JP6098831B2 - Heat ray shielding film, heat ray shielding laminated transparent base material, automobile and building - Google Patents

Description

  The present invention relates to a heat ray shielding film that exhibits excellent heat shielding properties, color tone, and weather resistance while containing a thermoplastic resin as a main component, a heat ray shielding laminated transparent substrate using the heat ray shielding film, and the heat ray shielding laminated transparent base. The present invention relates to an automobile in which a material is mounted as a window material, and a building in which the heat ray shielding laminated transparent base material is used as a window material.

  As safety glass used in window materials for automobiles or buildings, an intermediate layer containing a thermoplastic resin such as polyvinyl acetal resin or ethylene / vinyl acetate polymer is sandwiched between a plurality of facing glass plates (for example, two). The transparent base material which comprised the laminated glass is used. Furthermore, a transparent base material has been proposed for the purpose of reducing the cooling load and the heat of human heat by blocking incident solar energy by providing the intermediate layer with a heat ray shielding function.

  For example, Patent Document 1 discloses a laminated glass in which a soft resin layer containing a heat ray shielding metal oxide made of tin oxide or indium oxide having a fine particle diameter of 0.1 μm or less is sandwiched between two opposing plate glasses. Is disclosed.

  Patent Document 2 discloses that Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Mn, at least between two opposing glass plates. Metals such as Ta, W, V, and Mo, oxides of the metals, nitrides of the metals, sulfides of the metals, Sb and F dopants to the metals, and intermediate layers in which these composites are dispersed A laminated glass sandwiching a glass is disclosed.

In Patent Document 3, fine particles made of TiO ₂ , ZrO ₂ , SnO ₂ , and In ₂ O ₃ and a glass component made of organic silicon or an organic silicon compound are sandwiched between opposing transparent plate-like members. An automotive window glass is disclosed.

  Furthermore, in Patent Document 4, an intermediate layer composed of three layers is provided between at least two opposing transparent glass plates, and Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, In, Ni, Ag, Cu, Pt, Mn, Ta, W, V, Mo metal, metal oxide, metal nitride, metal sulfide, metal A laminated glass is disclosed in which a dope of Sb or F or a composite of these is dispersed and an intermediate layer of the first layer and the third layer is used as a resin layer.

  However, each of the conventional laminated glasses disclosed in Patent Documents 1 to 4 has a problem that the heat ray shielding function is not sufficient when high visible light transmittance is required.

  Furthermore, as a method for improving the heat ray shielding function of laminated glass, Patent Document 5 discloses that a metal oxide semiconductor, a near infrared absorber, and an ultraviolet absorber are mixed with a transparent synthetic resin and molded on a film. An ultraviolet and infrared shield is disclosed.

  On the other hand, the applicant forms an intermediate layer having a heat ray shielding function between two sheet glasses, and this intermediate layer is composed of hexaboride fine particles alone, or hexaboride fine particles and ITO fine particles and / or ATO fine particles. And a heat ray-shielding laminated glass comprising a heat ray shielding film containing vinyl resin, or a heat ray containing the fine particles formed on the surface of the intermediate layer facing the inside of at least one plate glass Patent Document 6 discloses a heat ray shielding laminated glass composed of a shielding film and a heat ray shielding film containing a vinyl resin interposed between the two plate glasses.

  As described in Patent Document 6, the optical properties of laminated glass for heat ray shielding in which hexaboride fine particles alone, or hexaboride fine particles and ITO fine particles and / or ATO fine particles are applied, has a transmittance in the visible light region. In addition, it exhibits strong absorption in the near infrared region and has minimum transmittance. As a result, the heat-shielding laminated glass is improved until the solar transmittance when the visible light transmittance is 70% or more is in the range of 50% compared to the conventional laminated glasses described in Patent Documents 1 to 4. It was done.

  In addition, the present inventors have disclosed, as Patent Document 7, a heat ray shielding laminated glass using a heat ray shielding film in which a composite tungsten compound is contained in a polyvinyl acetal resin as an intermediate layer.

  As described in Patent Document 7, the laminated glass for heat ray shielding is solar radiation transmission when the visible light transmittance is 70% or more as compared with the conventional laminated glass described in Patent Documents 1 to 4 and Patent Document 6. It was improved until the rate was around 35%.

  In addition, the inventors of the present invention have selected a selective wavelength absorbing material having a transmission profile in which the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 450 nm is 40% or less together with the composite tungsten oxide. Patent Document 8 discloses a heat ray shielding laminated transparent base material that is contained in a polyvinyl butyral resin to form a heat ray shielding film and is sandwiched between two transparent base materials.

  As described in Patent Document 8, the heat-shielding laminated glass has a solar transmittance of 32.5% or less when the visible light transmittance is 70% or more as compared with the conventional laminated glass described in Patent Document 7. Until it was improved.

JP-A-8-217500 JP-A-8-259279 Japanese Patent Laid-Open No. 4-160041 Japanese Patent Laid-Open No. 10-297945 JP 2004-37768 A JP 2001-89202 A WO2005 / 087680 WO2013 / 08080859 gazette

However, as a result of further studies by the present inventors, the following problems have been found. That is, in the laminated glass which concerns on the prior art described in patent documents 1-5, as above-mentioned, all are that the heat ray shielding function when a high visible light transmittance is calculated | required is not enough.
Furthermore, in the market, the heat shield function will be further improved in terms of improving comfort in automobiles and buildings, improving fuel efficiency by reducing automobile air-conditioner loads, and saving energy by reducing air-conditioner loads in buildings. The demand is high. From this viewpoint, the laminated glass for heat ray shielding described in Patent Documents 6 and 7 still had room for improvement.

  Although the laminated glass for heat ray shielding described in Patent Document 8 can solve the above problems, the absorption of visible light of the selective wavelength absorbing material changes the color of the heat ray shielding film, and has a strong yellowish color tone. There was a problem.

  The present invention has been made paying attention to the above problems. The problem to be solved is a heat ray shielding film that exhibits excellent heat shielding properties, color tone, and weather resistance while using a known thermoplastic resin such as polyvinyl acetal resin as a main component, and a heat ray using the heat ray shielding film. It is to provide a shielded transparent substrate, an automobile in which the heat ray shielded transparent substrate is mounted as a window material, and a building in which the heat ray shielded transparent substrate is used as a window material.

In order to solve the above-mentioned problems, the present inventors first conducted intensive research on a method for improving heat ray shielding characteristics while maintaining high visible light transmittance.
The present inventors paid attention to the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106. Specifically, the wavelength distribution of the weight coefficient used for calculating the visible light transmittance and the solar radiation energy in the short wavelength region were studied in detail. And the knowledge that it was possible to reduce only the solar radiation transmittance | permeability was maintained, keeping visible light transmittance | permeability high by shielding the short wavelength area | region of visible light suitably.
Based on this knowledge, the present inventors have selected wavelength absorption capable of efficiently absorbing light in a region where the composite tungsten oxide does not have sufficient absorption capability in addition to the composite tungsten oxide having strong near-infrared absorption capability. The inventors have conceived that the above object can be achieved by coexisting materials.

  Specifically, in order to prevent the visible light transmittance from being lowered as much as possible, ultraviolet light having a wavelength of 300 nm to 380 nm is used in spite of the common sense of using a conventional ultraviolet absorber that does not cut the visible light region as much as possible. In addition, a selective wavelength absorbing material that absorbs visible light from 380 nm to 480 nm strongly but does not absorb near the wavelength of 550 nm, which is a region that greatly contributes to the calculation of visible light transmittance, coexists with the composite tungsten oxide fine particles. I came up with the structure of making it happen.

  However, it was expected that the color of the heat ray shielding film would be changed by coexisting with a selective wavelength absorbing material that absorbs visible light. Therefore, the present inventors next applied the tint value calculated based on JIS Z 8701 from the spectral transmittance measurement of the heat ray shielding film, and the yellowness of the plastic calculated based on JIS K 7373 from the tint value (the present invention). In some cases, “YI” may be described in FIG. As a result, as a new concept, there is no absorption in the vicinity of the wavelength 550 nm, which is a region that greatly contributes to the calculation of the visible light transmittance, and there is a large influence on the YI of the heat ray shielding film and the heat ray shielding laminated transparent base material. And a selective wavelength absorbing material having a large absorption in the vicinity of a wavelength of 420 nm is coexisted with the composite tungsten oxide fine particles.

A selective wavelength absorbing material having no absorption near the wavelength of 550 nm, no absorption near the wavelength of 460 nm, and having a large absorption near the wavelength of 420 nm is combined with the composite tungsten oxide. The solar radiation transmittance was able to be lowered while maintaining the visible light transmittance, compared with the case of not coexisting. That is, the present inventors have completed the present invention by discovering that the heat ray shielding characteristics can be improved and the color tone capable of normally identifying the color of the transmitted image can be maintained.
In particular, when the selective wavelength absorbing material is an indole compound and / or a benzotriazole compound, and more preferably an indole compound, a benzotriazole compound and / or a benzotriazole derivative compound having a specific chemical formula, At the same time, it was found that it can be remarkably improved.
In addition, when the selective wavelength absorbing material is a benzotriazole compound, and more preferably a benzotriazole compound or a benzotriazole derivative compound having a specific chemical formula, a change in color tone or visibility when a heat ray shielding film is used for a long period of time. At the same time, it was also found that the light transmittance was small and the weather resistance was very good.

〔化学式２〕

〔化学式３〕

〔化学式４〕

〔化学式５〕

第２の発明は、
一般式Ｍ _ｙ ＷＯ _Ｚ （但し、Ｍは、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｃａ、Ｓｒ、Ｆｅ、Ｓｎ、Ａｌ、Ｃｕから選択される１種類以上の元素、０．１≦ｙ≦０．５、２．２≦ｚ≦３．０）で示され、かつ六方晶の結晶構造を持つ複合タングステン酸化物微粒子と、選択波長吸収材料と、熱可塑性樹脂とを含有する熱線遮蔽膜であって、
前記選択波長吸収材料は、波長５５０ｎｍの光の透過率が９０％以上であり、かつ波長４６０ｎｍの光の透過率が９０％以上であるときの波長４２０ｎｍの光の透過率が４０％以下の透過プロファイルを有し、
前記熱線遮蔽膜中における前記選択波長吸収材料の含有量が、０．０１質量％以上２．０質量％以下であることを特徴とする熱線遮蔽膜であり、
前記選択波長吸収材料が、〔化学式６〕〜〔化学式１０〕のいずれかで示されるベンゾトリアゾール化合物から選択される１種以上であることを特徴とする熱線遮蔽膜である。
〔化学式６〕

〔化学式７〕

〔化学式８〕

〔化学式９〕

〔化学式１０〕

第３の発明は、
一般式Ｍ _ｙ ＷＯ _Ｚ （但し、Ｍは、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｃａ、Ｓｒ、Ｆｅ、Ｓｎ、Ａｌ、Ｃｕから選択される１種類以上の元素、０．１≦ｙ≦０．５、２．２≦ｚ≦３．０）で示され、かつ六方晶の結晶構造を持つ複合タングステン酸化物微粒子と、選択波長吸収材料と、熱可塑性樹脂とを含有する熱線遮蔽膜であって、
前記選択波長吸収材料は、波長５５０ｎｍの光の透過率が９０％以上であり、かつ波長４６０ｎｍの光の透過率が９０％以上であるときの波長４２０ｎｍの光の透過率が４０％以下の透過プロファイルを有し、
前記熱線遮蔽膜中における前記選択波長吸収材料の含有量が、０．０１質量％以上２．０質量％以下であることを特徴とする熱線遮蔽膜であり、
前記選択波長吸収材料が、〔化学式１１〕で示されるインドール化合物であり、
前記〔化学式１１〕で示されるインドール化合物中におけるＲは、炭素数が１〜１０のアルキル基または炭素数が７〜１０のアラルキル基であることを特徴とする熱線遮蔽膜である。
〔化学式１１〕

第４の発明は、
一般式Ｍ _ｙ ＷＯ _Ｚ （但し、Ｍは、Ｃｓ、Ｒｂ、Ｋ、Ｔｌ、Ｉｎ、Ｂａ、Ｌｉ、Ｃａ、Ｓｒ、Ｆｅ、Ｓｎ、Ａｌ、Ｃｕから選択される１種類以上の元素、０．１≦ｙ≦０．５、２．２≦ｚ≦３．０）で示され、かつ六方晶の結晶構造を持つ複合タングステン酸化物微粒子と、選択波長吸収材料と、熱可塑性樹脂とを含有する熱線遮蔽膜であって、
前記選択波長吸収材料は、波長５５０ｎｍの光の透過率が９０％以上であり、かつ波長４６０ｎｍの光の透過率が９０％以上であるときの波長４２０ｎｍの光の透過率が４０％以下の透過プロファイルを有し、
前記熱線遮蔽膜中における前記選択波長吸収材料の含有量が、０．０１質量％以上２．０質量％以下であることを特徴とする熱線遮蔽膜であり、
前記選択波長吸収材料が〔化学式１２〕で示されるインドール化合物であることを特徴とする熱線遮蔽膜である。
〔化学式１２〕

第５の発明は、
前記熱可塑性樹脂が、ポリビニルアセタール樹脂、塩化ビニル樹脂、エチレン・酢酸ビニル共重合体という樹脂群から選択される１種の樹脂、
または、前記樹脂群から選択される２種以上の樹脂の混合物、
または、前記樹脂群から選択される２種以上の樹脂の共重合体、
のいずれかであることを特徴とする熱線遮蔽膜である。
第６の発明は、
前記熱可塑性樹脂がポリビニルブチラール樹脂であり、さらに可塑剤を含有することを特徴とする熱線遮蔽膜である。
第７の発明は、
前記複合タングステン酸化物微粒子が、Ｃｓ_０．３３ＷＯ_３、Ｒｂ_０．３３ＷＯ_３から選択される少なくとも１種であることを特徴とする熱線遮蔽膜である。
第８の発明は、
前記複合タングステン酸化物微粒子が、分散粒子径４０ｎｍ以下の微粒子であることを特徴とする熱線遮蔽膜である。
第９の発明は、
前記熱線遮蔽膜が、さらに紫外線吸収剤を含有することを特徴とする熱線遮蔽膜である。
第１０の発明は、
前記紫外線吸収剤が、ベンゾトリアゾール化合物、ベンゾフェノン化合物から選択される１種以上であることを特徴とする熱線遮蔽膜である。
第１１の発明は、
前記熱線遮蔽膜中における前記紫外線吸収剤の含有率が、０．０２質量％以上５．０質量％以下であることを特徴とする熱線遮蔽膜である。
第１２の発明は、
前記熱線遮蔽膜が、さらに多価金属塩を含有することを特徴とする熱線遮蔽膜である。
第１３の発明は、
前記多価金属塩がビス（２−エチル酪酸）マグネシウムであることを特徴とする熱線遮蔽膜である。
第１４の発明は、
複数枚の透明基材間に、本発明に係る熱線遮蔽膜が存在していることを特徴とする熱線遮蔽合わせ透明基材である。
第１５の発明は、
ＪＩＳ Ｋ ７３７３で算出される黄色度（ＹＩ）が、−２０．０以上１０．０以下であることを特徴とする熱線遮蔽合わせ透明基材である。
第１６の発明は、
ＪＩＳ Ｋ ７３７３で算出される黄色度（ＹＩ）が、−２０．０以上５．０以下であることを特徴とする熱線遮蔽合わせ透明基材である。
第１７の発明は、
前記透明基材の内、少なくとも１枚がガラスであることを特徴とする熱線遮蔽合わせ透明基材である。
第１８の発明は、
本発明に係る熱線遮蔽合わせ透明基材が、窓材として搭載されていることを特徴とする自動車である。
第１９の発明は、
本発明に係る熱線遮蔽合わせ透明基材が、窓材として使用されていることを特徴とする建造物である。 That is, the first invention for solving the above-described problem is
Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
The heat ray shielding film is characterized in that the content of the selective wavelength absorbing material in the heat ray shielding film is 0.01% by mass or more and 2.0% by mass or less,
The selective wavelength absorbing material is a benzotriazole compound represented by [Chemical Formula 1],
R1 in the benzotriazole compound represented by [Chemical Formula 1] is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an amino group, a linear or branched mono-substituted amino group, a linear or branched chain Disubstituted amino group, nitro group, carboxyl group, alkylcarbonyloxyalkyl group having 1 to 8 carbon atoms each, alkyloxycarbonylalkyl group having 2 to 10 carbon atoms in total, alkyl group, acyl group, acyl group A group selected from a group represented by a chemical formula 2; a group represented by a chemical formula 3; a group represented by a chemical formula 4; a group represented by a chemical formula 5; ,
R2 in the groups represented by the above [Chemical Formula 2] to [Chemical Formula 5] is an alkylene group having 1 to 8 carbon atoms,
R3 in the groups represented by the above [Chemical Formula 2] to [Chemical Formula 5] is a hydrogen atom or a methyl group,
R4 in the group represented by [Chemical Formula 4] is an alkylene group having 1 to 8 carbon atoms, which is a heat ray shielding film.
[Chemical Formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

The second invention is
Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
The heat ray shielding film is characterized in that the content of the selective wavelength absorbing material in the heat ray shielding film is 0.01% by mass or more and 2.0% by mass or less,
In the heat ray shielding film, the selective wavelength absorbing material is at least one selected from benzotriazole compounds represented by any one of [Chemical Formula 6] to [Chemical Formula 10].
[Chemical formula 6]

[Chemical formula 7]

[Chemical Formula 8]

[Chemical formula 9]

[Chemical formula 10]

The third invention is
Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
The heat ray shielding film is characterized in that the content of the selective wavelength absorbing material in the heat ray shielding film is 0.01% by mass or more and 2.0% by mass or less,
The selective wavelength absorbing material is an indole compound represented by [Chemical Formula 11],
R in the indole compound represented by [Chemical Formula 11] is a heat ray shielding film characterized by being an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
[Chemical formula 11]

The fourth invention is :
Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
The heat ray shielding film is characterized in that the content of the selective wavelength absorbing material in the heat ray shielding film is 0.01% by mass or more and 2.0% by mass or less,
In the heat ray shielding film, the selective wavelength absorbing material is an indole compound represented by [Chemical Formula 12].
[Chemical formula 12]

The fifth invention is :
The thermoplastic resin is one resin selected from a resin group of polyvinyl acetal resin, vinyl chloride resin, and ethylene / vinyl acetate copolymer;
Or a mixture of two or more resins selected from the resin group,
Or a copolymer of two or more resins selected from the resin group,
The heat ray shielding film is any of the above.
The sixth invention is :
The thermoplastic resin is a polyvinyl butyral resin, and further contains a plasticizer.
The seventh invention
The composite tungsten oxide fine particle is at least one selected from Cs _0.33 WO ₃ and Rb _0.33 WO ₃ .
The eighth invention
The composite tungsten oxide fine particles are fine particles having a dispersed particle diameter of 40 nm or less.
The ninth invention
The heat ray shielding film further comprises an ultraviolet absorber, and is a heat ray shielding film.
The tenth invention is
In the heat ray shielding film, the ultraviolet absorber is at least one selected from a benzotriazole compound and a benzophenone compound.
The eleventh invention is
The heat ray shielding film is characterized in that the content of the ultraviolet absorber in the heat ray shielding film is 0.02 mass% or more and 5.0 mass% or less.
The twelfth invention is
The heat ray shielding film further contains a polyvalent metal salt.
The thirteenth invention is
The heat ray shielding film, wherein the polyvalent metal salt is bis (2-ethylbutyrate) magnesium.
The fourteenth invention is
A heat ray shielding laminated transparent substrate, wherein the heat ray shielding film according to the present invention is present between a plurality of transparent substrates.
The fifteenth invention
A heat ray shielding laminated transparent base material having a yellowness degree (YI) calculated by JIS K 7373 of −20.0 or more and 10.0 or less.
The sixteenth invention is
It is a heat ray shielding laminated transparent base material characterized by having a yellowness degree (YI) calculated by JIS K 7373 of −20.0 or more and 5.0 or less.
The seventeenth invention
Among the transparent base materials, at least one of the transparent base materials is a heat ray shielding laminated transparent base material.
The eighteenth invention
The heat ray shielding laminated transparent base material which concerns on this invention is mounted as a window material, It is a motor vehicle characterized by the above-mentioned.
The nineteenth invention
The heat ray shielding laminated transparent base material according to the present invention is used as a window material.

  According to the present invention, by using a composite tungsten oxide fine particle and an appropriate selective wavelength absorbing material in combination with a heat ray shielding film such as a polyvinyl acetal resin as a main component, excellent optical characteristics and high weather resistance can be obtained. And a heat ray shielding film having a natural color tone could be obtained. And the heat ray shielding laminated transparent base material which exhibits the outstanding optical characteristic, high weather resistance, and the outstanding mechanical characteristic was able to be obtained by using the said heat ray shielding film. Furthermore, by mounting the heat ray shielding laminated transparent base material on a car as a window material, it has become possible to suppress a rise in the temperature inside the car in summer. Moreover, the said heat ray shielding matching transparent base material was used for the opening part of a building as a window material, and the building which can suppress the temperature rise in the building in summer was implement | achieved.

Hereinafter, embodiments of the present invention will be described in detail.
The heat ray shielding film according to the present invention contains a heat ray shielding component (composite tungsten oxide fine particles) and a selective wavelength absorbing material in a thermoplastic resin, and further includes a dispersant, an ultraviolet absorber, an optional plasticizer, and an optional material. Other additives are contained.

  Hereinafter, [1] components constituting the heat ray shielding film, [2] heat ray shielding film, and [3] heat ray shielding laminated transparent base material using the heat ray shielding film will be described in detail.

[1] Components constituting the heat ray shielding film
As described above, the heat ray shielding film according to the present invention contains a heat ray shielding component (composite tungsten oxide fine particles) and a selective wavelength absorbing material in a thermoplastic resin, and further includes a dispersant, an ultraviolet absorber, and, if desired. Other additives are contained. Therefore, (1) heat ray shielding component (composite tungsten oxide fine particles), (2) dispersant, (3) selective wavelength absorbing material, (4) ultraviolet absorber, (5) thermoplastic resin, (6) plasticizer, (7) Adhesive strength modifier, (8) Infrared absorbing organic compound, (9) Other additives will be described in detail in this order.

(1) Heat ray shielding component (composite tungsten oxide fine particles)
The composite tungsten oxide fine particles have a general formula MyWO _Z (where M is one or more selected from Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn, Al, Cu). Element, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and having a hexagonal crystal structure is preferable.

In the composite tungsten oxide fine particles, examples of preferable composite tungsten oxide fine particles include Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . However, if the values of y and z are within the above ranges, useful heat ray shielding characteristics can be obtained. The addition amount of the additive element M is preferably 0.1 or more and 0.5 or less, and more preferably around 0.33. This is because the value theoretically calculated from the hexagonal crystal structure is 0.33, and preferable optical characteristics can be obtained with the addition amount before and after this. Moreover, about the range of z, 2.2 <= z <= 3.0 is preferable. This is because the same mechanism works as the above-described tungsten oxide material represented by WO _x in the composite tungsten oxide material represented by MyWO _Z , and the above-described element is also obtained when z ≦ 3.0. This is because free electrons are supplied by adding M. However, from the viewpoint of optical characteristics, 2.45 ≦ z ≦ 3.00 is more preferable.

  The particle diameter of the composite tungsten oxide fine particles can be appropriately selected depending on the purpose of use of the heat ray shielding film. For example, when the heat ray shielding film is used for applications requiring transparency, the composite tungsten oxide fine particles preferably have a dispersed particle diameter of 40 nm or less. If the composite tungsten oxide fine particles have a dispersed particle diameter of 40 nm or less, the light is not completely blocked by scattering, the visibility in the visible light region is maintained, and at the same time, the transparency is efficiently maintained. Because it can.

When the heat ray shielding film according to the present invention is applied to, for example, an automobile roof or a side window and particularly importance is attached to transparency in the visible light region, it is preferable to further consider the reduction of scattering by the composite tungsten oxide fine particles. In consideration of further scattering reduction, the dispersed particle diameter of the composite tungsten oxide fine particles should be 30 nm or less, preferably 25 nm or less.
This is because if the composite tungsten oxide fine particles have a small dispersed particle diameter, light scattering in the visible light region having a wavelength of 400 nm to 780 nm due to geometric scattering or Mie scattering is reduced. By reducing the scattering of the light having the wavelength, it is possible to avoid a situation in which the heat ray shielding film has an appearance like a frosted glass when strong light is irradiated and the clear transparency is lost.
This is because when the composite tungsten oxide fine particles have a dispersed particle diameter of 40 nm or less, the above-described geometrical scattering or Mie scattering is reduced and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the transparency is improved as the dispersed particle diameter is reduced. Furthermore, it is preferable that the dispersed tungsten oxide fine particles have a dispersed particle diameter of 25 nm or less because the scattered light is extremely reduced.

  As described above, from the viewpoint of avoiding light scattering, it is preferable that the dispersed tungsten oxide fine particles have a small dispersed particle diameter. On the other hand, if the dispersed particle diameter of the composite tungsten oxide fine particles is 1 nm or more, industrial production is easy.

The amount of the composite tungsten oxide fine particles contained in the heat-ray shielding film, per unit area 0.05g ^{/ m 2} ~5.0g ^/ m 2 is desirable.

(2) Dispersant The dispersant according to the present invention is used for uniformly dispersing the above-described composite tungsten oxide fine particles according to the present invention in a thermoplastic resin described later.
The dispersant according to the present invention has a thermal decomposition temperature of 250 ° C. or higher measured using a differential thermal / thermogravimetric simultaneous measurement apparatus (hereinafter sometimes referred to as TG-DTA), urethane, acrylic, A dispersant having a styrene main chain is preferred. Here, the thermal decomposition temperature is a temperature at which weight reduction due to thermal decomposition of the dispersant begins in the measurement based on JIS K 7120 using TG-DTA.
This is because when the thermal decomposition temperature is 250 ° C. or higher, the dispersant is hardly decomposed during kneading with the thermoplastic resin. As a result, the browning of the heat ray shielding film due to the decomposition of the dispersant, the reduction of the visible light transmittance, and the situation where the original optical characteristics cannot be obtained can be avoided.

  In addition, the dispersant is preferably a dispersant having an amine-containing group, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group. These functional groups are adsorbed on the surface of the composite tungsten oxide fine particles, prevent aggregation of the composite tungsten oxide fine particles, and have an effect of uniformly dispersing the fine particles even in the heat ray shielding film. Specific examples include acrylic-styrene copolymer dispersants having a carboxyl group as a functional group, and acrylic dispersants having an amine-containing group as a functional group. The dispersant having a functional group containing an amine is preferably one having a molecular weight Mw of 2,000 to 200,000 and an amine value of 5 to 100 mgKOH / g. Moreover, in the dispersing agent which has a carboxyl group, the thing of molecular weight Mw2000-200000 and an acid value of 1-50 mgKOH / g is preferable.

  The addition amount of the dispersant is desirably in the range of 10 parts by weight to 1000 parts by weight, and more preferably in the range of 30 parts by weight to 400 parts by weight with respect to 100 parts by weight of the composite tungsten oxide fine particles. This is because if the added amount of the dispersant is in the above range, the composite tungsten oxide fine particles are uniformly dispersed in the thermoplastic resin, and the physical properties of the obtained heat ray shielding film are not adversely affected.

(3) Selected Wavelength Absorbing Material The selected wavelength absorbing material according to the present invention is a material that selectively and strongly absorbs only light in a certain wavelength region.
As described above, the present inventors have considered the wavelength distribution of the weight coefficient used in the visible light transmittance calculation described in JIS R 3106, and further described in JIS Z 8701 and JIS K 7373. The YI calculation method for plastics was examined. As a result of the examination, the light near the wavelength of 420 nm that cannot be sufficiently shielded by the composite tungsten oxide fine particles alone is strongly absorbed, and near the wavelength of 550 nm, which is a wavelength region that greatly contributes to the visible light transmittance calculation. The inventors have conceived a configuration in which a selective wavelength absorbing material that does not absorb light and does not absorb light having a wavelength of about 460 nm that greatly affects YI coexists with the composite tungsten oxide fine particles. The composite tungsten oxide fine particles can be obtained by using a configuration in which a selective wavelength absorbing material that strongly absorbs light in the vicinity of the wavelength of 420 nm and has no absorption near the wavelengths of 460 nm and 550 nm coexists with the composite tungsten oxide fine particles. Compared with the case of using alone, the lower solar transmittance could be obtained without increasing the YI of the heat-shielding transparent base material.

Further, for example, when a heat ray shielding laminated transparent base material is used as a member that requires high visibility, such as an automobile roof or a side window, strong light such as direct sunlight, headlamps, etc. When the base material is irradiated, fine particles such as composite tungsten oxide fine particles are strongly scattered in the short wavelength region of visible light, and the phenomenon that the heat ray shielding film in the heat ray shielding laminated transparent substrate becomes cloudy blue and white is a problem. There was a case.
Here, the inventors of the present invention have the phenomenon that the above-mentioned selective wavelength absorbing material absorbs the scattered light in the short wavelength region of visible light generated by being scattered by fine particles such as composite tungsten oxide fine particles, thereby causing the phenomenon of cloudiness to be pale. It was conceived that the effect of suppressing the generation and enhancing the transparency of the heat-shielding transparent substrate according to the present invention can also be exhibited.

As the optical characteristics of the selective wavelength absorbing material according to the present invention, the selected wavelength absorbing material itself excluding the absorption of the medium and the substrate has a light transmittance of 90% or more at a wavelength of 550 nm and a light transmittance of a wavelength of 460 nm. Is 90% or more, the transmittance of light having a wavelength of 420 nm is preferably 40% or less. Furthermore, when the transmittance of light having a wavelength of 550 nm is 90% or more and the transmittance of light having a wavelength of 460 nm is 90% or more, the transmittance of light having a wavelength of 420 nm is more preferably 15% or less.
This is because, as the selective wavelength absorbing material itself, when the transmittance of light at a wavelength of 550 nm is 90% or more and the transmittance of light at a wavelength of 460 nm is 90% or more, the transmittance of light at a wavelength of 420 nm is 40% or less. When a material having a profile is selected and the selected wavelength-absorbing material and the composite tungsten oxide fine particles are used in combination, the visible light transmittance does not decrease, the YI of the base material does not significantly increase, and the wavelength This is because sufficient absorption of light near 420 nm can be obtained. As a result, compared to the case where the composite tungsten oxide fine particles are used alone, the color tone is not greatly changed and the solar radiation transmittance is lowered, so that the heat shielding characteristics are improved.

  Specific examples of the selective wavelength absorbing material used in the present invention include benzotriazole compounds, benzotriazole derivative compounds, benzophenone compounds, hydroxyphenylalanine compounds, indole compounds, and azomethine compounds. In particular, a benzotriazole compound, a benzotriazole derivative compound, or an indole compound is preferable. This is because benzotriazole compounds, benzotriazole derivative compounds or indole compounds have sharp absorption peaks compared to UV absorbers such as benzophenone compounds and hydroxyphenyltriazine compounds having similar absorption characteristics, and therefore absorb light at a wavelength of around 420 nm. This is because even when a sufficient amount is added to the heat ray shielding film, the increase in YI of the substrate is very small.

When a benzotriazole compound is used as the selective wavelength absorption material according to the present invention, it is preferable to use a compound represented by [Chemical Formula 1]. This is because the compound represented by [Chemical Formula 1] has a characteristic of having a strong absorption peak at a wavelength of 360 nm to 390 nm, but has a weak absorption of a wavelength that affects the YI of the heat ray shielding film. Furthermore, the absorbance at the absorption peak is very high as compared with general benzotriazole compounds, the solubility in polyvinyl butyral resin is high, and the weather resistance is also excellent.
[Chemical Formula 1]

〔化学式３〕

〔化学式４〕

〔化学式５〕

In the above [Chemical Formula 1], R1 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an amino group, a linear or branched mono-substituted amino group, a linear or branched di-substituted amino group. , Nitro group, carboxyl group, alkylcarbonyloxyalkyl group having 1 to 8 carbon atoms each, alkyloxycarbonylalkyl group having 2 to 10 carbon atoms in total, aryl group, acyl group, sulfo group , A cyano group, or a group represented by [Chemical Formula 2], a group represented by [Chemical Formula 3], a group represented by [Chemical Formula 4], or a group represented by [Chemical Formula 5],
R2 is an alkylene group having 1 to 8 carbon atoms,
R3 is a hydrogen atom or a methyl group,
R4 is a C1-C8 alkylene group.
[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

〔化学式７〕

〔化学式８〕

〔化学式９〕

〔化学式１０〕

Furthermore, as the selective wavelength absorbing material according to the present invention, a benzotriazole compound represented by any one of [Chemical Formula 6] to [Chemical Formula 10] can be used particularly preferably. This is because when the compound having these chemical formulas has a light transmittance at a wavelength of 550 nm of 90% or more and a light transmittance at a wavelength of 460 nm of 90% or more, the light transmittance at a wavelength of 420 nm is 0.1%. This is because the absorbance of light having a wavelength of 420 nm is very low as follows, and is higher than that of a similar compound, and in addition, it has high weather resistance as compared with other selective wavelength absorbing materials.
[Chemical formula 6]

[Chemical formula 7]

[Chemical Formula 8]

[Chemical formula 9]

[Chemical formula 10]

〔化学式１２〕

On the other hand, when an indole compound is used as the selective wavelength absorbing material according to the present invention, it is preferable to use a compound represented by [Chemical Formula 11]. Here, in [Chemical Formula 11], R is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a butyl group, and 2-ethylhexyl group, and examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group. Among them, among the indole compounds represented by [Chemical Formula 11], the indole compound in which R is a methyl group, that is, the compound represented by [Chemical Formula 12] has a light transmittance of 90% or more and a wavelength of 460 nm. When the transmittance of light of 90 nm or more is 90% or more, the transmittance of light having a wavelength of 420 nm is very low as 0.1% or less, and the absorbance of light having a wavelength of 420 nm is higher than that of a similar compound. It is particularly preferable as the selective wavelength absorbing material according to the above.
However, even if it is not the indole compound represented by [Chemical Formula 11], it has an indole skeleton, the indole compound itself excluding the absorption of the medium and the substrate has a light transmittance of 90% or more and a wavelength of 460 nm. When the light transmittance is 90% or more, any indole compound having a light transmittance of 40% or less at a wavelength of 420 nm can be suitably used as the selective wavelength absorbing material according to the present invention.
[Chemical formula 11]

[Chemical formula 12]

The content of the selective wavelength absorbing material in the heat ray shielding film is preferably 0.01% by mass or more and 2.0% by mass or less. This is because if the content is 0.01% by mass or more, the heat shielding property is significantly improved as compared with the case where the selective wavelength absorbing material is not coexisting.
Moreover, if it is 2.0 mass% or less, it is because the absorption of the light of the wavelength which affects YI will not become strong too much, and the color tone of a heat ray shielding film will be maintained. If it is 2.0% by mass or less, the selective wavelength absorbing material does not precipitate in the heat ray shielding film, and does not significantly affect the strength, adhesive strength, and penetration resistance of the film.

  The selective wavelength absorbing material may be added to the heat ray shielding film as long as the selected wavelength absorbing material is uniformly dispersed in the heat ray shielding film, and is preferably a method that does not impair the transparency of the obtained heat ray shielding film. Used.

(4) Ultraviolet absorber In the heat ray shielding film according to the present invention, as the selective wavelength absorbing material, for example, an indole compound or an azomethine compound, a specific benzotriazole compound or a benzotriazole derivative compound is used as a light having a wavelength of 420 nm. In such a case, it is preferable to add an ultraviolet absorber.

The first reason why it is preferable to further add an ultraviolet absorber to the heat ray shielding film according to the present invention is that indole compounds and azomethine compounds efficiently absorb visible light having a short wavelength, but an ultraviolet absorber is added. This is because effective absorption can be obtained even in the ultraviolet region.
By sufficiently cutting light in the ultraviolet region, a higher temperature rise deterrence effect can be obtained. Further, it is possible to sufficiently prevent the influence of ultraviolet rays, sunburn, furniture, and deterioration of the interior of a vehicle or a building on which the heat ray shielding laminated transparent base material according to the present invention is mounted.

The second reason is that by adding an ultraviolet absorber, the photodegradation of the selective wavelength absorbing material due to sunlight or the like can be suppressed.
As a result, even when the heat ray shielding laminated transparent base material according to the present invention is actually used for a long time as a window material for automobiles and buildings, an ultraviolet absorber is further added to the heat ray shielding film according to the present invention. By doing so, it is possible to suppress light degradation of the selected wavelength absorbing material due to sunlight or the like.

〔化学式１６〕

Examples of the ultraviolet absorbers described above include organic ultraviolet absorbers such as benzophenone compounds, salicylic acid compounds, HALS compounds, benzotriazole compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds, and inorganic materials such as zinc oxide, titanium oxide, and cerium oxide. Examples include ultraviolet absorbers, and among them, benzotriazole compounds and benzophenone compounds are particularly preferable. This is because the benzotriazole compound and the benzophenone compound have very high visible light transmittance and high durability against long-term exposure to strong ultraviolet rays even when a concentration sufficient to absorb ultraviolet rays is added.
Preferred specific examples of the ultraviolet absorber include [Chemical Formula 15] and [Chemical Formula 16].
[Chemical formula 15]

[Chemical formula 16]

  It is preferable that the content rate of the ultraviolet absorber in a heat ray shielding film is 0.02 mass% or more and 5.0 mass% or less. If the content is 0.02% by mass or more, ultraviolet light that cannot be absorbed by the selected wavelength absorbing material can be sufficiently absorbed, and photodegradation of the selected wavelength absorbing material can be sufficiently prevented. It is. In addition, when the content is 5.0% by mass or less, the ultraviolet absorber does not precipitate in the heat ray shielding film, and does not significantly affect the strength, adhesive force, and penetration resistance of the film.

  On the other hand, some of the benzotriazole compounds have a large light absorption coefficient at a wavelength of 420 nm. Therefore, by adding a considerable amount of these compounds to the heat ray shielding film, when the light transmittance at a wavelength of 550 nm is 90% or more and the light transmittance at a wavelength of 460 nm is 90% or more, a wavelength of 420 nm is obtained. The effect of reducing the light transmittance to 40% or less can also be exhibited. According to the said structure, these compounds will serve as the effect of a selective wavelength absorption material and a ultraviolet absorber.

  On the other hand, compounds such as benzophenone compounds, triazine compounds, benzotriazolyl compounds, and benzoyl compounds have light absorption coefficients at a wavelength of 420 nm, although they are lower than indole compounds and azomethine compounds. Therefore, even when a considerable amount of these compounds is added to the heat ray shielding film, when the light transmittance at a wavelength of 550 nm is 90% or more and the light transmittance at a wavelength of 460 nm is 90% or more, the wavelength is 420 nm. The light transmittance of 40% or less can be exhibited. Even with this configuration, these compounds also serve as the effects of the selective wavelength absorbing material and the ultraviolet absorber.

(5) Thermoplastic resin As a thermoplastic resin used for the heat ray shielding film according to the present invention, any thermoplastic resin used for a known laminated transparent substrate can be used. In particular, polyvinyl acetal resin and ethylene / vinyl acetate copolymer are preferable from the viewpoints of adhesion to a transparent substrate, weather resistance, penetration resistance, and the like. However, any thermoplastic resin that is generally used as an interlayer film for a laminated transparent substrate for windows of buildings or a laminated transparent substrate for automobile windows can be suitably used as the thermoplastic resin according to the present invention.
The polyvinyl acetal resin is preferably a polyvinyl butyral resin from the viewpoints of adhesion, weather resistance, penetration resistance, and the like. Further, in consideration of the physical properties of the heat ray shielding film, a plurality of types of polyvinyl acetal resins having different degrees of acetalization may be used in combination. Furthermore, a copolyvinyl acetal resin obtained by reacting a plurality of types of aldehydes in combination during acetalization can also be preferably used.
From this viewpoint, the preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 60%, and the upper limit is 75%.

The polyvinyl acetal resin can be prepared by acetalizing polyvinyl alcohol with an aldehyde.
The polyvinyl alcohol is usually obtained by saponifying polyvinyl acetate. Generally, polyvinyl alcohol having a saponification degree of 80 to 99.8 mol% is used.
Moreover, the preferable minimum of the polymerization degree of the said polyvinyl alcohol is 200, and an upper limit is 3000. When the degree of polymerization is 200 or more, resistance to penetration of the manufactured heat ray shielding laminated transparent base material is maintained, and safety is maintained. On the other hand, if it is 3000 or less, the moldability of the resin film is maintained, the rigidity of the resin film is also maintained in a preferable range, and the workability is maintained.

  The aldehyde is not particularly limited, and generally, an aldehyde having 1 to 10 carbon atoms such as n-butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, acetaldehyde or the like is used. It is done. Of these, n-butyraldehyde, n-hexylaldehyde, and n-valeraldehyde are preferable, and butyraldehyde having 4 carbon atoms is more preferable.

(6) Plasticizer When the thermoplastic resin according to the present invention alone does not have sufficient flexibility and adhesion to a transparent substrate, for example, when the thermoplastic resin according to the present invention is a polyvinyl acetal resin, It is preferable to add a plasticizer. On the other hand, in the case of using a thermoplastic resin that is improved in flexibility and adhesion with a transparent substrate by copolymerization or the like because of the properties of the resin itself and excellent in flexibility and adhesion with a transparent substrate, a plasticizer is not necessarily used. It is not necessary to take the composition to add. Examples of the thermoplastic resin that does not require the addition of a plasticizer as a component of the heat ray shielding film according to the present invention include an ethylene / vinyl acetate copolymer. Of course, even if the resin does not require the addition of a plasticizer, it is possible to add a plasticizer as desired in order to further improve flexibility and adhesion to a transparent substrate.
As the plasticizer, a substance generally used as a plasticizer for the thermoplastic resin according to the present invention can be used. For example, as a plasticizer used for a heat ray shielding film mainly composed of polyvinyl acetal resin, a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, or a plasticizer that is an ester type such as a polyhydric alcohol organic acid ester compound. And phosphoric acid plasticizers such as organic phosphoric acid plasticizers. Any plasticizer is preferably liquid at room temperature. In particular, a plasticizer that is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferred.

The ester compound synthesized from the polyhydric alcohol and fatty acid is not particularly limited. For example, glycol such as triethylene glycol, tetraethylene glycol, tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl Examples thereof include glycol ester compounds obtained by reaction with monobasic organic acids such as acid, n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonyl acid), and decyl acid. In addition, ester compounds of tetraethylene glycol, tripropylene glycol, and the above-mentioned monobasic organic are also included.
Of these, triethylene glycol fatty acid esters such as triethylene glycol dihexanate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-octanoate, and triethylene glycol di-2-ethylhexanate are suitable. is there. The fatty acid ester of triethylene glycol has various properties such as compatibility with polyvinyl acetal and cold resistance in a well-balanced manner, and is excellent in processability and economy.

  Note that the choice of plasticizer is low in hydrolyzability. From this viewpoint, triethylene glycol di-2-ethylhexanate, triethylene glycol di-2-ethylbutyrate, and tetraethylene glycol di-2-ethylhexanate are preferable.

(7) Adhesive strength adjusting agent It is also preferable to add an optional adhesive strength adjusting agent to the heat ray shielding film according to the present invention.
Although the said adhesive force regulator is not specifically limited, An alkali metal salt and / or an alkaline-earth metal salt are used suitably. The acid which comprises the said metal salt is not specifically limited, For example, inorganic acids, such as carboxylic acids, such as octyl acid, hexyl acid, butyric acid, acetic acid, formic acid, or hydrochloric acid, nitric acid, are mentioned. Among the alkali metal salts and / or alkaline earth metal salts, a carboxylic acid magnesium salt having 2 to 16 carbon atoms and a carboxylic acid potassium salt having 2 to 16 carbon atoms are preferable.
The carboxylic acid magnesium salt and potassium salt of the organic acid having 2 to 16 carbon atoms are not particularly limited, and examples thereof include magnesium acetate, potassium acetate, magnesium 2-ethylbutyrate, magnesium propionate, potassium propionate, and 2-ethylbutane. Magnesium acid, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like are preferably used. Among these, magnesium 2-ethylbutyrate has a high performance as an adhesive force regulator, and is also known to have an effect of improving the weather resistance of the composite tungsten oxide fine particles in a heat ray shielding film mainly composed of polyvinyl acetal resin. It is preferable.

These adhesive strength modifiers may be used alone or in combination of two or more.
In addition, when sodium, potassium, magnesium, calcium, or cerium carboxylate is used as an adhesive strength modifier, the action as an original adhesive strength modifier and the above-described improved weather resistance of the composite tungsten oxide fine particles are improved. It can also have an effect.

(8) Infrared-absorbing organic compound In the present invention, an infrared-absorbing organic compound having strong absorption in the near-infrared region may be further added to the heat ray shielding film as desired.
The infrared-absorbing organic compound is more preferably a material that strongly absorbs light in the range from the visible long wavelength region to the near infrared region having a wavelength of 650 nm to 1000 nm. This is because the synergistic effect when the infrared absorbing organic compound having the optical characteristics and the composite tungsten oxide fine particles having strong absorption in the wavelength region of 800 nm or more coexist is large. This is because a higher heat shielding performance can be obtained as compared with the case of using it alone.

  Examples of infrared absorbing organic compounds used for this purpose include phthalocyanine compounds, naphthalocyanine compounds, imonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, triphenylmethane compounds, quinone compounds, azo compounds, pentadiene compounds, azomethine compounds, squarylium. Compounds, organometallic complexes, cyanine compounds and the like can be used. Furthermore, from the viewpoint described above, a diimonium compound and a phthalocyanine compound are preferable.

  The content of the infrared absorbing organic compound in the heat ray shielding film according to the present invention is preferably 0.02% by mass or more and 0.2% by mass or less. If the mixing ratio of the addition amount of the infrared absorbing organic compound is 0.02% by mass or more, the infrared absorbing organic compound strongly enhances light in the visible light long wavelength region from the wavelength range of 650 nm to 1000 nm to the near infrared region. The effect to absorb is acquired and it is preferable. Moreover, if the mixing ratio of the addition amount of the infrared-absorbing organic compound is 0.2% by mass or less in the above-mentioned weight ratio, the wavelength that is a wavelength region that greatly contributes to the calculation of the visible light transmittance by the infrared-absorbing organic compound Since it is possible to avoid absorption of light in the vicinity of 550 nm and light in the vicinity of a wavelength of 460 nm that affects the yellow value of the film, a decrease in visible light transmittance and an increase in the yellow value can be avoided. As a result, even if the visible light transmittance is combined, the heat shielding property and the color are secured, which is preferable.

(9) Other Additives The heat ray shielding film according to the present invention can further contain general additives as desired. For example, azo dyes, cyanine dyes, quinoline dyes, perylene dyes, carbon black, etc., which are generally used for coloring thermoplastic resins to give an arbitrary color tone as desired. It may be added. Particularly in the present invention, since the light on the short wavelength side of visible light is absorbed, the transmitted light color is slightly yellowish. Therefore, it is preferable to adjust the color tone of the heat ray shielding film by adding a compound such as a dye or a pigment.
As other additives, a coupling agent, a surfactant, an antistatic agent, an antioxidant, and the like can be added.

[2] Heat ray shielding film In order to produce the heat ray shielding film according to the present invention,
(I) After obtaining a dispersion in which the composite tungsten oxide fine particles and the dispersant are dispersed in a general organic solvent, the composite tungsten oxide fine particles are dispersed in the solid dispersant by removing the organic solvent. What is necessary is just to manufacture the composite tungsten oxide fine particle dispersion in a state. Or
(Ii) In the case of using a thermoplastic resin that needs to use a plasticizer as the heat ray shielding film according to the present invention, the composite tungsten oxide fine particles and the dispersant described above are part of the plasticizer added to the thermoplastic resin. It can also be dispersed to produce a composite tungsten oxide fine particle dispersion.

  Then, the manufactured composite tungsten oxide fine particle dispersion, or the manufactured composite tungsten oxide fine particle dispersion, the selective wavelength absorbing material, the polyvinyl acetal resin, the plasticizer as necessary, and preferably the ultraviolet absorption. It can be produced by mixing the agent with other additives and adhesive strength modifiers as desired, kneading, and then molding the film into a film by a known method such as extrusion molding or calendar molding. I can do it. Further, if an infrared absorbing organic compound is added to the heat ray shielding film as desired, higher heat ray shielding characteristics can be obtained.

  Hereinafter, a method for producing a composite tungsten oxide fine particle dispersion and a method for producing a composite tungsten oxide fine particle dispersion will be described.

(1) Manufacturing method of composite tungsten oxide fine particle dispersion The composite tungsten oxide fine particles and the dispersant are added to and mixed with an organic solvent, and the composite tungsten oxide fine particles are dispersed in an organic solvent using a general dispersion method. Can be obtained. Specifically, a dispersion method such as a bead mill, a ball mill, a sand mill, or ultrasonic dispersion can be used.
As the organic solvent, those having a boiling point of 120 ° C. or less are preferably used. If the boiling point is 120 ° C. or lower, it is easy to remove by a drying step, which is a subsequent step, particularly by drying under reduced pressure. As a result, removal in the reduced-pressure drying step proceeds rapidly, contributing to the productivity of the composite tungsten oxide fine particle-containing composition. Furthermore, since the vacuum drying process proceeds easily and sufficiently, it can be avoided that an excess organic solvent remains in the composite tungsten oxide fine particle-containing composition according to the present invention. As a result, it is possible to avoid the occurrence of problems such as the generation of bubbles when forming the heat ray shielding film. Specific examples include toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol, and ethanol. Any boiling point can be used as long as it has a boiling point of 120 ° C. or lower and can uniformly disperse the composite tungsten oxide fine particles. Can be selected.

  Moreover, as a method for removing the organic solvent from the organic solvent dispersion of the composite tungsten oxide fine particles, a method of drying under reduced pressure is preferable. Specifically, a composite tungsten oxide fine particle-containing composition is dried under reduced pressure with stirring to separate the composite tungsten oxide fine particle-containing composition from the organic solvent component. Examples of the apparatus used for drying under reduced pressure include a vacuum stirring type dryer, but any apparatus having the above functions may be used, and the apparatus is not particularly limited. Moreover, the pressure of the pressure reduction of a drying process is selected suitably.

  By using the reduced-pressure drying method, the removal efficiency of the solvent is improved, and the composite tungsten oxide fine particle-containing composition is not exposed to high temperature for a long time, so that aggregation of dispersed fine particles does not occur. preferable. Furthermore, productivity is increased, and it is easy to collect the evaporated organic solvent, which is preferable from the environmental consideration.

(2) Manufacturing method of composite tungsten oxide fine particle dispersion The composite tungsten oxide fine particles and the dispersant are added to and mixed with the plasticizer, and the plasticizer dispersion of the composite tungsten oxide fine particles using a general dispersion method. Can be obtained. Specifically, a dispersion method such as a bead mill, a ball mill, a sand mill, or ultrasonic dispersion can be used.

  The concentration of the composite tungsten oxide fine particles in the plasticizer is preferably 50% by mass or less. If the concentration of the composite tungsten oxide fine particles in the plasticizer is 50% by mass or less, the fine particles are hardly aggregated, easily dispersed, a sudden increase in viscosity can be avoided, and handling is easy.

[3] Heat ray shielding laminated transparent base material The heat ray shielding laminated transparent base material using the heat ray shielding film according to the present invention has various forms.
For example, a heat ray shielding laminated inorganic glass using inorganic glass as a transparent substrate is obtained by laminating and integrating a plurality of opposing inorganic glasses that are sandwiched by the heat ray shielding film according to the present invention by a known method. can get. The obtained heat-shielding laminated inorganic glass can be used mainly as an inorganic glass for an automobile front or a window of a building.

Furthermore, the structure which uses the heat ray shielding film concerning this invention and the infrared rays reflective film mentioned later together as a heat ray shielding film, and makes it a heat ray shielding laminated transparent base material is also preferable. When the structure is adopted, the infrared reflective film is sandwiched between a heat ray shielding film and a transparent resin film to be integrated to form a multilayer film. The obtained multilayer film is sandwiched between a plurality of opposing inorganic glasses and laminated and integrated by a known method to obtain a heat-shielding laminated inorganic glass.
Here, considering that the heat ray shielding laminated inorganic glass is used in an automobile, the structure in which the infrared reflection film is present outside the heat ray shielding film according to the present invention in consideration of the temperature rise suppressing effect in the automobile. preferable.

  The heat shielding property of the heat ray shielding laminated transparent base material according to the present invention is indicated by the solar radiation transmittance with respect to the visible light transmittance. Visible light transmittance and solar radiation transmittance are defined in JIS R 3106. The lower the solar radiation transmittance relative to the visible light transmittance, the more the heat ray shielding laminated transparent base material has better heat shielding properties. Specifically, when the visible light transmittance is 70%, the solar radiation transmittance is preferably 32.5% or less, more preferably 31% or less, and further preferably 30% or less.

  In particular, when the heat ray shielding laminated transparent base material according to the present invention is used for a window material such as a windshield of an automobile, a high heat ray shielding ability is required while satisfying the transmittance of 70% or more stipulated by the Road Transport Vehicle Law. It is because it is said. Incidentally, if the solar radiation transmittance of the heat-shielding laminated transparent base material is 32.5% or less, the power consumption of the air conditioner when the outside air temperature is 30 ° C or higher is compared with the case where ordinary laminated glass is installed. Reduced by more than 5%. As a result, particularly in an automobile using a battery such as a hybrid car or an electric car, consumption of the battery can be suppressed, so that a significant effect is seen in extending the cruising distance. Therefore, it can be expected to contribute to improving the fuel efficiency of automobiles and reducing greenhouse gas emissions, and in the future, it is expected to become an essential member in the design of automobiles.

When the heat ray shielding laminated transparent base material according to the present invention is used as a window material in an automobile or a building, it is preferable to have a natural color tone (transparent or achromatic color). In particular, assuming that the heat-shielding transparent substrate according to the present invention is used for a windshield of an automobile, it is preferable that the color of the fluoroscopic image can be normally identified in order to ensure safety during driving.
From this viewpoint, for the heat ray shielding film according to the present invention, for example, in the color discrimination test based on JIS R 3211 and JIS R 3212 that define the performance required for laminated glass for automobiles, the color of the fluoroscopic image is normal. It is preferred that it be identifiable.
Here, when the YI of the heat ray shielding film according to the present invention is −20.0 or more and 10.0 or less, the color of the fluoroscopic image can be normally identified. And the YI of the heat ray shielding film according to the present invention can be set to -20.0 or more and 10.0 or less by adopting the configuration of the addition amount of the selective wavelength absorbing material according to the present invention described above. In addition, it is more preferable that YI of the heat ray shielding film is −20.0 or more and 5.0 or less because the color of the fluoroscopic image can be further easily identified.

A transparent resin is used as a transparent substrate, and it is used in the same manner as the above inorganic glass, or in combination with the above inorganic glass, and a heat ray shielding film is sandwiched between opposing transparent substrates, so that the heat ray shielding transparent A substrate can be obtained. The application of the heat ray shielding laminated transparent base material is the same as that of the heat ray shielding laminated inorganic glass described above.
In addition, if desired, the heat ray shielding film according to the present invention can be used alone, or the heat ray shielding film according to the present invention can be used on one side or both sides of a transparent substrate such as inorganic glass or transparent resin. Is possible.

Here, the infrared reflective film used together with the heat ray shielding film according to the present invention described above will be described.
In consideration of optical characteristics when used in combination with the heat ray shielding film according to the present invention, the infrared reflective film has almost no absorption of sunlight in the visible light region, from the long wavelength region of visible light to the near infrared region, specifically It is preferable from the viewpoint of the heat ray shielding function that it reflects only the wavelength range of 700 nm to 1200 nm.
Specifically, as the optical characteristics of the infrared reflective film, the visible light transmittance is preferably 85% or more, the solar reflectance 18% or more, the visible light transmittance 88% or more, and the solar reflectance 21% or more. Is more preferable.
Furthermore, considering the use of a heat-shielding transparent substrate as a windshield for automobiles and window materials for buildings, the infrared reflective film according to the present invention emits electromagnetic waves in the wavelength region used for mobile phones and ETC. What permeate | transmits is preferable. Therefore, a film with a resin multilayer film that transmits electromagnetic waves and a film that reflects infrared rays with a cholesteric liquid crystal are preferable to a film with metal film that has conductivity and does not transmit electromagnetic waves.

[4] Summary As described above in detail, the composite tungsten oxide fine particle dispersion according to the present invention, or the composite tungsten oxide fine particle dispersion according to the present invention, a selective wavelength absorbing material, a thermoplastic resin, The heat ray shielding film according to the present invention can be produced by kneading with a plasticizer as necessary, and further forming into a film by a known method.
And by presenting the heat ray shielding film according to the present invention so as to be sandwiched between a plurality of opposed transparent substrates, it exhibits a low solar transmittance while maintaining high transparency in the visible light region, The production of a heat-shielded transparent base material according to the present invention has become possible.
The composite tungsten oxide fine particles are combined with the selected wavelength absorbing material having no absorption near the wavelength of 550 nm, no absorption near the wavelength of 460 nm, and large absorption near the wavelength of 420 nm. Compared with the case where the tungsten oxide fine particles are used alone, higher heat ray shielding characteristics can be exhibited.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
In addition, the transmittance of light having a wavelength of 420 nm, a wavelength of 460 nm, and a wavelength of 550 nm of the selective wavelength absorbing material in each example is a quartz glass cell having an optical path length of 1 cm obtained by dissolving a liquid in which the selective wavelength absorbing material is dissolved at an appropriate concentration. And measured using a spectrophotometer U-4000 manufactured by Hitachi, Ltd. The baseline was drawn with only the organic solvent used for dissolution in the same cell. As the organic solvent for dissolving the selected wavelength absorbing material, one kind arbitrarily selected from toluene, methyl isobutyl ketone, and N-methyl-2-pyrrolidinone according to the solvent solubility of the selected wavelength absorbing material was used.
The visible light transmittance and the solar radiation transmittance of the heat ray shielding laminated transparent base material were calculated based on JIS R 3106 from the transmittance of light having a wavelength of 300 to 2100 nm measured using a spectrophotometer U-4000. In addition, the said solar transmittance is an parameter | index which shows the heat ray shielding performance of a heat ray shielding matching transparent base material. If the solar radiation transmittance is lower when the visible light transmittance is substantially constant, it can be said that the heat ray shielding performance is higher. This time, the visible light transmittance was unified within a range of 70.0 to 70.5%, and the level of solar radiation transmittance at this time was used as a criterion for determining superiority or inferiority of the heat ray shielding performance.
On the other hand, YI of the heat ray shielding laminated transparent base material was calculated based on JIS Z 8701 and JIS K 7373 from the transmittance of light with a wavelength of 380 to 780 nm measured using a spectrophotometer U-4000.

[Example 1]
20% by mass of composite tungsten oxide fine particles Cs _0.33 WO ₃ (hereinafter referred to as fine particles a) and an acrylic dispersant having an amine-containing group as a functional group (amine value 48 mgKOH / g, decomposition temperature 250) C.) 10% by mass of an acrylic dispersant (hereinafter referred to as Dispersant a) and 70% by mass of triethylene glycol di-2-ethylhexanoate (hereinafter referred to as Plasticizer a). . These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of fine particles a (hereinafter referred to as fine particle dispersion A).
Here, the dispersion average particle diameter of the tungsten oxide fine particles in the fine particle dispersion A was measured with a Nikkiso Microtrac particle size distribution meter and found to be 21 nm.

A mixture obtained by mixing 38% by mass of a plasticizer with respect to polyvinyl butyral resin, a predetermined amount of the fine particle dispersion A, and a benzotriazole compound represented by [Chemical formula 6] as a selective wavelength absorbing material (light transmittance at a wavelength of 550 nm) 99%, and the transmittance at a wavelength of 420 nm when the transmittance of light at a wavelength of 460 nm is 90%) is 0%), and the content of the selective wavelength absorbing material in the composition for manufacturing a heat ray shielding film is 0.05 It added so that it might become a mass%, and visible light transmittance | permeability when it was set as a laminated transparent base material will be 70.0-70.5%, and the composition for manufacture of a heat ray shielding film was prepared.
The composition for producing this heat ray shielding film was kneaded at 200 ° C. with a twin-screw extruder, and the heat ray shielding film according to Example 1 was obtained as a sheet having a thickness of 1.0 mm by extrusion calendering from a T die.
[Chemical formula 6]

  The obtained heat ray shielding film according to Example 1 was sandwiched between two opposing 3 mm-thick clear glasses and laminated together by a known method to obtain a heat ray shielding laminated transparent base material according to Example 1.

  As for the optical characteristics of the heat ray shielding laminated transparent substrate according to Example 1, the solar radiation transmittance was 29.3% and the YI was 4.5 when the visible light transmittance was 70.0%. Moreover, when the weather resistance test of the heat ray shielding laminated transparent base material was conducted, the color change ΔE was 2.9. These results are shown in Table 1.

実施例４〜６においては、〔化学式７〕で示されるベンゾトリアゾール化合物（波長５５０ｎｍの光の透過率を９９％、波長４６０ｎｍの光の透過率を９０％としたときの波長４２０ｎｍの透過率は０％）を用いた。
〔化学式７〕

実施例７〜９においては、〔化学式８〕で示されるベンゾトリアゾール化合物（波長５５０ｎｍの光の透過率を９９％、波長４６０ｎｍの光の透過率を９０％としたときの波長４２０ｎｍの透過率は０％）を用いた。
〔化学式８〕

実施例１０においては、〔化学式９〕で示されるベンゾトリアゾール化合物（波長５５０ｎｍの光の透過率を９９％、波長４６０ｎｍの光の透過率を９０％としたときの波長４２０ｎｍの透過率は０％）を用いた。
〔化学式９〕

実施例１１においては、〔化学式１０〕で示されるベンゾトリアゾール化合物（波長５５０ｎｍの光の透過率を９９％、波長４６０ｎｍの光の透過率を９０％としたときの波長４２０ｎｍの透過率は０％）を用いた。
〔化学式１０〕

実施例１２〜１４においては、〔化学式１２〕で示されるインドール化合物であるオリヱント化学工業製ＢＯＮＡＳＯＲＢ ＵＡ−３９１１（ＣＡＳ Ｎｏ．１４２６７６−９３−５。波長５５０ｎｍの光の透過率を９９％、波長４６０ｎｍの光の透過率を９０％としたときの波長４２０ｎｍの透過率は０％）を用いた。
〔化学式１２〕

実施例１５においては、〔化学式１３〕で示されるアゾメチン化合物であるオリヱント化学工業製ＢＯＮＡＳＯＲＢ ＵＡ−３７０１（ＣＡＳ Ｎｏ．５５５６７−５９−４。波長５５０ｎｍの光の透過率を９８％、波長４６０ｎｍの光の透過率を９０％としたときの波長４２０ｎｍの透過率は０％）を用いた。
〔化学式１３〕

実施例１６においては、〔化学式１４〕で示されるベンゾフェノン化合物である大和化成製ＤＡＩＮＳＯＲＢ Ｐ−６（ＣＡＳ Ｎｏ．１３１−５５−４。波長５５０ｎｍの光の透過率を９７％、波長４６０ｎｍの光の透過率を９２％としたときの波長４２０ｎｍの透過率は２５％）を用いた。
〔化学式１４〕

[Examples 2 to 16]
Except for changing the kind of the selective wavelength absorbing material described in Example 1 and the content of the selective wavelength absorbing material in the composition for producing a heat ray shielding film as shown in Table 1, the same manner as in Example 1 was performed. The heat ray shielding laminated transparent base material which concerns on Examples 2-16 was obtained. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Examples 2-16, and the color change (DELTA) E at the time of a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the optical property measurement results of the heat-shielding transparent substrates according to Examples 2 to 16 and the color change ΔE during the weather resistance test.
In Examples 2 to 3, the benzotriazole compound represented by [Chemical Formula 6] described above was used as the selective wavelength absorbing material.
[Chemical formula 6]

In Examples 4 to 6, the benzotriazole compound represented by [Chemical Formula 7] (the transmittance at a wavelength of 420 nm when the transmittance of light at a wavelength of 550 nm is 99% and the transmittance of light at a wavelength of 460 nm is 90% is 0%) was used.
[Chemical formula 7]

In Examples 7 to 9, the benzotriazole compound represented by [Chemical Formula 8] (the transmittance at a wavelength of 420 nm when the transmittance of light at a wavelength of 550 nm is 99% and the transmittance of light at a wavelength of 460 nm is 90% is 0%) was used.
[Chemical Formula 8]

In Example 10, the benzotriazole compound represented by [Chemical Formula 9] (the transmittance at a wavelength of 420 nm when the transmittance of light at a wavelength of 550 nm is 99% and the transmittance of light at a wavelength of 460 nm is 90% is 0%. ) Was used.
[Chemical formula 9]

In Example 11, the benzotriazole compound represented by [Chemical Formula 10] (the transmittance at a wavelength of 420 nm when the transmittance of light at a wavelength of 550 nm is 99% and the transmittance of light at a wavelength of 460 nm is 90% is 0%. ) Was used.
[Chemical formula 10]

In Examples 12 to 14, BONOSORB UA-3911 (CAS No. 142676-93-5 manufactured by Orient Chemical Industries, which is an indole compound represented by [Chemical Formula 12]. Light transmittance at a wavelength of 550 nm is 99%, wavelength is 460 nm. The transmittance at a wavelength of 420 nm when the light transmittance of 90% is 90%) was used.
[Chemical formula 12]

In Example 15, BONASORB UA-3701 (CAS No. 55567-59-4, manufactured by Orient Chemical Co., Ltd.), which is an azomethine compound represented by [Chemical Formula 13], light having a wavelength of 550 nm with a transmittance of 98% and a wavelength of 460 nm The transmittance at a wavelength of 420 nm when the transmittance is 90% is 0%).
[Chemical formula 13]

In Example 16, DAINSORB P-6 (CAS No. 131-55-4, manufactured by Daiwa Kasei Co., Ltd.), which is a benzophenone compound represented by [Chemical Formula 14], has a transmittance of 97% for light having a wavelength of 550 nm and light having a wavelength of 460 nm. The transmittance at a wavelength of 420 nm when the transmittance is 92% is 25%).
[Chemical formula 14]

[Example 17]
The benzotriazole compound represented by [Chemical Formula 15] is further added to the composition for producing a heat ray shielding film as an ultraviolet absorber, and the content of the ultraviolet absorber in the composition for producing a heat ray shielding film is 0.3% by mass. A heat ray shielding laminated transparent base material according to Example 17 was obtained in the same manner as Example 1 except that the above addition was made. Then, the optical characteristics of the heat-shielding transparent transparent base material in Example 17 and the color change ΔE during the weather resistance test were measured in the same manner as in Example 1. Table 2 shows the measurement results of the optical properties of the heat-shielding transparent substrate according to Example 17 and the color change ΔE during the weather resistance test.

[Examples 18 to 19]
The type of the selected wavelength absorbing material and the content of the selected wavelength absorbing material in the composition for manufacturing the heat ray shielding film, the type of the ultraviolet absorber, and the content of the ultraviolet absorber in the composition for producing the heat ray shielding film are shown. The heat-shielding laminated transparent base material according to Examples 18 and 19 was obtained in the same manner as in Example 17 except that it was changed to 1. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Examples 18 and 19 and the color change (DELTA) E at the time of a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the optical property measurement results of the heat-shielding laminated transparent base materials according to Examples 18 and 19 and the color change ΔE during the weather resistance test.

〔化学式１６〕

実施例１９においては、選択波長吸収材料として〔化学式１２〕で示されるインドール化合物を用い、紫外線吸収剤として〔化学式１５〕で示されるベンゾトリアゾール化合物を用いた。
〔化学式１２〕

〔化学式１５〕

In Example 18, a benzotriazole compound represented by [Chemical Formula 6] was used as the selective wavelength absorbing material, and a benzotriazole compound represented by [Chemical Formula 16] was used as the ultraviolet absorber.
[Chemical formula 6]

[Chemical formula 16]

In Example 19, an indole compound represented by [Chemical Formula 12] was used as the selective wavelength absorbing material, and a benzotriazole compound represented by [Chemical Formula 15] was used as the ultraviolet absorber.
[Chemical formula 12]

[Chemical formula 15]

[Example 20]
Other than adding magnesium 2-ethylbutyrate as a polyvalent metal salt to the composition for producing a heat ray shielding film so that the content of the polyvalent metal salt in the composition for producing a heat ray shielding film is 0.04% Obtained a heat ray shielding laminated transparent base material according to Example 20 in the same manner as in Example 17. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 17, and the color change (DELTA) E in a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the measurement results of the optical properties of the heat-shielding transparent substrate according to Example 20 and the color change ΔE during the weather resistance test.

[Comparative Example 1]
A heat ray shielding laminated transparent base material according to Comparative Example 1 was obtained in the same manner as in Example 1 except that the selective wavelength absorbing material was not added. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said comparative example 1, and color change (DELTA) E in a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the measurement results of the optical properties of the heat-shielding transparent substrate according to Comparative Example 1 and the color change ΔE in the weather resistance test.

[Comparative Example 2]
A heat ray shielding laminated transparent substrate according to Comparative Example 2 is obtained in the same manner as in Example 1 except that the content of the selective wavelength absorbing material in the composition for producing a heat ray shielding film is 0.005% by mass. It was. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said comparative example 2, and the color change (DELTA) E in a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the measurement results of optical properties of the heat-shielding transparent transparent substrate according to Comparative Example 2 and the color change ΔE in the weather resistance test.

[Comparative Example 3]
A quinophthalone compound represented by [Chemical Formula 17] as a selective wavelength absorbing material (CI Solvent Yellow 33, CAS No. 8003-22-3. Light transmittance at a wavelength of 550 nm is 99%, light transmittance at a wavelength of 460 nm Example 1 except that the transmittance at a wavelength of 420 nm with respect to 90% is 55%), and the content of the selective wavelength absorbing material in the composition for manufacturing a heat ray shielding film is 0.01% by mass. In the same manner as above, a heat ray shielding laminated transparent base material according to Comparative Example 3 was obtained. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said comparative example 3, and the color change (DELTA) E in a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the optical property measurement results of the heat ray shielding laminated transparent base material according to Comparative Example 3 and the color change ΔE in the weather resistance test.
[Chemical formula 17]

[Example 21]
20% by mass of composite tungsten oxide fine particles Rb _0.33 WO ₃ (hereinafter referred to as fine particles b), 10% by mass of dispersant a, and 70% by mass of plasticizer a were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a plasticizer dispersion of fine particles b (hereinafter referred to as fine particle dispersion B).
Here, the dispersed particle size of the composite tungsten oxide fine particles in the fine particle dispersion B was 27 nm as measured with a Nikkiso Microtrac particle size distribution meter.
A heat ray shielding laminated transparent substrate according to Example 21 was obtained in the same manner as in Example 1 except that the fine particle dispersion B was used as an alternative to the fine particle dispersion A. And the optical characteristic of the heat ray shielding laminated transparent base material concerning the said Example 21 and the color change (DELTA) E in a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the measurement results of optical properties of the heat-shielding transparent substrate according to Example 21 and the color change ΔE in the weather resistance test.

[Example 22]
20% by mass of fine particles a, 10% by mass of dispersant a, and 70% by mass of toluene were weighed. These were loaded into a paint shaker containing 0.3 mmφZrO ₂ beads and pulverized and dispersed for 10 hours to obtain a dispersion of composite tungsten oxide fine particles (hereinafter abbreviated as fine particle dispersion C).
Here, the dispersed particle diameter of the composite tungsten oxide fine particles in the fine particle dispersion C was measured with a Nikkiso Microtrac particle size distribution meter, and found to be 24 nm.
Dispersant a was further added to dispersion C, and the dispersion was prepared so that the weight ratio of dispersant a and composite tungsten oxide fine particles was [dispersant a / composite tungsten oxide fine particles] = 3. Next, toluene was removed from the fine particle dispersion C using a spray dryer to obtain a composite tungsten oxide fine particle dispersion powder (hereinafter abbreviated as dispersion powder C).

A predetermined amount of dispersed powder A and a benzotriazole compound represented by [Chemical Formula 6] as a selective wavelength absorbing material are added to a thermoplastic resin ethylene-vinyl acetate copolymer in a composition for producing a heat ray shielding film. Is added so that the visible light transmittance is 70.0 to 70.5% when the content of the selected wavelength absorbing material is 0.05% by mass and the laminated transparent base material is used. A composition was prepared. In addition, the plasticizer was not added to the composition for manufacturing a heat ray shielding resin film.
[Chemical formula 6]

This composition for producing the heat ray shielding resin film was kneaded at 220 ° C. using a twin screw extruder, and was extruded from a T die to form a sheet having a thickness of 1.0 mm by the calender roll method. Obtained.
The obtained heat ray shielding film according to Example 22 was sandwiched between two opposing 3 mm-thick clear glasses and laminated together by a known method to obtain a heat ray shielding laminated transparent base material according to Example 22.
Then, the optical characteristics of the heat ray shielding laminated transparent base material according to Example 22 and the color change ΔE in the weather resistance test were measured in the same manner as in Example 1. Table 2 shows the optical property measurement results of the heat ray shielding laminated transparent base material according to Example 22 and the color change ΔE in the weather resistance test.

[Example 23]
A heat ray shielding laminated transparent base material according to Example 23 was obtained in the same manner as in Example 1 except that two opposing 2 mm thick green glasses were used as the transparent base material sandwiching the heat ray shielding film. And the optical characteristic of the heat ray shielding laminated transparent base material which concerns on the said Example 23, and the color change (DELTA) E in a weather resistance test were measured similarly to Example 1. FIG. Table 2 shows the measurement results of optical properties of the heat-shielding laminated transparent base material according to Example 23 and the color change ΔE in the weather resistance test.

Table 1 shows the transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 550 nm and a wavelength of 460 nm is 90% or more in the selected wavelength absorbing material itself excluding the absorption of the medium and the substrate.
[Chemical Formula 6], [Chemical Formula 7], [Chemical Formula 8], [Chemical Formula 9], a benzotriazole compound represented by [Chemical Formula 10] used in Examples 1 to 23, an indole compound represented by [Chemical Formula 12], [ The light transmittance at a wavelength of 420 nm of the azomethine compound represented by [Chemical Formula 13] and the benzophenone compound represented by [Chemical Formula 14] is 40% or less, but the quinophthalone compound represented by [Chemical Formula 17] used in Comparative Example 3 The transmittance of light with a wavelength of 420 nm was higher than 40%.

[Evaluation of Examples 1 to 23 and Comparative Examples 1 to 3]
In Examples 1-23, the solar radiation transmittance lower than the comparative example 1 which did not coexist the selection wavelength absorption material is obtained by coexisting the selection wavelength absorption material with the composite tungsten oxide fine particles in an appropriate ratio. It was. Further, the YI of the heat ray shielding laminated transparent base material did not exceed 10, and there was little change in color tone due to the coexistence of the selective wavelength absorbing material.
In particular, in Examples 1 to 11, Examples 17 to 18, and Examples 20 to 23, the use of a highly weatherable benzotriazole compound as the selective wavelength absorbing material resulted in deterioration of the selected wavelength absorbing material in the weather resistance test. Was suppressed, and the change in color tone was less.
Moreover, in Examples 17-20, the solar radiation transmittance lower than what combined only the selective wavelength absorption material with the composite tungsten oxide microparticles | fine-particles was obtained by having coexisted the ultraviolet absorber, and in addition, The change in color tone in the weather resistance test was even smaller. Especially in Example 20 which used a polyvalent metal salt together, the color tone change of the laminated transparent base material before and after a weather resistance test was suppressed more.

  On the other hand, since the selective wavelength absorbing material was not used in Comparative Example 1, the solar radiation transmittance was 33% or more when the visible light transmittance was 70%, and the ultraviolet absorber, the polyvalent metal salt, and the selective wavelength absorption. Since none of the materials was contained, the composite tungsten oxide fine particles were greatly colored by ultraviolet rays, and the change in color tone in the weather resistance test was also large. In Comparative Example 2, sufficient absorption was not obtained because the addition amount of the selective wavelength absorbing material was small, and only the same solar transmittance as Comparative Example 1 in which the selective wavelength absorbing material was not coexisted was obtained. In Comparative Example 3, as the selective wavelength absorbing material, the light transmittance at a wavelength of 550 nm and a wavelength of 460 nm is used, and the quinophthalone compound having a weak absorption at a wavelength of 420 nm is used. The color tone of the base material has changed greatly.

Claims (19)

Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
Content of the said selective wavelength absorption material in the said heat ray shielding film is 0.01 mass% or more and 2.0 mass% or less,
The selective wavelength absorbing material is a benzotriazole compound represented by [Chemical Formula 1],
R1 in the benzotriazole compound represented by [Chemical Formula 1] is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, an amino group, a linear or branched mono-substituted amino group, a linear or branched chain Disubstituted amino group, nitro group, carboxyl group, alkylcarbonyloxyalkyl group having 1 to 8 carbon atoms each, alkyloxycarbonylalkyl group having 2 to 10 carbon atoms in total, alkyl group, acyl group, acyl group A group selected from a group represented by a chemical formula 2; a group represented by a chemical formula 3; a group represented by a chemical formula 4; a group represented by a chemical formula 5; ,
R2 in the groups represented by the above [Chemical Formula 2] to [Chemical Formula 5] is an alkylene group having 1 to 8 carbon atoms,
R3 in the groups represented by the above [Chemical Formula 2] to [Chemical Formula 5] is a hydrogen atom or a methyl group,
R4 is heat-ray shielding film which is a alkylene group having 1 to 8 carbon atoms in the group represented by [Formula 4].
[Chemical Formula 1]

[Chemical formula 2]

[Chemical formula 3]

[Chemical formula 4]

[Chemical formula 5]

Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
Content of the said selective wavelength absorption material in the said heat ray shielding film is 0.01 mass% or more and 2.0 mass% or less,
The heat ray shielding film, wherein the selective wavelength absorbing material is at least one selected from benzotriazole compounds represented by any one of [Chemical Formula 6] to [Chemical Formula 10].
[Chemical formula 6]

[Chemical formula 7]

[Chemical Formula 8]

[Chemical formula 9]

[Chemical formula 10]

Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
Content of the said selective wavelength absorption material in the said heat ray shielding film is 0.01 mass% or more and 2.0 mass% or less,
The selective wavelength absorbing material is an indole compound represented by [Chemical Formula 11],
Wherein R is in indole compound represented by [Chemical Formula 11], heat-ray shielding film, wherein the alkyl group or the carbon number of 1 to 10 carbon atoms is an aralkyl group having 7 to 10.
[Chemical formula 11]

Formula _M y WO _Z (where, M is, Cs, Rb, K, Tl , In, Ba, Li, Ca, Sr, 1 or more elements selected Fe, Sn, Al, from Cu, 0.1 ≦ y ≦ 0.5, 2.2 ≦ z ≦ 3.0) and a composite tungsten oxide fine particle having a hexagonal crystal structure, a selective wavelength absorbing material, and a heat ray containing a thermoplastic resin A shielding film,
The selective wavelength absorbing material has a transmittance of light having a wavelength of 550 nm of 90% or more and a transmittance of light having a wavelength of 420 nm when the transmittance of light having a wavelength of 460 nm is 90% or more. Have a profile,
Content of the said selective wavelength absorption material in the said heat ray shielding film is 0.01 mass% or more and 2.0 mass% or less,
The heat ray shielding film, wherein the selective wavelength absorbing material is an indole compound represented by [Chemical Formula 12].
[Chemical formula 12]

The thermoplastic resin is one resin selected from a resin group of polyvinyl acetal resin, vinyl chloride resin, and ethylene / vinyl acetate copolymer;
Or a mixture of two or more resins selected from the resin group,
Or a copolymer of two or more resins selected from the resin group,
The heat ray shielding film according to claim 1, wherein the heat ray shielding film is any one of the above . The heat ray shielding film according to claim 1, wherein the thermoplastic resin is a polyvinyl butyral resin and further contains a plasticizer. 7. The heat ray shielding film according to claim 1, wherein the composite tungsten oxide fine particles are at least one selected from Cs _0.33 WO ₃ and Rb _0.33 WO ₃ . The heat ray shielding film according to any one of claims 1 to 7, wherein the composite tungsten oxide fine particles are fine particles having a dispersed particle diameter of 40 nm or less. The heat-ray shielding film is further heat-ray shielding film according to any one of claims 1 to 8 you, characterized in that it contains an ultraviolet absorber. The heat ray shielding film according to claim 9, wherein the ultraviolet absorber is one or more selected from a benzotriazole compound and a benzophenone compound. The heat ray shielding film according to claim 9 or 10, wherein a content of the ultraviolet absorber in the heat ray shielding film is 0.02 mass% or more and 5.0 mass% or less. The heat ray shielding film according to any one of claims 1 to 11, wherein the heat ray shielding film further contains a polyvalent metal salt. The heat ray shielding film according to claim 12, wherein the polyvalent metal salt is bis (2-ethylbutyrate) magnesium. A heat ray shielding laminated transparent base material, wherein the heat ray shielding film according to any one of claims 1 to 13 is present between a plurality of transparent base materials. The heat ray shielding laminated transparent base material according to claim 14 , wherein the yellowness degree (YI) calculated by JIS K 7373 is −20.0 or more and 10.0 or less. The heat ray shielding laminated transparent base material according to claim 14 , wherein the yellowness (YI) calculated by JIS K 7373 is -20.0 or more and 5.0 or less. The heat ray shielding laminated transparent base material according to claim 14 , wherein at least one of the transparent base materials is glass. An automobile, wherein the heat ray shielding laminated transparent base material according to any one of claims 14 to 17 is mounted as a window material. The building characterized by using the heat ray shielding laminated transparent base material in any one of Claim 14 to 17 as a window material.