JP2008231367A - Composition for forming transparent layer having ultraviolet heat ray shielding property, transparent layer and use thereof - Google Patents

Abstract

A composition for forming a transparent layer having excellent shielding properties against heat rays and ultraviolet rays and having good weather resistance, and the transparent layer and its use are provided.
A transparent material containing indium tin oxide (ITO) powder and zinc oxide (ZnO) powder as a shielding material for ultraviolet rays and heat rays, or containing antimony tin oxide (ATO) powder together with ITO powder and ZnO powder. A composition for forming a layer, wherein the shielding material powder is dispersed in the presence of a protective agent made of an organic compound having a phosphoric acid group or a sulfonic acid group, and has a visible light transmittance (% Tv) of 60%. As described above, a composition for forming a transparent layer having an ultraviolet transmittance of 20% or less and a ratio of visible light transmittance (% Tv) to solar transmittance (% Ts) ([% Tv] / [% Ts]) of 1.0 or more. , And the transparent layer and its use.
[Selection figure] None

Description

The present invention relates to a composition that forms a transparent layer having excellent shielding properties against heat rays and ultraviolet rays and having good weather resistance, and the transparent layer and use thereof. The composition of the present invention and the transparent layer thereof are used as materials or members for various types of vehicle window glass, building material window glass, or medical machine window glass, transparent parts of packaging, transparent parts of exhibition facilities, and transparent parts of equipment. Can be widely applied.

Conventionally, it is known to use indium tin oxide powder (ITO powder) as a heat ray shielding material (Patent Documents 1 to 3). 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. Antimony tin oxide powder (ATO powder) is also known as a heat ray shielding material. ATO powder is cheaper than ITO powder and is easy to reduce haze, but there is a problem that transparency, heat ray shielding performance and weather resistance are inferior to ITO powder. Moreover, since both ITO powder and ATO powder have low shielding properties against ultraviolet rays, they cannot sufficiently shield ultraviolet rays.

On the other hand, zinc oxide powder (ZnO powder) is known as an ultraviolet shielding material (Patent Documents 4 and 5). However, conventionally, paints, coating films, cosmetics and the like to which ZnO powder is added have a problem that they are generally poor in stability and low in weather resistance. In addition, it is conceivable to use ATO powder and ITO powder together, but since the isoelectric points of ITO powder and ATO powder are greatly different, it is difficult to obtain a uniformly dispersed solution even if these are simply mixed, Even if ATO powder and ITO powder are used in combination, a desired effect cannot be obtained, and a specific application example has not been known.
Japanese Patent No. 3250125 Japanese Patent No. 2715859 Japanese Patent No. 2715860 Japanese Patent Laid-Open No. 11-302625 JP-A-10-120419

The present invention solves the above-mentioned conventional problems, uses ITO powder and ZnO powder together, has a good dispersion stability of the powder, and has a transparent layer having excellent shielding properties against both heat rays and infrared rays. And a transparent layer and the like are provided.

（５）スルホン酸基を有する保護剤が下記一般式〔２〕で表されるスルホネート化合物である上記(１)〜上記(３)の何れかに記載する透明層形成用組成物。

（６）ＩＴＯ粉末とＺｎＯ粉末の混合粉末の分散液、またはＩＴＯ粉末とＺｎＯ粉末とＡＴＯ粉末の混合粉末の分散液、該分散液からなる塗料、ペースト、またはこれらによって形成された塗膜ないしフィルムである上記(１)〜上記(５)の何れかに記載する透明層形成用組成物。
（７） 上記(１)〜上記(６)の何れかに記載する組成物によって形成された透明層であって、可視光線透過率(％Ｔv)６０％以上、紫外線透過率２０％以下、可視光線透過率(％Ｔv)の日射透過率(％Ｔs)に対する比（[％Tv]/[％Ts]）１.０以上である紫外線熱線遮蔽性透明層。
（８）可視光線透過率(％Ｔv)８０％以上、紫外線透過率１５％以下、熱線遮蔽比（[％Tv]/[％Ts]）１.４以上である上記(７)に記載する紫外線熱線遮蔽性透明層。
（９）上記(７)または上記(８)に記載する紫外線熱線遮蔽性透明層を有する車両用窓ガラス、建材用窓ガラス、または医療機械用窓ガラス、包装物の透明部、展示設備の透明部、機器の透明部。 The present invention relates to a composition for forming a heat ray ultraviolet ray-shielding transparent layer that has solved the above problems by having the following constitution, its transparent layer and use.
(1) A composition for forming a transparent layer, comprising indium tin oxide (ITO) powder and zinc oxide (ZnO) powder dispersedly as a shielding material for ultraviolet rays and heat rays.
(2) The composition for forming a transparent layer as described in (1) above, which contains antimony tin oxide (ATO) powder together with ITO powder and ZnO powder.
(3) The ITO powder and ZnO powder, or the ITO powder, ZnO powder, and ATO powder are dispersed in the presence of a protective agent made of an organic compound having a phosphate group or a sulfonate group (1) or The composition for forming a transparent layer as described in (2) above.
(4) The composition for forming a transparent layer according to any one of (1) to (3) above, wherein the protective agent containing a phosphate group is a phosphoric acid polyester represented by the following general formula [1].

(5) The transparent layer forming composition as described in any one of (1) to (3) above, wherein the protective agent having a sulfonic acid group is a sulfonate compound represented by the following general formula [2].

(6) A dispersion of a mixed powder of ITO powder and ZnO powder, or a dispersion of a mixed powder of ITO powder, ZnO powder and ATO powder, a paint or paste made of the dispersion, or a coating film or film formed thereof The composition for forming a transparent layer according to any one of (1) to (5) above.
(7) A transparent layer formed by the composition described in any one of (1) to (6) above, wherein visible light transmittance (% Tv) is 60% or more, ultraviolet transmittance is 20% or less, visible The ultraviolet ray heat-shielding transparent layer having a ratio of light transmittance (% Tv) to solar radiation transmittance (% Ts) ([% Tv] / [% Ts]) of 1.0 or more.
(8) The ultraviolet ray described in (7) above, having a visible light transmittance (% Tv) of 80% or more, an ultraviolet transmittance of 15% or less, and a heat ray shielding ratio ([% Tv] / [% Ts]) of 1.4 or more. Heat ray shielding transparent layer.
(9) Vehicle window glass, building material window glass, or window glass for medical equipment having the ultraviolet heat ray shielding transparent layer described in (7) or (8) above, transparent part of packaging, transparency of display equipment Part, transparent part of equipment.

The composition of the present invention contains ITO powder and ZnO powder as an ultraviolet and heat ray shielding material, or contains ATO powder together with ITO powder and ZnO powder, and these are dispersed stably and uniformly. The transparent layer formed by the composition of the invention has an excellent shielding effect and weather resistance against heat rays and ultraviolet rays.

In the present invention, since the shielding material powder such as ITO powder or ZnO powder is preferably dispersed in the presence of a protective agent made of an organic compound having a phosphate group or a sulfonate group, the dispersion state stability is improved. Since these shielding material powders are uniformly dispersed, the shielding effect against heat rays and ultraviolet rays is excellent.

Specifically, with the composition of the present invention, the visible light transmittance (% Tv) is 60% or more, the ultraviolet light transmittance is 20% or less, and the ratio of the visible light transmittance (% Tv) to the solar transmittance (% Ts) ( [% Tv] / [% Ts]) 1.0 or more, preferably, visible light transmittance (% Tv) 80% or more, ultraviolet transmittance 15% or less, heat ray shielding ratio ([% Tv] / [% Ts] ) A transparent layer having an ultraviolet heat ray shielding property of 1.4 or more can be formed.

The composition for forming a transparent layer of the present invention can be used in the form of a dispersion, a paint, a paste, and the like, and can easily form a transparent layer such as a coating film or a film. It can be widely applied to glass, window glass for building materials, or window glass for medical equipment, transparent parts of packaging, transparent parts of exhibition facilities, transparent parts of equipment, and the like.

The composition of the present invention is characterized in that it contains dispersed ITO powder and ZnO powder as a shielding material for ultraviolet rays and heat rays, and contains ATO powder together with ITO powder and ZnO powder, and has high shielding properties against heat rays and ultraviolet rays. It is a composition for forming a transparent layer.

  As the ITO powder and the ATO powder, a powder having an average particle size of 0.2 μm or less is suitable, and a powder having a particle size of 0.1 μm or less is preferable. As the ZnO powder, a powder having an average particle size of 0.1 μm or less is appropriate, and a powder having a particle size of 0.04 μm or less is preferable.

The ITO powder is preferably a powder having a Sn weight ratio [Sn / (Sn + In)] of 1 to 20%. When Sn is less than 1%, the heat ray shielding performance tends to be inferior, and since the In component increases, it is expensive. On the other hand, if the Sn weight ratio is more than 20%, the heat ray shielding performance tends to be inferior as described above, which is not preferable. The ATO powder is preferably a powder having a Sb weight ratio [Sn / (Sn + In)] of 1 to 20%. When the weight ratio of Sb is less than 1% or more than 20%, it tends to be inferior in heat ray shielding performance, which is not preferable.

The chromaticity of the Lab color system of the ITO powder and ATO powder is related to the heat ray shielding property, and the ITO powder is preferably b / L = −0.05 or less, and the ATO powder is b / L = −0.1 or less. Is preferred. In the case of ITO powder, when b / L = −0.05, the heat ray shielding performance tends to be inferior. In the case of ATO powder, when b / L = −0.1 or more, the heat ray shielding performance tends to be inferior.

The amount of ZnO in the shielding material powder is suitably 0.1 to 75 wt%, preferably 0.5 to 50 wt%, and more preferably 1.0 to 30.0 wt%. When the amount of ZnO is less than 0.1 wt%, the ultraviolet shielding effect is lowered, and when it is more than 75 wt%, the ITO powder amount or the total amount of ITO powder and ATO powder is relatively reduced, and the heat ray shielding effect is lowered, which is not preferable. .

The ITO powder, ZnO powder, and ATO powder are preferably dispersed in the presence of an organic compound (protective agent) having a phosphoric acid group or a sulfonic acid group (—SO ₃ group, sulfonate group). Either a phosphoric acid group-containing protective agent or a sulfonic acid group-containing protective agent may be used, but it is better to use both in combination. The surface of the shielding material powder (ITO powder, ZnO powder, ATO powder) is protected by the protective agent, the shielding material powder is uniformly dispersed in the liquid, and a stable dispersion and paint can be obtained.

As a protective agent containing a phosphoric acid group, for example, a phosphoric acid polyester represented by the following general formula [1] can be used. The molecular weight is 3000 or less, preferably 1600 or less, and the acid value is 40 or more.

As a protective agent having a sulfonic acid group, for example, a sulfonate compound represented by the following general formula [2] can be used. This preferably has a molecular weight of 3000 or less.

Even a commonly used dispersant that does not contain a phosphoric acid group or a sulfonic acid group cannot obtain a uniform dispersion state even when the shielding material powder is added to the solvent in the presence of these. Even when a protective agent having a phosphoric acid group or a sulfonic acid group is used, a uniform dispersion state cannot be obtained if a dispersing agent that inhibits the action is used in combination. For example, a protective agent having a phosphoric acid group or a sulfonic acid group is generally an acidic compound, and when an alkaline dispersant is used in combination with this, a dispersion having excellent stability cannot be obtained.

By dispersing the shielding material powder in a solvent in the presence of a protective agent containing a phosphoric acid group or a sulfonic acid group, the shielding material powder is uniformly dispersed, and a stable dispersion and paint can be obtained. The transparent film formed by this highly dispersible paint has excellent shielding properties against heat rays and ultraviolet rays and weather resistance, and has transparency superior to a coating film containing ATO powder alone. A coating film having a haze lower than that of the coating film contained alone can be obtained. Furthermore, it has excellent weather resistance.

According to the composition of the present invention, the visible light transmittance (% Tv) is 60% or more, the ultraviolet light transmittance is 20% or less, and the ratio of the visible light transmittance (% Tv) to the solar transmittance (% Ts) ([% Tv ] / [% Ts]) A transparent layer having an ultraviolet shielding property and a heat ray shielding property of 1.0 or more can be formed. The heat ray shielding ratio ([% Tv] / [% Ts]) represents the heat ray shielding performance, and the higher the ratio, the higher the heat ray shielding effect.

In general, a transparent film containing almost the same amount of ITO powder and ATO powder alone, in the case of an ITO powder-containing film, the visible light transmittance (% Tv) is around 90%, and the solar transmittance (% Ts) is In the case of an ATO powder-containing film, the visible light transmittance (% Tv) is around 80% and the solar radiation transmittance (% Ts) is around 65%. Further, the ultraviolet transmittance is about 40%, and the ultraviolet shielding effect is low. On the other hand, the transparent film containing ZnO powder having the same content as the above has a low ultraviolet transmittance of about 1%, but the visible light transmittance (% Tv) is about 80%, and the transparency is low. The transmittance (% Ts) is about 85% and the heat ray shielding property is low.

On the other hand, according to the composition of the present invention, the visible light transmittance (% Tv) is 60% or more, preferably 80% or more, more preferably 90% or more, and the ultraviolet transmittance is 20% or less, preferably 15%. In the following, a transparent layer (transparent film) having a heat ray shielding ratio ([% Tv] / [% Ts]) of 1.0 or more, preferably 1.4 or more can be formed, and has high transparency and ultraviolet shielding properties. In addition, a transparent layer having excellent heat ray shielding properties can be formed.

The composition of the present invention can be used in various forms such as a dispersion, a paint, a paste, a coating film formed by these, or a film. A solvent such as a dispersion is not limited, and alcohols, ketones, water, aromatic hydrocarbons, and the like can be used.

Ultraviolet heat ray shielding film formed by the composition of the present invention is used for window glass of various vehicles such as automobiles, window glass of building materials, window glass of various devices such as medical instruments, transparent part of packaging, transparent part of exhibition equipment, equipment. It can be widely applied to the transparent part of.

Examples of the present invention are shown below together with comparative examples.
[Shielding powder, preparation method, transmittance]
(1) As shielding material powder, ITO powder (average particle size 35 nm, b / L-0.2), ATO powder (average particle size 30 nm, b / L-0.2), ZnO powder (average particle size 0. 02 μm) was used.
(2) As a dispersion protective agent, phosphoric acid polyester, sodium dialkylsulfosuccinate, a sulfo group-containing titanium coupling agent, and an amine group-containing compound were used. As shown in Table 1, the dispersion protective agent was used for each shielding material powder, and 10 wt% was added to the shielding material powder.
(3) Each shielding material powder was dispersed in toluene in the presence of a dispersion protective agent to prepare a dispersion, and each shielding material dispersion was mixed. Table 1 shows the amount ratio of the shielding material powder and the type of the dispersion protective agent.
(4) Toluene, butanol, and a photopolymerization initiator are added to a UV curable acrylic resin, and the mixture is stirred and mixed. The dispersion is added to the mixture while stirring, and the quantity ratio of resin to powder (resin / powder) is 35 / 65 paints were formed.
(5) The paint is applied to a PET film (thickness 75 μm) with a converter, dried at room temperature for 1 minute, dried by heating at 70 ° C. for 30 seconds, and further cured by UV irradiation to obtain a film thickness of 3 to 5 μm. The coating film was formed.
(6) The visible light transmittance (% Tv) and solar radiation transmittance (% Ts) of this coating film were measured. Visible light transmittance (% Tv) and solar radiation transmittance (% Ts) were measured using a spectrophotometer (Hitachi U-4000) with [% Tv] [% Ts] of the PET film as the baseline. Further, the dispersion and the coating liquid were stored at 40 ° C. for 30 days, and the stability was examined. Furthermore, the weather resistance of the coating film was measured based on the standard (JIS K 7350). The results are shown in Table 1.

[Examples 1-8]
For Examples 1 to 8 of the present invention, Table 1 shows the results of the preparation conditions of the dispersion, the stability of the dispersion and paint, and the transmittance of the coating film.

[Comparative Examples 1-3]
Comparative Example 1 using ITO powder alone, Comparative Example 2 using ATO powder alone, and Comparative Example 3 with different types of protective agents, preparation conditions of the dispersion, stability of the dispersion and paint, The transmittance results are shown in Table 2.

The coating films of Examples 1 to 8 have high transparency, are excellent in ultraviolet shielding properties and heat ray shielding properties, and have good weather resistance. On the other hand, Comparative Example 3 in which the protective agent is not appropriate has poor stability of the dispersion and paint, and cannot form a coating film.

Claims (9)

A composition for forming a transparent layer, characterized by containing indium tin oxide (ITO) powder and zinc oxide (ZnO) powder as a shielding material for ultraviolet rays and heat rays.
The composition for forming a transparent layer according to claim 1, comprising antimony tin oxide (ATO) powder together with ITO powder and ZnO powder.
The ITO powder and ZnO powder, or the ITO powder, ZnO powder, and ATO powder are dispersed in the presence of a protective agent made of an organic compound having a phosphate group or a sulfonate group. The composition for forming a transparent layer to be described.
The composition for forming a transparent layer according to any one of claims 1 to 3, wherein the protective agent containing a phosphate group is a phosphoric acid polyester represented by the following general formula [1].

The composition for forming a transparent layer according to any one of claims 1 to 3, wherein the protective agent having a sulfonic acid group is a sulfonate compound represented by the following general formula [2].

A dispersion of a mixed powder of ITO powder and ZnO powder, or a dispersion of a mixed powder of ITO powder, ZnO powder and ATO powder, a paint or paste made of the dispersion, or a coating or film formed by these. The composition for transparent layer formation in any one of Claims 1-5.
A transparent layer formed by the composition according to claim 1, wherein the visible light transmittance (% Tv) is 60% or more, the ultraviolet light transmittance is 20% or less, and the visible light transmittance (% The ultraviolet ray heat-shielding transparent layer having a ratio of Tv) to solar radiation transmittance (% Ts) ([% Tv] / [% Ts]) of 1.0 or more.
The ultraviolet ray heat shielding transparency according to claim 7, wherein the visible ray transmittance (% Tv) is 80% or more, the ultraviolet ray transmittance is 15% or less, and the heat ray shielding ratio ([% Tv] / [% Ts]) is 1.4 or more. layer.
The window glass for vehicles, the window glass for building materials, or the window glass for medical equipment having the ultraviolet heat ray shielding transparent layer according to claim 7 or claim 8, the transparent part of the package, the transparent part of the exhibition facility, the transparency of the equipment Department.