticizer include, for example, triethylene glycol-di-2-ethylbutyrate, triethylene glycol-di-2-ethylhexoate, triethylene glycol dicaprylate, triethylene glycol diester. -N-octate, triethylene glycol-di-n-heptate, tetraethylene glycol-di-n-heptate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol-di-2-ethylbutyrate, 1 1,3-propylene glycol-di-2-ethylbutyrate, 1,4-propylene glycol-di-2-ethylbutyrate, 1,4-butylene glycol-di-2-ethylbutyrate, 1,2-butylene glycol Di-2-ethylene butyrate Diethylene glycol-di-2-ethylbutyrate, diethylene glycol-di-2-ethylhexoate, dipropylene glycol-di-2-ethylbutyrate, triethylene glycol-di-2-ethylpentoate, tetraethylene glycol-di -2-ethyl butyrate, diethylene glycol dicapryate and the like.

Examples of the organic phosphate plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphite, and the like.

Among the plasticizers, dihexyl adipate (DHA), triethylene glycol-di-2-ethylhexanoate (3GO), tetraethylene glycol-di-2-ethylhexanoate (4GO), triethylene glycol-di- From the group consisting of 2-ethylbutyrate (3GH), tetraethylene glycol-di-2-ethylbutyrate (4GH), tetraethylene glycol-di-heptanoate (4G7), and triethylene glycol-di-heptanoate (3G7) At least one selected may contain a metal salt of a carboxylic acid having 5 or 6 carbon atoms as an adhesive strength adjusting agent, thereby preventing a decrease in the adhesive strength between the interlayer film and the glass over time and preventing whitening. And the adhesive strength can be prevented from decreasing with time.Among these, triethylene glycol-di-2-ethylhexanoate (3GO), triethylene glycol-di-2-ethylbutyrate (3GH), tetraethylene glycol-di-2-ethylhexanoate (4GO) ) And dihexyl adipate (DHA) are particularly preferred because they are less susceptible to hydrolysis.

In the dispersion of the present invention, the plasticizer is in a liquid state and serves as a dispersion medium for dispersing the heat ray shielding material powder in the resin. The content of the plasticizer is preferably 20% by mass or more. If the content of the plasticizer is less than this, a liquid with good dispersibility cannot be obtained. On the other hand, when the content of the plasticizer is larger than this, the content of the heat ray shielding material powder is relatively reduced, and a sufficient heat ray shielding effect cannot be obtained.

The dispersion of the present invention contains alcohol as an organic solvent. Alcohol is easy to adjust to heat ray shielding material powder such as ITO powder and ATO powder, and has good compatibility with the plasticizer, so that the dispersibility of the heat ray shielding material powder can be improved. In addition, it has an effect of preventing a solvent shock, and also has an effect of suppressing fluctuations in dispersion characteristics depending on the type of plasticizer. The content of alcohol in the dispersion is preferably 1 to 20% by mass. If there is too much alcohol, the amount of low boiling point solvent increases, making it unsuitable for the production process of the intermediate film.

The kind of alcohol contained in the dispersion liquid of the present invention is not limited. For example, selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, lauryl alcohol, diacetone alcohol, cyclohexanol, ethylene glycol, diethylene glycol and triethylene glycol At least one is preferred.

The dispersion of the present invention contains a dispersion protective agent. As a dispersion protective agent, a phosphoric acid polyester represented by the following formula [1] can be used. The phosphoric acid polyester preferably has a molecular weight of 1600 or less and an acid value of 40 or less.

〔式中、Ｒ₁はアルキル基またはアルキルアリル基、Ｒ₂は水素またはＲ₁(ＣＨ₂ＣＨ₂Ｏ)_n基、ｎはエチレンオキシド付加モル数〕

[Wherein R ₁ is an alkyl group or an alkylallyl group, R ₂ is hydrogen or R ₁ (CH ₂ CH ₂ O) _n group, and n is the number of moles of ethylene oxide added)

Moreover, the sulfonic acid group containing compound represented by following formula [2] can be used as a dispersion protective agent. Examples of the sulfonic acid group-containing compound include sodium phenol sulfonate, potassium alkylbenzene sulfonate, sodium alkylbenzene sulfonate, sodium lauryl sulfate, sodium dialkylsulfosuccinate, disodium lauryl polyoxyethylene sulfosuccinate, coconut oil fatty acid Examples include methyl taurine sodium, ammonium polyoxyethylene styrene phenyl ether sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyalkyl decyl ether sulfate and the like.

〔式中、Ｒ₃は金属塩またはエーテルを含有した基、Ｒ₄はアルキル基またはアルキルアリル基〕

[Wherein R ₃ is a group containing a metal salt or ether, R ₄ is an alkyl group or an alkylallyl group]

Furthermore, as the sulfonic acid group-containing compound of the above formula [2] used as a dispersion protective agent, a sulfonic acid group-containing coupling agent can be used. Examples of the sulfonic acid group-containing coupling agent include triethoxysilane containing a sulfone group, triisopropoxy titanium containing a sulfone group, tributoxyaluminum containing a sulfone group, and tributoxyzirconium containing a sulfone group.

By including the dispersion protective agent, the surface of the heat ray shielding material powder such as ITO powder or ATO powder is covered with the dispersion protective agent, and a stable dispersion state can be obtained. The content of the dispersion protective agent is preferably 0.1 to 50% by mass with respect to the heat ray shielding material. A more preferable content of the dispersion protective agent is 1 to 20% with respect to the heat ray shielding material.

The dispersion of the present invention contains a dispersion stabilizer. As the dispersion stabilizer, for example, a compound having at least one atom selected from the group consisting of nitrogen, phosphorus, and chalcogen group atoms is preferable. These compounds are easy to adjust to heat ray shielding powder such as ITO powder and ATO powder, and can provide a good dispersion effect. Such a compound is, for example, selected from the group consisting of sulfate ester compounds, phosphate ester compounds, ricinoleic acid, polyricinoleic acid, polycarboxylic acids, polyhydric alcohol surfactants, polyvinyl alcohol and polyvinyl butyral. At least one kind is suitable.

Examples of the phosphate ester compounds include polyoxyethylene alkyl ether phosphates, alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, and the like.

Furthermore, as the dispersion stabilizer, chelates, inorganic acids, organic acids and the like are suitable. As the chelate, for example, ethylenediaminetetraacetic acid, β-diketone and the like can be used. Β-diketones are preferred because of their excellent compatibility with plasticizers and resins, and among them, acetylacetone is particularly preferred. Other examples of β diketones may include benzoyl trifluoroacetone and dipivaloylmethane.

As the inorganic acid used as the dispersion stabilizer, for example, hydrochloric acid, nitric acid and the like can be used, and as the organic acid, for example, aliphatic carboxylic acid, aliphatic dicarboxylic acid, aromatic carboxylic acid, aromatic dicarboxylic acid and the like can be used. Can be used. Specific examples include benzoic acid, phthalic acid, salicylic acid, and the like. Among these, C2-C18 aliphatic carboxylic acids are preferable, and examples thereof include acetic acid, propionic acid, n-butyric acid, 2-ethylbutyric acid, n-hexanoic acid, 2-ethylhexanoic acid, and n-octanoic acid. It is done. These inorganic acids and organic acids are effective in preventing aggregation of heat ray shielding material powders such as ITO powder and ATO powder.

In the dispersion liquid of the present invention, the combination of the plasticizer and the dispersion stabilizer as the dispersion medium is, for example, when triethylene glycol-di-2-ethylhexanoate (3GO) is used as the plasticizer. Alcohol is used, and the above phosphoric acid ester compound, an organic acid such as 2 ethylhexanoic acid, and acetylacetone may be used as a dispersion stabilizer. With such a configuration of the dispersion medium, heat ray shielding material powder such as ITO powder and ATO powder can be dispersed at a high concentration and with good dispersibility. In addition, as alcohol, methanol, ethanol, isopropanol, diacetone alcohol, etc. are preferable.

In the dispersion of the present invention, the content of the dispersion stabilizer is preferably 0.1 to 50% by mass with respect to the heat ray shielding material. If the content of the dispersion stabilizer is less than this, it is difficult to obtain a sufficient effect. On the other hand, even if the content of the dispersion stabilizer is more than this, the effect does not change much.

The dispersion of the present invention contains 0.05 to 10.0% by mass of water with respect to the content of the heat ray shielding material powder (the total amount when mixed powder is contained). By including this amount of water, haze can be reduced, and moreover, it becomes difficult to be affected by moisture due to inevitable mixing that is affected by humidity in the atmosphere, so it is possible to stabilize the quality It becomes.

The amount of water contained in the dispersion is suitably 0.05 to 10.0% by mass, preferably 0.1 to 1.5% by mass, based on the content of the heat ray shielding material powder. When the amount of water contained in the dispersion is less than 0.05% by mass, the effect is insufficient, and when it exceeds 10.0% by mass, dispersion failure occurs and haze deteriorates. For example, butyral resin or the like is difficult to dissolve, which is not preferable.

According to the present invention, a dispersion for forming a heat ray shielding film having a visible light transmittance (% Tv) of 84% or more, a solar radiation transmittance (% Ts) of 64% or less, and a haze of 0.65% or less is obtained. be able to. Further, the dispersion of the present invention can make the reflection yellow index (YI) smaller in absolute value than -23 (close to zero).

In the dispersion liquid of the present invention, the one using a mixed powder of ITO powder and ATO powder as the heat ray shielding material powder has a higher visible light transmittance (% Tv) than that using ATO powder alone, to 86% or more. Furthermore, the haze is lower than that using ITO powder alone and can be controlled to 0.63 or less, and the reflection yellow index (YI) is smaller than −22.5 (the absolute value is reduced to zero). Close)

The present invention is specifically illustrated by examples and comparative examples. The dispersion of the heat ray shielding material powder was stirred with ZrO ₂ introduced into the liquid. The evaluation method is shown below. The composition of the dispersion, visible light transmittance (% Tv), solar transmittance (% Ts), haze, and reflection yellow index (YI) are shown in Tables 1 to 1.

(Measurement of spectral characteristics)
The prepared dispersion was diluted with triethylene glycol-di-2-ethylhexanoate until the content of the heat shielding material powder became 0.7% by mass. This diluted solution is put in a glass cell having an optical path length of 1 mm, and a visible light transmittance (% Tv) of 380 nm to 780 nm is used according to a standard (JIS R 3216-1998) using a self-recording spectrophotometer (U-4000 manufactured by Hitachi, Ltd.). ) Was measured, and the solar transmittance (% Ts) at 300 nm to 2100 nm was measured.

[Haze measurement]
The haze was measured according to the standard (JIS K 7136) using a dispersion liquid diluted in the same manner as the spectroscopic property measurement sample and using a haze computer (HZ-2 manufactured by Suga Test Instruments Co., Ltd.).

[Measurement of YI]
The dispersion liquid diluted in the same manner as the spectroscopic property measurement sample is used as a sample, and 6.73 g of this diluted solution sample is put into a reflective liquid cell (No. 15), and a color computer (SM-T manufactured by Suga Test Instruments Co., Ltd.) is used. The reflection yellow index (YI) was measured from the reflectance of visible light (380 nm to 780 nm) in accordance with the standard (JIS K 7105) with the dark box for shielding external light.

[Synthesis of ITO powder]
After mixing 900 mL of InCl ₃ aqueous solution (containing 350 g of In metal) and 144 g of 55% SnCl ₄ aqueous solution, this mixed aqueous solution was reacted with 6 L of alkaline aqueous solution containing 1900 g of NH ₄ HCO _{3 at} a liquid temperature of 60 ° C. for 30 minutes. The precipitate was repeatedly washed with ion-exchanged water by tilting. When the electrical conductivity of the supernatant reaches 5000 Ω · cm or more, the precipitated In / Sn coprecipitated hydroxide is filtered off, dried overnight at 110 ° C, calcined at 550 ° C for 3 hours in air, and then pulverized. The aggregate was loosened to obtain about 440 g of ITO powder. This synthesis process was carried out in two batches to obtain a total of about 880 g of ITO powder. In addition, in order to eliminate the characteristic variation for every synthetic batch as much as possible, it put into the same plastic bag and mixed so that ITO powder might become uniform.

[Surface treatment of ITO powder]
After impregnating 40 g of the ITO powder prepared by the above method with a surface treatment solution obtained by mixing absolute ethanol and distilled water (mixing ratio is 5 parts by weight of distilled water with respect to 95 parts by weight of ethanol), it is put in a glass petri dish and then nitrogen Heat treatment was performed at 330 ° C. for 2 hours in a gas atmosphere. This surface treatment was performed 20 batches at a time to obtain a total of about 800 g of surface-treated ITO powder. In addition, in order to eliminate the characteristic difference for each surface treatment batch, the ITO powder was mixed well so that the ITO powder that had been cooled and placed in a plastic bag was uniformly treated. Hereinafter, this surface-treated ITO powder is referred to as “ITO powder P”.

As the ATO powder, ATO powder (trade name: conductive powder T-1) manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd. was used. As the SnO ₂ powder, SnO ₂ powder (trade name: conductive powder S2000) manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd. was used. As the Al ₂ O ₃ powder, Al ₂ O ₃ powder (trade name: Alumina C) manufactured by Nippon Aerosil Co., Ltd. was used. As the TiO ₂ powder, TiO ₂ powder (trade name: P-25) manufactured by Nippon Aerosil Co., Ltd. was used. As the SiO ₂ powder, SiO ₂ powder (trade name: R972) manufactured by Nippon Aerosil Co., Ltd. was used. ZrO ₂ powder was prepared by hydrolyzing zirconium tetrachloride and heat treatment.

[Example 1]
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 1.
ITO powder P (40 g), distilled water (0.040 g), triethylene glycol-di-2-ethylhexanoate [3G] (47.7 g), absolute ethanol (5.1 g), phosphoric acid polyester (2. 0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

[Example 2]
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 1.
ITO powder P (40 g), distilled water (0.080 g), triethylene glycol-di-2-ethylhexanoate [3GO] (47.6 g), absolute ethanol (5.1 g), phosphoric acid polyester (2. 0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 3
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 1.
ITO powder P (40 g), distilled water (0.40 g), triethylene glycol-di-2-ethylhexanoate [3GO] (47.3 g), absolute ethanol (5.1 g), phosphoric acid polyester (2. 0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 4
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 1.
ITO powder P (40 g), distilled water (2.8 g), triethylene glycol-di-2-ethylhexanoate [3GO] (44.9 g), absolute ethanol (5.1 g), phosphoric acid polyester (2. 0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 5
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 1.
ATO powder (40 g), distilled water (0.080 g), triethylene glycol-di-2-ethylhexanoate [3GO] (43.6 g), absolute ethanol (5.1 g), phosphoric acid polyester (3.0 g) ), Dialkylsulfosuccinic acid sodium salt (3.0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 6
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 2.
ITO powder P (28 g), ATO powder (12 g), distilled water (0.17 g), triethylene glycol-di-2-ethylhexanoate [3GO] (46.3 g), absolute ethanol (5.1 g), Phosphoric acid polyester (2.3 g), dialkylsulfosuccinic acid sodium salt (0.90 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 7
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 2.
ITO powder P (20 g), ATO powder (20 g), distilled water (0.17 g), triethylene glycol-di-2-ethylhexanoate [3GO] (45.5 g), absolute ethanol (5.1 g), Phosphoric acid polyester (2.5 g), dialkylsulfosuccinic acid sodium salt (1.5 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 8
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 2.
ITO powder P (12 g), ATO powder (28 g), distilled water (0.17 g), triethylene glycol-di-2-ethylhexanoate [3GO] (44.7 g), absolute ethanol (5.1 g), Phosphoric acid polyester (2.7 g), dialkylsulfosuccinic acid sodium salt (2.1 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 9
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 2.
ITO powder P (28 g), ATO powder (12 g), distilled water (0.70 g), triethylene glycol-di-2-ethylhexanoate [3GO] (46.5 g), absolute ethanol (4.4 g), Phosphoric acid polyester (2.3 g), dialkylsulfosuccinic acid sodium salt (0.90 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 10
To prepare a dispersion by mixing the following materials. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 2.
ITO powder P (40 g), distilled water (0.17 g), tetraethylene glycol-di-2-ethylhexanoate [4GO] (47.5 g), absolute ethanol (5.1 g), phosphoric acid polyester (2. 0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 11
To prepare a dispersion by mixing the following materials. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 3.
ITO powder P (40 g), distilled water (0.17 g), DHA (47.5 g), absolute ethanol (5.1 g), phosphoric acid polyester (2.0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 12
To prepare a dispersion by mixing the following materials. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 3.
ITO powder P (28 g), ATO powder (12 g), distilled water (0.17 g), triethylene glycol-di-2-ethylhexanoate [3GO] (46.5 g), absolute ethanol (4.9 g), Phosphoric polyester (2.3 g), sulfonic acid group-containing coupling agent (0.90 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 13
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 3.
ITO powder P (40 g), distilled water (0.17 g), triethylene glycol-di-2-ethylhexanoate [3GO] (47.6 g), absolute ethanol (4.7 g), methanol (0.30 g) , Phosphoric acid polyester (2.0 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 14
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 3.
ITO powder P (28 g 9, ATO powder (12 g), distilled water (0.17 g), triethylene glycol-di-2-ethylhexanoate (3GO) (46.4 g), absolute ethanol (4.7 g), isopropanol [IPA] (0.30 g), phosphoric acid polyester (2.3 g), sulfonic acid group-containing coupling agent (0.90 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1 0.0g)

Example 15
To prepare a dispersion by mixing the following materials. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 3.
ITO powder P (28 g), ATO powder (12 g), distilled water (0.17 g), triethylene glycol-di-2-ethylhexanoate [3GO] (46.4 g), absolute ethanol (4.7 g), Methanol (0.30 g), phosphoric acid polyester (2.3 g), sulfonic acid group-containing coupling agent (0.90 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g) )

Example 16
To prepare a dispersion by mixing the following materials. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 4.
ITO powder P (36 g), SnO ₂ powder (4.0 g), distilled water (0.08 g), triethylene glycol-di-2-ethylhexanoate [3GO] (46.4 g), absolute ethanol (5. 1 g), phosphoric acid polyester (2.1 g), sulfonic acid group-containing triisopropoxy titanium (0.30 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 17
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 4.
ITO powder P (36 g), Al ₂ O ₃ powder (4.0 g), distilled water (0.20 g), triethylene glycol-di-2-ethylhexanoate [3GO] (47.1 g), absolute ethanol ( 5.1 g), phosphoric acid polyester (2.0 g), sulfonic acid group-containing triisopropoxy titanium (0.40 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 18
To prepare a dispersion by mixing the following materials. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 4.
ITO powder P (36 g), TiO ₂ powder (4.0 g), distilled water (0.20 g), triethylene glycol di-2-ethylhexanoate [3GO] (47.2 g), absolute ethanol (5. 1 g), phosphoric acid polyester (2.0 g), sulfonic acid group-containing coupling agent (0.40 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 19
To prepare a dispersion by mixing the following materials. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 4.
ITO powder P (36 g), ZnO powder (4.0 g), distilled water (0.20 g), triethylene glycol di-2-ethylhexanoate [3GO] (47.1 g), absolute ethanol (5.1 g) ), Phosphoric acid polyester (2.0 g), sulfonic acid group-containing coupling agent (0.40 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

Example 20
The following materials were mixed to prepare a dispersion. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 4.
ITO powder P (36 g), SiO ₂ powder (4.0 g), distilled water (0.20 g), triethylene glycol-di-2-ethylhexanoate [3GO] (47.1 g), absolute ethanol (5. 1 g), phosphoric acid polyester (2.0 g), sulfonic acid group-containing coupling agent (0.40 g), 2-ethylhexanoic acid (4.0 g), 2,4-pentanedione (1.0 g)

[Comparative Examples 1-5]
Dispersions were prepared by mixing the materials shown in Table 5. The dispersion was measured for visible light transmittance (% Tv), solar radiation transmittance (% Ts), haze, and reflection yellow index (YI). The results are shown in Table 5.

Claims (9)

In a dispersion liquid containing heat ray shielding material powder, plasticizer, alcohol, dispersion protective agent, and dispersion stabilizer, 0.05% by mass to 10.0% by mass of water is included with respect to the content of the heat ray shielding material powder. A dispersion for forming a heat ray shielding film characterized by
2. The dispersion for forming a heat ray shielding film according to claim 1, wherein the visible light transmittance (% Tv) is 84% or more, the solar radiation transmittance (% Ts) is 64% or less, and the haze is 0.65% or less.
The dispersion for forming a heat ray shielding film according to claim 1 or 2, wherein the heat ray shielding material powder is a mixed powder of ATO powder and ITO powder, ATO powder, or ITO powder.
Heat ray shielding powder is mixed powder of ITO powder and Al ₂ O ₃ powder, mixed powder of ITO powder and ZnO powder, mixed powder of ITO powder and TiO ₂ powder, mixed powder of ITO powder and SnO ₂ powder, or The dispersion for forming a heat ray shielding film according to claim 1 or 2, which is a mixed powder of ITO powder and SiO ₂ powder.
The dispersion protective agent is represented by the following formula [1] [wherein R ₁ is an alkyl group or alkylallyl group, R ₂ is hydrogen or R ₁ (CH ₂ CH ₂ O) _n group, and n is the number of moles of ethylene oxide added]. The dispersion for forming a heat ray shielding film according to any one of claims 1 to 4, wherein the dispersion is a phosphoric acid polyester.

The dispersion protective agent is a sulfonic acid group-containing compound represented by the following formula [2] (wherein R ₃ is a group containing a metal salt or ether, and R ₄ is an alkyl group or an alkylallyl group): The dispersion for forming a heat ray shielding film according to claim 4.

Dispersion protective agent is polyester phosphate, sodium phenolsulfonate, potassium alkylbenzenesulfonate, sodium alkylbenzenesulfonate, sodium lauryl sulfate, sodium dialkylsulfosuccinate, disodium lauryl polyoxyethylene sulfosuccinate, palm oil fatty acid methyl taurine 7. One or two of sodium, polyoxyethylene styrene phenyl ether ammonium sulfate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyalkyl decyl ether sulfate, and sulfone group-containing coupling agent. A dispersion for forming a heat ray shielding film as described above.
The dispersion for forming a heat ray shielding film according to any one of claims 1 to 7, wherein the dispersion stabilizer is one or more of phosphoric acid ester, sulfuric acid ester, β-diketone, and aliphatic carboxylic acid.
An interlayer film for laminated glass or a laminated glass using the dispersion liquid according to any one of claims 1 to 8.