JP2000319554A - Coating liquid for forming heat-ray and ultraviolet-ray shielding film, and heat-ray and ultraviolet-ray shielding film prepared by using the liquid - Google Patents
Coating liquid for forming heat-ray and ultraviolet-ray shielding film, and heat-ray and ultraviolet-ray shielding film prepared by using the liquidInfo
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- JP2000319554A JP2000319554A JP11125463A JP12546399A JP2000319554A JP 2000319554 A JP2000319554 A JP 2000319554A JP 11125463 A JP11125463 A JP 11125463A JP 12546399 A JP12546399 A JP 12546399A JP 2000319554 A JP2000319554 A JP 2000319554A
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- Prior art keywords
- ultraviolet
- shielding film
- ray
- forming
- ultraviolet ray
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラス、プラスチ
ック、その他の熱線・紫外線遮蔽機能を必要とする透明
基材に応用可能な熱線・紫外線遮蔽材料に関するもので
あり、より詳しくは、太陽光線の特定の波長を選択的に
吸収または反射する成分を含み、常温硬化が可能である
熱線・紫外線遮蔽膜形成用塗布液およびこれを用いて形
成した熱線・紫外線遮蔽膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray / ultraviolet ray shielding material applicable to glass, plastic, and other transparent substrates requiring a heat ray / ultraviolet ray ray shielding function. The present invention relates to a coating solution for forming a heat ray / ultraviolet ray shielding film which contains a component which selectively absorbs or reflects a specific wavelength, and which can be cured at room temperature, and a heat ray / ultraviolet ray shielding film formed using the same.
【０００２】[0002]
【従来の技術】太陽光線は、近赤外線（熱線）、可視光
線、紫外線の３つに大きく分けられる。このうち、長波
長領域の近赤外線は熱エネルギーとして人体に感じる光
であり、室内、車内の温度上昇の原因となる。また、短
波長領域の紫外線は、日焼け、しみ、発癌、視力障害な
ど人体への悪影響があり、また、物品の機械的強度の低
下、色褪せ等の外観劣化、食品劣化、印刷物の色調低下
なども引き起こす。2. Description of the Related Art Sunlight rays are roughly classified into three types: near infrared rays (heat rays), visible rays, and ultraviolet rays. Of these, near-infrared light in the long wavelength region is light that is perceived by the human body as heat energy, and causes a rise in temperature in a room or vehicle. In addition, ultraviolet rays in the short wavelength region have an adverse effect on the human body such as sunburn, spots, carcinogenesis, visual impairment, and also decrease in mechanical strength of articles, appearance deterioration such as discoloration, food deterioration, color tone of printed matter, and the like. cause.
【０００３】これらの不要な熱線や有害な紫外線を同時
に遮蔽するために、熱線・紫外線遮蔽膜を基材上に形成
し、熱線・紫外線遮蔽機能を有するガラス、プラスチッ
ク、フィルムなどが使用されている。In order to simultaneously shield these unnecessary heat rays and harmful ultraviolet rays, a heat ray / ultraviolet ray shielding film is formed on a substrate, and glass, plastic, film, etc. having a heat ray / ultraviolet ray shielding function are used. .
【０００４】従来の熱線・紫外線遮蔽膜には、貴金属
（Ａｕ、Ａｇなど）や銅（Ｃｕ）、窒化チタン（Ｔｉ
Ｎ）、アルミニウム（Ａｌ）などの伝導電子を多量にも
つ金属材料が使用されているが、これらの材料では近赤
外線だけでなく可視光領域の光も同時に反射もしくは吸
収する性質があり、可視光透過率が低いという欠点があ
った。このため、建材、乗り物、電話ボックス等の透明
基材にこれらの材料を利用する場合は、可視光領域の透
過率を高くするために膜厚を薄くする必要があった。Conventional heat ray / ultraviolet ray shielding films include noble metals (Au, Ag, etc.), copper (Cu), and titanium nitride (Ti).
N), aluminum (Al), and other metal materials having a large amount of conduction electrons are used. These materials have the property of simultaneously reflecting or absorbing not only near-infrared light but also light in the visible light region. There is a disadvantage that the transmittance is low. Therefore, when these materials are used for transparent base materials such as building materials, vehicles, and telephone boxes, it is necessary to reduce the film thickness in order to increase the transmittance in the visible light region.
【０００５】通常これらの材料を用いた薄膜の形成には
スパッタリング法や蒸着法が利用されるが、これらの方
法では大がかりな真空装置を必要とするため生産性に劣
り、膜の製造コストが高くなった。また、大面積の成膜
が困難であった。[0005] Usually, a sputtering method or a vapor deposition method is used to form a thin film using these materials. However, these methods require a large-scale vacuum apparatus, and thus are inferior in productivity and high in film production cost. became. Also, it was difficult to form a large area film.
【０００６】熱線・紫外線遮蔽材料を含有する塗布液を
用いて遮蔽膜を基材上に形成することで、簡単かつ低コ
ストで熱線・紫外線遮蔽機能をもつ基材を製造すること
ができる。例えば、光の波長よりも１桁以上微細な微粒
子を分散した塗布液の開発が試みられているが、上記従
来の金属材料では微粒子化による酸化が問題となり、ま
た、Ａｕの使用ではコストが高くなって好ましくない。[0006] By forming a shielding film on a substrate using a coating solution containing a heat ray / ultraviolet ray shielding material, a substrate having a heat ray / ultraviolet ray shielding function can be manufactured simply and at low cost. For example, attempts have been made to develop a coating solution in which fine particles that are one or more digits smaller than the wavelength of light are dispersed. However, in the above-described conventional metal materials, oxidation due to fine particles becomes a problem, and the cost is high when Au is used. It is not preferable.
【０００７】また、可視光透過率が高く、かつ熱線遮蔽
機能をもつ材料としてアンチモン含有酸化錫（ＡＴＯ）
や錫含有酸化インジウム（ＩＴＯ）などが知られてい
る。これを微細化して塗布液とすることも行われている
が、近赤外光の遮蔽能はあまり大きくなく、十分な熱線
遮蔽効果を得るためには多量の添加が必要であり、コス
トが高くなる。また膜強度が大きく低下してしまうため
実用的でなかった。Further, antimony-containing tin oxide (ATO) is used as a material having a high visible light transmittance and a heat ray shielding function.
And tin-containing indium oxide (ITO) are known. Although this is also refined into a coating liquid, the shielding ability of near-infrared light is not very large, and a large amount of addition is necessary to obtain a sufficient heat ray shielding effect, and the cost is high. Become. In addition, the film strength was greatly reduced, so that it was not practical.
【０００８】建築物の窓や自動車の窓ガラスなど、既に
使用されている基材に対しても熱線・紫外線遮蔽材料を
含有する塗布液を用いて熱線・紫外線遮蔽膜を形成し、
熱線・紫外線遮蔽機能をもたせることができる。既に使
用されている基材に対して熱線・紫外線遮蔽膜を形成す
る場合、常温で硬化が可能であれば、硬化に特別な装置
を準備する必要がなく有利である。このように塗布液が
常温硬化可能であって、しかも熱線及び紫外線を遮蔽す
る膜が形成できれば応用が広がるが、そのような塗布液
は知られていなかった。A heat ray / ultraviolet ray shielding film is formed on a substrate already used, such as a window of a building or a window glass of an automobile, by using a coating liquid containing a heat ray / ultraviolet ray shielding material,
It can have a heat ray / ultraviolet ray shielding function. When a heat ray / ultraviolet ray shielding film is formed on a substrate that has already been used, if curing can be performed at room temperature, there is no need to prepare a special device for curing, which is advantageous. If the coating solution can be cured at room temperature and a film that blocks heat rays and ultraviolet rays can be formed in such a manner, the application will be expanded, but such a coating solution has not been known.
【０００９】紫外線吸収剤としては、短波長領域の紫外
線を効率よく吸収する透明材料として、ベンゾフェノン
やベンゾトリアゾールなどの有機紫外線吸収剤が知られ
ている。これらの紫外線吸収剤は単独で塗膜を形成する
ことができず、通常は、添加剤として用いられる。これ
ら紫外線吸収剤は長期間使用すると蒸散などが起こり、
基材の紫外線遮蔽能が劣化する問題があった。このため
基材の紫外線遮蔽能を長時間持続させるためには紫外線
吸収剤を多量に使用することが必要であった。As a UV absorber, an organic UV absorber such as benzophenone or benzotriazole is known as a transparent material that efficiently absorbs ultraviolet rays in a short wavelength region. These ultraviolet absorbers cannot form a coating film alone and are usually used as additives. When these UV absorbers are used for a long time, transpiration occurs,
There was a problem that the ultraviolet shielding ability of the base material deteriorated. For this reason, it was necessary to use a large amount of an ultraviolet absorber in order to maintain the ultraviolet shielding ability of the substrate for a long time.
【００１０】多量の紫外線吸収剤を使用すると紫外線吸
収剤が表面にしみ出したり（以下これを、「ブリードア
ウト」という。）、基材に曇りが生じたりするため、塗
膜形成の目的に対しては実用化の障害となっていた。When a large amount of an ultraviolet absorbent is used, the ultraviolet absorbent exudes to the surface (hereinafter referred to as "bleed-out"), and the base material becomes cloudy. This has been an obstacle to commercialization.
【００１１】[0011]
【発明が解決しようとする課題】そこで本発明は、上記
従来技術の問題点を解決し、透明基材に応用でき、常温
での塗膜形成が可能な熱線・紫外線遮蔽膜形成用塗布液
およびこれを用いて形成できる、熱線・紫外線遮蔽能が
高く、紫外線吸収剤のブリードアウトのない熱線・紫外
線遮蔽膜を提供することを目的とする。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and can be applied to a transparent substrate and can form a coating film at normal temperature. An object of the present invention is to provide a heat ray / ultraviolet ray shielding film which can be formed by using this, has a high heat ray / ultraviolet ray shielding ability, and has no bleed-out of an ultraviolet ray absorbent.
【００１２】[0012]
【課題を解決するための手段】発明者らは上記従来の問
題点を解決するため、近赤外光遮蔽材料として自由電子
を多量に保有するＬａＢ6やＧｄＢ6のような６ホウ化物
微粒子に着目し、更に紫外線遮蔽材料として硬化性紫外
線吸収剤を含む組成物を合成し、これらを含む熱線・紫
外線遮蔽膜形成用塗布液および熱線・紫外線遮蔽膜を発
明するに至った。Means for Solving the Problems In order to solve the above-mentioned conventional problems, the present inventors have developed a method for forming a near-infrared light shielding material by using hexaboride fine particles such as LaB 6 and GdB 6 having a large amount of free electrons. Attention was paid to further synthesizing a composition containing a curable ultraviolet absorber as an ultraviolet shielding material, and invented a coating solution for forming a heat ray / ultraviolet ray shielding film and a heat ray / ultraviolet ray shielding film containing these.
【００１３】すなわち、本発明の熱線・紫外線遮蔽膜形
成用塗布液は、近赤外光遮蔽材料と、硬化性紫外線吸収
剤と、希釈溶媒と、硬化触媒とを含有し、常温で硬化可
能である熱線・紫外線遮蔽膜形成用塗布液であって、該
近赤外光遮蔽材料が、平均粒径２００ｎｍ以下の６ホウ
化物（ＣｅＢ6、ＧｄＢ6、ＴｂＢ6、ＤｙＢ6、Ｈｏ
Ｂ 6、ＹＢ6、ＳｍＢ6、ＥｕＢ6、ＥｒＢ6、ＴｍＢ6、Ｙ
ｂＢ6、ＬｕＢ6、ＳｒＢ6、ＣａＢ6、ＬａＢ6、Ｐｒ
Ｂ6、及びＮｄＢ6のうちの１種以上）微粒子からなり、
該硬化性紫外線吸収剤は少なくとも、２、２’、４、
４’−テトラヒドロキシベンゾフェノンとイソシアノ基
をもつアルコキシシランとを触媒の存在下で反応させて
得られた一般式（１）で示される硬化性紫外線吸収剤を
含むことを特徴とする。That is, the heat ray / ultraviolet ray shielding film type of the present invention
The coating liquid for the composition is composed of a near-infrared light shielding material and
Curing agent, diluting solvent, and curing catalyst
Coating liquid for forming a heat ray / ultraviolet ray shielding film,
The near-infrared light shielding material is made of 6
(CeB6, GdB6, TbB6, DyB6, Ho
B 6, YB6, SmB6, EuB6, ErB6, TmB6, Y
bB6, LuB6, SrB6, CaB6, LaB6, Pr
B6, And NdB6One or more of the above) fine particles,
The curable UV absorber is at least 2, 2 ', 4,
4'-tetrahydroxybenzophenone and isocyano group
With an alkoxysilane having a carboxylic acid in the presence of a catalyst
The obtained curable ultraviolet absorber represented by the general formula (1)
It is characterized by including.
【００１４】[0014]
【化２】 Embedded image
【００１５】但し、一般式（１）中のＸは、加水分解に
よってシラノールを生じるアルコキシル基を示し、一般
式（１）中のＲは、炭素数１〜３のアルキレン鎖を示
す。However, X in the general formula (1) represents an alkoxyl group that produces silanol by hydrolysis, and R in the general formula (1) represents an alkylene chain having 1 to 3 carbon atoms.
【００１６】加水分解によってシラノールを生じるアル
コキシル基Ｘには、例えば、メトキシ基、エトキシ基、
プロポキシ基、ブトキシ基等が挙げられる。The alkoxyl group X that produces silanol by hydrolysis includes, for example, a methoxy group, an ethoxy group,
And a propoxy group and a butoxy group.
【００１７】前記硬化性紫外線吸収剤の含有量は、塗布
液に対して０．５〜５３ｗｔ％であることが好ましい。The content of the curable ultraviolet absorber is preferably 0.5 to 53% by weight based on the coating solution.
【００１８】また、前記熱線・紫外線遮蔽膜形成用塗布
液には、ＣｅＯ2、ＺｎＯ、Ｆｅ2Ｏ 3、及び、ＦｅＯＯ
Ｈのうちの１種以上からなる平均粒径１００ｎｍ以下の
微粒子の無機紫外線遮蔽成分を更に含有させてもよい。Further, the coating for forming the heat ray / ultraviolet ray shielding film.
The liquid is CeOTwo, ZnO, FeTwoO Three, And FeOO
H having an average particle diameter of 100 nm or less
A fine particle inorganic ultraviolet shielding component may be further contained.
【００１９】また、前記熱線・紫外線遮蔽膜形成用塗布
液には、固形分として更に、アクリル樹脂、または／及
び、コロイダルシリカを含めてもよい。Further, the coating solution for forming a heat ray / ultraviolet ray shielding film may further contain an acrylic resin and / or colloidal silica as a solid content.
【００２０】また、本発明の熱線・紫外線遮蔽膜は、上
記いずれかの熱線・紫外線遮蔽膜形成用塗布液を基材に
塗布し、硬化して得られる。Further, the heat ray / ultraviolet ray shielding film of the present invention is obtained by applying any one of the above-mentioned heat ray / ultraviolet ray shielding film forming coating liquid to a base material and curing.
【００２１】[0021]
【発明の実施の形態】本発明の熱線・紫外線遮蔽膜形成
用塗布液及び膜における近赤外光遮蔽材料は、６ホウ化
物（ＣｅＢ6、ＧｄＢ6、ＴｂＢ6、ＤｙＢ6、ＨｏＢ6、
ＹＢ6、ＳｍＢ 6、ＥｕＢ6、ＥｒＢ6、ＴｍＢ6、Ｙｂ
Ｂ6、ＬｕＢ6、ＳｒＢ6、ＣａＢ6、ＬａＢ 6、ＰｒＢ6、
ＮｄＢ6）微粒子であり、これらの１種単独で、あるい
は２種以上が混合されて使用される。DESCRIPTION OF THE PREFERRED EMBODIMENTS Formation of heat ray / ultraviolet ray shielding film of the present invention
Near-infrared light shielding material in coating solution and film for
Object (CeB6, GdB6, TbB6, DyB6, HoB6,
YB6, SmB 6, EuB6, ErB6, TmB6, Yb
B6, LuB6, SrB6, CaB6, LaB 6, PrB6,
NdB6) Fine particles, one of which alone or
Are used as a mixture of two or more.
【００２２】これら６ホウ化物微粒子は暗い青紫色など
を呈する粉末であるが、粒径が可視光波長に比べて十分
小さく、薄膜中に分散した状態においては膜に可視光透
過性が生じる。しかし赤外光の遮蔽能は十分強く保持で
きる。実験によれば、これらの微粒子を十分細かく且つ
均一に分散した膜では、透過率が波長４００〜７００ｎ
ｍの間に極大値をもち、且つ７００〜１８００ｎｍの間
に極小値をもつことが観察される。可視光波長が３８０
〜７８０ｎｍであり、視感度が５５０ｎｍ付近をピーク
とする釣鐘型であることを考慮すると、このような膜で
は可視光を有効に透過しそれ以外の波長の光を有効に吸
収・反射することが理解できる。These hexaboride fine particles are powders exhibiting a dark blue-violet color or the like, but have a particle size sufficiently smaller than the wavelength of visible light, and when dispersed in a thin film, the film has visible light transmittance. However, the ability to shield infrared light can be maintained sufficiently strong. According to experiments, in a film in which these fine particles are sufficiently finely and uniformly dispersed, the transmittance has a wavelength of 400 to 700 n.
It is observed that it has a local maximum between m and a local minimum between 700 and 1800 nm. Visible light wavelength is 380
Considering that the film has a bell shape with a luminosity factor of around 550 nm, such a film can effectively transmit visible light and effectively absorb and reflect light of other wavelengths. It can be understood.
【００２３】６ホウ化物微粒子の平均粒径は２００ｎｍ
以下が良く、１００ｎｍ以下がより好ましい。平均粒径
が２００ｎｍを超えると微粒子同士の凝集傾向が強くな
り、塗布液中の微粒子の沈降の原因となるからである。
また、２００ｎｍを超える粒子もしくはそれらの凝集し
た粗大粒子の存在は、それによる光散乱により可視光透
過率低下の原因となるので好ましくない。The average particle diameter of the hexaboride fine particles is 200 nm.
Or less, and more preferably 100 nm or less. If the average particle size exceeds 200 nm, the tendency of the fine particles to coagulate becomes stronger, which causes sedimentation of the fine particles in the coating solution.
Further, the presence of particles having a size exceeding 200 nm or their aggregated coarse particles is not preferable because it causes a reduction in visible light transmittance due to light scattering.
【００２４】６ホウ化物微粒子は近赤外線と紫外線の遮
蔽能をもつが、紫外線の吸収は比較的小さい。このた
め、十分な紫外線吸収能をもたせるためには紫外線吸収
剤の添加が必要である。The hexaboride fine particles have a near-infrared ray and ultraviolet ray shielding ability, but absorb relatively little ultraviolet ray. For this reason, it is necessary to add an ultraviolet absorber in order to have a sufficient ultraviolet absorbing ability.
【００２５】本発明における硬化性紫外線吸収剤は、
２、２’、４、４’−テトラヒドロキシベンゾフェノン
とγ−イソシアネートプロピルトリメトキシシランやγ
−イソシアネートプロピルトリエトキシシラン等のイソ
シアノ基をもつアルコキシシランをジブチルスズジラウ
レート、ジブチルスズジオクトエート、ジオクチルスズ
ジラウレート等の触媒の存在下で反応させて合成される
反応物で、一般式（１）で表される。The curable ultraviolet absorber according to the present invention comprises:
2,2 ′, 4,4′-tetrahydroxybenzophenone and γ-isocyanatopropyltrimethoxysilane or γ
A reactant synthesized by reacting an alkoxysilane having an isocyano group such as isocyanatopropyltriethoxysilane in the presence of a catalyst such as dibutyltin dilaurate, dibutyltin dioctoate, or dioctyltin dilaurate; represented by the general formula (1): Is done.
【００２６】本発明の硬化性紫外線吸収剤は分子内にベ
ンゾフェノン系の骨格をもち、これが紫外線の吸収に寄
与する。また、分子端のアルコキシル基は加水分解して
反応性の高いシラノールを生じ、これが縮合重合するこ
とによって自身で高分子化、あるいは他のバインダー成
分と結合することができる。なおこの硬化性紫外線吸収
剤はアルコキシル基が加水分解し、シラノールが縮合重
合したオリゴマーの形態でも存在しうる。The curable ultraviolet absorber of the present invention has a benzophenone skeleton in the molecule, which contributes to the absorption of ultraviolet light. In addition, the alkoxyl group at the molecular end is hydrolyzed to generate highly reactive silanol, which can be polymerized by itself or combined with other binder components by condensation polymerization. The curable ultraviolet absorber may be present in the form of an oligomer obtained by hydrolysis of an alkoxyl group and condensation polymerization of silanol.
【００２７】本発明の熱線・紫外線遮蔽膜形成用塗布液
は、この硬化性紫外線吸収剤を少なくとも一種類含有す
るものであるが、その硬化は硬化性紫外線吸収剤のアル
コシキル基の加水分解とそれに続くシラノールの縮合重
合による高分子化によって起こり、他のバインダー成分
は必須ではない。このように紫外線吸収剤自体が重合し
堅牢な塗膜を形成するため紫外線吸収剤のブリードアウ
トはない。The coating solution for forming a heat ray / ultraviolet ray shielding film of the present invention contains at least one kind of the curable ultraviolet absorbent. The curing is carried out by hydrolysis of the alkoxy group of the curable ultraviolet absorbent and the hydrolysis thereof. This is caused by the subsequent polymerization of silanol by condensation polymerization, and other binder components are not essential. As described above, since the ultraviolet absorbent itself is polymerized to form a robust coating film, there is no bleed out of the ultraviolet absorbent.
【００２８】また、この硬化性紫外線吸収剤には湿気硬
化性があるが、常温での硬化速度を実用的なものとする
ために、硬化触媒の添加が必須である。硬化触媒として
はパラトルエンスルホン酸などの一般的な酸触媒を用い
ることができる。Although the curable ultraviolet absorber has moisture curability, it is necessary to add a curing catalyst in order to make the curing speed at room temperature practical. A general acid catalyst such as paratoluenesulfonic acid can be used as the curing catalyst.
【００２９】熱線・紫外線遮蔽膜形成用塗布液中の希釈
溶媒は特に限定されるものではなく、塗布条件や、塗布
環境、塗布液中の固形分の種類に合わせて選択可能であ
る。例えば、メタノール、エタノール、イソブチルアル
コール等のアルコール類、エチレングリコールモノメチ
ルエーテル、エチレングリコールモノエチルエーテル等
のエーテルアルコール類、酢酸メチル、酢酸エチル等の
エステル類、メチルエチルケトン、シクロヘキサノン等
のケトン類など各種溶媒が使用可能である。また用途に
よって１種または２種以上の溶媒を組み合わせて使用し
ても良い。The diluting solvent in the coating solution for forming a heat ray / ultraviolet shielding film is not particularly limited, and can be selected according to the coating conditions, the coating environment, and the type of solids in the coating solution. For example, various solvents such as alcohols such as methanol, ethanol and isobutyl alcohol, ether alcohols such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, esters such as methyl acetate and ethyl acetate, and ketones such as methyl ethyl ketone and cyclohexanone. Can be used. One or more solvents may be used in combination depending on the application.
【００３０】また、塗布液中の硬化性紫外線吸収剤を含
む合成物の含有量は、ＺｎＯ、ＣｅＯ2、Ｆｅ2Ｏ3、Ｆ
ｅＯＯＨなどの無機紫外線吸収剤と併用しない場合は、
１２〜５３ｗｔ％であることが望ましい。含有量が１２
ｗｔ％未満であると塗布硬化して得られる熱線・紫外線
遮蔽膜の紫外線遮蔽能が低く、５３ｗｔ％を超えるとそ
の他の固形分を添加しない場合でも塗布液の粘度が上昇
し塗布性が悪化する。The content of the composition containing the curable ultraviolet absorber in the coating solution is ZnO, CeO 2 , Fe 2 O 3 , F
When not used with an inorganic ultraviolet absorber such as eOOH,
It is desirable that the content be 12 to 53 wt%. 12 content
When the amount is less than wt%, the ultraviolet ray shielding ability of the heat ray / ultraviolet ray shielding film obtained by coating and curing is low. When the amount exceeds 53% by weight, the viscosity of the coating solution increases even if no other solid content is added, and the coating property deteriorates. .
【００３１】但し、ＺｎＯ、ＣｅＯ2、Ｆｅ2Ｏ3、Ｆｅ
ＯＯＨなどの無機紫外線吸収剤と併用して用いられる場
合は、塗布液中の濃度はこれより低くても良く、０．５
〜１２ｗｔ％の添加濃度でも充分実用性のある日射遮蔽
膜形成用塗布液として使用可能である。However, ZnO, CeO 2 , Fe 2 O 3 , Fe
When used in combination with an inorganic ultraviolet absorber such as OOH, the concentration in the coating solution may be lower than this,
Even an addition concentration of 12 wt% can be used as a sufficiently practical coating liquid for forming a solar shading film.
【００３２】塗布液中の固形分として、アクリル樹脂、
ウレタン樹脂等の有機樹脂、コロイダルシリカ、Ａｌ2
Ｏ3、ＴｉＯ2、ＺｒＯ2等の無機超微粒子、種々のシラ
ンカップリング剤等を１種または２種以上添加してもよ
い。これによって塗布液の塗布性の改良、塗布膜の硬度
の改良、基材への密着力の改良などが成される。As the solid content in the coating liquid, acrylic resin,
Organic resin such as urethane resin, colloidal silica, Al 2
One or more inorganic ultrafine particles such as O 3 , TiO 2 , and ZrO 2 , various silane coupling agents, and the like may be added. As a result, the coating properties of the coating solution are improved, the hardness of the coating film is improved, and the adhesion to the substrate is improved.
【００３３】本発明の塗布液をガラス、プラスチック
板、フィルムなどの基材に塗布し常温で硬化させること
によって、基材上に長期間安定な紫外線遮蔽能をもつ熱
線・紫外線遮蔽膜を形成することができる。塗布液の塗
布方法は特に限定されるものではなく、スピンコート
法、スプレーコート法、ディップコート法、スクリーン
印刷法、布や刷毛による方法等、液を平坦にかつ薄く均
一に塗布できる方法であればいかなる方法でもよい。By coating the coating solution of the present invention on a substrate such as glass, plastic plate or film and curing at room temperature, a heat ray / ultraviolet ray shielding film having a long term stable ultraviolet ray shielding ability is formed on the substrate. be able to. The method of applying the coating liquid is not particularly limited, and any method that can apply the liquid flat and thin uniformly, such as a spin coating method, a spray coating method, a dip coating method, a screen printing method, a method using a cloth or a brush, and the like. Any method may be used.
【００３４】基材上に形成された熱線・紫外線遮蔽膜
は、基材に長期間安定な熱線・紫外線遮蔽機能を付与す
るとともに、基材そのものの紫外線による劣化を抑制す
る。The heat ray / ultraviolet ray shielding film formed on the base material provides the base material with a stable heat ray / ultraviolet ray shielding function for a long period of time and suppresses deterioration of the substrate itself due to ultraviolet rays.
【００３５】[0035]
【実施例】以下に本発明の実施例、比較例を示して本発
明を更に詳細に説明する。The present invention will be described in more detail with reference to the following examples and comparative examples.
【００３６】実施例１ ・・・ ＬａＢ6微粒子（平均
粒径６７ｎｍ）１０ｇ、ジアセトンアルコール８６ｇ及
び微粒子分散用カップリング剤４ｇを混合し、直径４ｍ
ｍのジルコニアボールを用いて１５０時間ボールミル混
合をおこないＬａＢ6微粒子の分散液１００ｇを作製し
た（Ａ液）。Example 1 10 g of LaB 6 fine particles (average particle diameter 67 nm), 86 g of diacetone alcohol and 4 g of a coupling agent for dispersing fine particles were mixed, and the diameter was 4 m.
Using a zirconia ball having a diameter of 150 m, ball mill mixing was performed for 150 hours to prepare 100 g of a dispersion of LaB 6 fine particles (solution A).
【００３７】２，２’，４，４’−テトラヒドロキシベ
ンゾフェノン５７ｇとγ−イソシアネートプロピルトリ
エトキシシラン７７ｇをビーカーにとり、ジブチルスズ
ジラウレートを１ｇ加えてメカニカルスターラーで混合
攪拌を行った。発熱反応が起こるがそのまま約１時間放
置冷却し、目的の反応性紫外線吸収剤を含む赤褐色、高
粘度の液を得た（合成液１）。57 g of 2,2 ', 4,4'-tetrahydroxybenzophenone and 77 g of γ-isocyanatopropyltriethoxysilane were placed in a beaker, 1 g of dibutyltin dilaurate was added, and the mixture was stirred with a mechanical stirrer. An exothermic reaction occurs, but the solution is left standing for about 1 hour and cooled to obtain a red-brown, high-viscosity liquid containing the desired reactive ultraviolet absorber (synthetic liquid 1).
【００３８】１３．５ｇの合成液１と１３．１ｇのエタ
ノールを混合攪拌し、均一に溶解した。更に溶媒として
エチレングリコールモノメチルエーテル４３ｇとエチレ
ングリコールモノブチルエーテル２５ｇ、硬化触媒とし
てパラトルエンスルホン酸（一水和物）０．４ｇを加え
て混合攪拌した。更にＡ液を５ｇ加えて混合攪拌し、熱
線・紫外線遮蔽膜形成用塗布液を得た。塗布液の固形分
は１４．６ｗｔ％、ＬａＢ6の含有量は０．５ｗｔ％、
合成液１の含有量は１３．５ｗｔ％である。13.5 g of Synthetic Solution 1 and 13.1 g of ethanol were mixed and stirred to dissolve uniformly. Further, 43 g of ethylene glycol monomethyl ether and 25 g of ethylene glycol monobutyl ether were added as solvents, and 0.4 g of paratoluenesulfonic acid (monohydrate) was added as a curing catalyst, followed by mixing and stirring. Further, 5 g of solution A was added and mixed and stirred to obtain a coating solution for forming a heat ray / ultraviolet ray shielding film. The solid content of the coating solution is 14.6 wt%, the content of LaB 6 is 0.5 wt%,
The content of the synthesis solution 1 is 13.5 wt%.
【００３９】この熱線・紫外線遮蔽膜形成用塗布液を３
ｍｍのソーダライム系ガラス基板上にバーコーターを用
いて塗布し、常温で硬化して塗布膜を得た。塗布膜の透
過率を日立製作所製の分光光度計を用いて測定し、ＪＩ
Ｓ Ｒ ３１０６に従って可視光透過率（τｖ）、日射
透過率（τｅ）を、ＩＳＯ ９０５０に従って紫外線透
過率（τｕｖ）を算出した。塗布硬化してから常温の室
内に放置し、３０日後に膜表面の観察を行ってブリード
アウトの有無を調べた。またテーバー摩耗試験機で摩耗
輪ＣＳ１２ｆを用いて荷重２５０ｇ、５０回転の摩耗試
験を行い、試験前後のヘイズの変化量（ΔＨ）で膜の摩
耗強度を評価した。The coating solution for forming the heat ray / ultraviolet shielding film was
It was applied on a soda-lime glass substrate having a thickness of 2 mm using a bar coater and cured at room temperature to obtain a coating film. The transmittance of the coating film was measured using a spectrophotometer manufactured by Hitachi, Ltd.
The visible light transmittance (τv) and the solar radiation transmittance (τe) were calculated according to SR 3106, and the ultraviolet transmittance (τuv) was calculated according to ISO 9050. After coating and curing, the film was allowed to stand in a room at room temperature, and after 30 days, the surface of the film was observed to check for bleed-out. Further, a wear test was performed using a wear wheel CS12f with a load of 250 g and 50 rotations using a Taber abrasion tester, and the abrasion strength of the film was evaluated based on the change in haze before and after the test (ΔH).
【００４０】指触乾燥までの硬化時間は４０分であっ
た。τｖは７５．１％、τｅは５４．３％であり、可視
光透過性があり、近赤外光の遮蔽能があることがわかっ
た。τｕｖは０．０３％であり紫外光の遮蔽能も優れて
いる。The curing time until touch drying was 40 minutes. τv was 75.1% and τe was 54.3%, indicating that the film has visible light transmittance and has a near infrared light shielding ability. τuv is 0.03%, and the ability to block ultraviolet light is excellent.
【００４１】３０日後の膜面にブリードアウトは観察さ
れなかった。すなわち上記塗布液は一般式（１）で示さ
れるように、ベンゾフェノン骨格がイソシアノ基をもつ
アルコキシシランと酸素原子を介して結合しているため
に、紫外線吸収能を有するベンゾフェノン骨格がバイン
ダー中に安定化してブリードアウトを抑制したものであ
る。No bleed-out was observed on the film surface after 30 days. That is, as shown in the general formula (1), since the benzophenone skeleton is bonded to an alkoxysilane having an isocyano group via an oxygen atom, the coating solution has a stable benzophenone skeleton having an ultraviolet absorbing ability in a binder. And bleed-out is suppressed.
【００４２】爪では全く傷がつかない強固な膜が形成さ
れており、テーバー摩耗試験によるヘイズの劣化ΔＨ値
は１９％となった。A strong film that was not damaged at all was formed on the nail, and the haze deterioration ΔH value by Taber abrasion test was 19%.
【００４３】以上の評価結果を表１にまとめて示す。以
下の実施例、比較例でも同様の評価を行い、結果を表１
に示す。Table 1 summarizes the above evaluation results. The same evaluation was performed in the following Examples and Comparative Examples.
Shown in
【００４４】実施例２ ・・・ ＣｅＢ6微粒子（平均
粒径４６ｎｍ）１０ｇ、ジアセトンアルコール８６ｇ及
び微粒子分散用カップリング剤４ｇを混合し、直径４ｍ
ｍのジルコニアボールを用いて１５０時間ボールミル混
合をおこないＬａＢ6微粒子の分散液１００ｇを作製し
た（Ｂ液）。Example 2 10 g of CeB 6 fine particles (average particle diameter: 46 nm), 86 g of diacetone alcohol and 4 g of a coupling agent for fine particle dispersion were mixed, and the diameter was 4 m.
Using a zirconia ball having a diameter of 150 m, ball mill mixing was performed for 150 hours to prepare 100 g of a dispersion of LaB 6 fine particles (solution B).
【００４５】２，２’，４，４’−テトラヒドロキシベ
ンゾフェノン５７ｇとγ−イソシアネートプロピルトリ
メトキシシラン７７ｇをビーカーにとり、ジブチルスズ
ジラウレートを１ｇ加えてメカニカルスターラーで混合
攪拌を行った。発熱反応が起こるがそのまま約１時間放
置冷却し、目的の反応性紫外線吸収剤を含む赤褐色、高
粘度の液を得た（合成液２）。57 g of 2,2 ', 4,4'-tetrahydroxybenzophenone and 77 g of γ-isocyanatopropyltrimethoxysilane were placed in a beaker, 1 g of dibutyltin dilaurate was added, and the mixture was stirred with a mechanical stirrer. Although an exothermic reaction occurred, the solution was left standing for about 1 hour and cooled to obtain a red-brown, high-viscosity liquid containing the desired reactive ultraviolet absorber (synthetic liquid 2).
【００４６】１３．５ｇの合成液２と１３．１ｇのエタ
ノールを混合攪拌し、均一に溶解した。更に溶媒として
エチレングリコールモノメチルエーテル４３ｇとエチレ
ングリコールモノブチルエーテル２５ｇ、硬化触媒とし
てパラトルエンスルホン酸（一水和物）０．４ｇを加え
て混合攪拌した。更にＢ液を５ｇ加えて混合攪拌し、熱
線・紫外線遮蔽膜形成用塗布液を得た。塗布液の固形分
は１４．６ｗｔ％、ＣｅＢ6の含有量は０．５ｗｔ％、
合成液２の含有量は１３．５ｗｔ％である。13.5 g of Synthetic Solution 2 and 13.1 g of ethanol were mixed and stirred to dissolve uniformly. Further, 43 g of ethylene glycol monomethyl ether and 25 g of ethylene glycol monobutyl ether were added as solvents, and 0.4 g of paratoluenesulfonic acid (monohydrate) was added as a curing catalyst, followed by mixing and stirring. Further, 5 g of the solution B was added and mixed and stirred to obtain a coating solution for forming a heat ray / ultraviolet shielding film. The solid content of the coating solution is 14.6 wt%, the content of CeB 6 is 0.5 wt%,
The content of the synthesis solution 2 is 13.5 wt%.
【００４７】この熱線・紫外線遮蔽膜形成用塗布液を３
ｍｍのソーダライム系ガラス基板上にバーコーターを用
いて塗布し、常温で硬化して熱線・紫外線遮蔽膜を得
た。This coating solution for forming a heat ray / ultraviolet ray shielding film was
A soda lime-based glass substrate was coated using a bar coater and cured at room temperature to obtain a heat ray / ultraviolet ray shielding film.
【００４８】比較例１ ・・・ 比較のため３ｍｍのソ
ーダライム系ガラス基板のτｖ、τｅ、τｕｖも表１に
示した。Comparative Example 1 .tau.v, .tau.e, and .tau.uv of a 3 mm soda lime glass substrate are also shown in Table 1 for comparison.
【００４９】比較例２ ・・・ 紫外線吸収剤として
２，２’，４，４’−テトラヒドロキシベンゾフェノン
を５ｇ、樹脂バインダーとしてラッカータイプの常温硬
化ウレタン樹脂（溶剤はイソプロピルアルコールで固形
分３０％）を１６．７ｇ、希釈溶剤としてイソブチルア
ルコール４８．３ｇとプロピレングリコールモノエチル
エーテル２５ｇを混合攪拌した。更にＡ液を５ｇ加えて
混合攪拌し、熱線・紫外線遮蔽膜形成用塗布液を得た。
この塗布液中の固形分は１０．７ｗｔ％、ＬａＢ 6の含
有量は０．５ｗｔ％である。また、紫外線吸収剤の含有
量は５ｗｔ％である。Comparative Example 2 As an ultraviolet absorber
2,2 ', 4,4'-tetrahydroxybenzophenone
5g, lacquer type normal temperature hardening as resin binder
Urethane resin (solvent is solid with isopropyl alcohol
(30%) for isobutylamine as a diluting solvent.
48.3 g of alcohol and propylene glycol monoethyl
25 g of ether was mixed and stirred. Add 5 g of solution A
After mixing and stirring, a coating solution for forming a heat ray / ultraviolet shielding film was obtained.
The solid content in this coating solution is 10.7 wt%, LaB 6Including
The amount is 0.5 wt%. Also contains UV absorber
The amount is 5% by weight.
【００５０】この熱線・紫外線遮蔽膜形成用塗布液を３
ｍｍのソーダライム系ガラス基板上にバーコーターを用
いて塗布し、常温で硬化して熱線及び紫外線遮蔽膜を得
た。This heat ray / ultraviolet ray shielding film forming coating solution was
It was applied on a soda lime glass substrate having a thickness of 2 mm using a bar coater and cured at room temperature to obtain a heat ray and ultraviolet ray shielding film.
【００５１】硬化３０日後の観察でブリードアウトが見
られた。これは紫外線吸収剤の２，２’，４，４’−テ
トラヒドロキシベンゾフェノンがバインダーと反応する
機構なしにはバインダー中に安定して存在することがで
きないことを示すものである。ΔＨは３２％であり膜強
度は弱い。Bleed out was observed 30 days after curing. This indicates that the UV absorber 2,2 ', 4,4'-tetrahydroxybenzophenone cannot be stably present in the binder without a mechanism for reacting with the binder. ΔH is 32%, and the film strength is weak.
【００５２】実施例３ ・・・ ９．０ｇの合成液１と
８．７ｇのエタノールを混合攪拌し、均一に溶解した。
更に溶媒としてエチレングリコールモノメチルエーテル
４８ｇとエチレングリコールモノブチルエーテル２５
ｇ、硬化触媒としてパラトルエンスルホン酸（一水和
物）０．３ｇを加えて混合攪拌した。更にＡ液５ｇと無
機紫外線吸収剤であるＦｅＯＯＨ微粒子の分散液（固形
分２０ｗｔ％）を４ｇ加えて混合攪拌し、熱線・紫外線
遮蔽膜形成用塗布液を得た。この塗布液中の固形分は１
０．８ｗｔ％、ＬａＢ6含有量は０．５ｗｔ％、合成液
１の含有量は９．０ｗｔ％である。Example 3 9.0 g of Synthetic Solution 1 and 8.7 g of ethanol were mixed and stirred to dissolve uniformly.
Further, as a solvent, ethylene glycol monomethyl ether (48 g) and ethylene glycol monobutyl ether (25) were used.
g and 0.3 g of paratoluenesulfonic acid (monohydrate) as a curing catalyst were added and mixed and stirred. Further, 5 g of the liquid A and 4 g of a dispersion (solid content: 20 wt%) of FeOOH fine particles as an inorganic ultraviolet absorber were added and mixed and stirred to obtain a coating solution for forming a heat ray / ultraviolet shielding film. The solid content in this coating solution is 1
0.8 wt%, the content of LaB 6 is 0.5 wt%, and the content of the synthetic solution 1 is 9.0 wt%.
【００５３】この熱線・紫外線遮蔽膜形成用塗布液を３
ｍｍのソーダライム系ガラス基板上にバーコーターを用
いて塗布し、常温で硬化して熱線・紫外線遮蔽膜を得
た。This heat ray / ultraviolet ray shielding film forming coating solution was
A soda lime-based glass substrate was coated using a bar coater and cured at room temperature to obtain a heat ray / ultraviolet ray shielding film.
【００５４】τｕｖは０．３１％であり、硬化性紫外線
吸収剤の量が少ない場合でも無機紫外線吸収剤の併用で
充分な紫外線遮蔽能が得られることがわかる。Τuv is 0.31%, and it can be seen that even when the amount of the curable ultraviolet absorber is small, sufficient ultraviolet shielding ability can be obtained by using the inorganic ultraviolet absorber in combination.
【００５５】比較例３ ・・・ ２６ｇの合成液１と１
２．５ｇのエタノールを混合し、更に溶媒としてエチレ
ングリコールモノブチルエーテル７．５ｇ、硬化触媒と
してパラトルエンスルホン酸（一水和物）０．２５ｇを
加えて混合攪拌した。更にＡ液を２．５ｇを加えて混合
攪拌し、熱線・紫外線遮蔽膜形成用塗布液を得た。この
塗布液中の固形分は５４．７ｗｔ％、ＬａＢ6の含有量
は０．５１ｗｔ％、合成液１の含有量は５３．３ｗｔ％
である。Comparative Example 3 26 g of Synthetic Solutions 1 and 1
2.5 g of ethanol was mixed, 7.5 g of ethylene glycol monobutyl ether was further added as a solvent, and 0.25 g of paratoluenesulfonic acid (monohydrate) was added as a curing catalyst, followed by mixing and stirring. Further, 2.5 g of the liquid A was added and mixed and stirred to obtain a coating liquid for forming a heat ray / ultraviolet ray shielding film. The solid content in this coating solution was 54.7% by weight, the content of LaB 6 was 0.51% by weight, and the content of synthesis solution 1 was 53.3% by weight.
It is.
【００５６】この熱線・紫外線遮蔽膜形成用塗布液は粘
度が高く、３ｍｍのソーダライム系ガラス基板上に均一
に塗布することができなかった。The coating solution for forming a heat ray / ultraviolet ray shielding film had a high viscosity and could not be uniformly applied on a 3 mm soda lime glass substrate.
【００５７】実施例４ ・・・ １３．５ｇの合成液１
と１３．１ｇのエタノールを混合攪拌し、均一に溶解し
た。更に溶媒としてエチレングリコールモノメチルエー
テル４０ｇとエチレングリコールモノブチルエーテル２
５ｇ、硬化触媒としてパラトルエンスルホン酸（一水和
物）０．４ｇを加えて混合攪拌した。更にＡ液５ｇと日
産化学製コロイダルシリカ（溶剤はイソプロピルアルコ
ールで固形分３０％）１５．０ｇを加えて混合攪拌し、
熱線・紫外線遮蔽膜形成用塗布液を得た。この塗布液中
の固形分は１９．１ｗｔ％、ＬａＢ6の含有量は０．４
５ｗｔ％、合成液１の含有量は１２．１ｗｔ％である。Example 4 13.5 g of synthetic solution 1
And 13.1 g of ethanol were mixed and stirred to dissolve uniformly. Further, as a solvent, 40 g of ethylene glycol monomethyl ether and ethylene glycol monobutyl ether 2
5 g and 0.4 g of paratoluenesulfonic acid (monohydrate) as a curing catalyst were added and mixed and stirred. Further, 5 g of Solution A and 15.0 g of colloidal silica manufactured by Nissan Chemical Co., Ltd. (solvent: isopropyl alcohol, solid content: 30%) were added, and mixed and stirred.
A coating solution for forming a heat ray / ultraviolet shielding film was obtained. The solid content in this coating solution was 19.1 wt%, and the content of LaB 6 was 0.4.
The content of the synthetic solution 1 was 5 wt% and the content of the synthesis liquid 1 was 12.1 wt%.
【００５８】この熱線・紫外線遮蔽膜形成用塗布液を３
ｍｍのソーダライム系ガラス基板上にバーコーターを用
いて塗布し、常温で硬化して熱線・紫外線遮蔽膜を得
た。ΔＨは１４％でコロイダルシリカの添加によって膜
の摩耗強度が改善された。This heat ray / ultraviolet ray shielding film forming coating solution was
A soda lime-based glass substrate was coated using a bar coater and cured at room temperature to obtain a heat ray / ultraviolet ray shielding film. ΔH was 14%, and the wear strength of the film was improved by the addition of colloidal silica.
【００５９】実施例５ ・・・ １３．５ｇの合成液１
と１３．１ｇのエタノールを混合攪拌し、均一に溶解し
た。更に溶媒としてエチレングリコールモノメチルエー
テル４０ｇとエチレングリコールモノブチルエーテル２
５ｇ、硬化触媒としてパラトルエンスルホン酸（一水和
物）０．４ｇを加えて混合攪拌した。更にＡ液５ｇとア
クリル樹脂をジアセトンアルコールで加熱溶解した溶液
（固形分３０ｗｔ％）１５．０ｇを加えて混合攪拌し、
熱線・紫外線遮蔽膜形成用塗布液を得た。この塗布液中
の固形分は１９．１ｗｔ％、ＬａＢ6の含有量は０．４
５ｗｔ％、合成液１の含有量は１２．１ｗｔ％である。Example 5 13.5 g of synthetic solution 1
And 13.1 g of ethanol were mixed and stirred to dissolve uniformly. Further, as a solvent, 40 g of ethylene glycol monomethyl ether and ethylene glycol monobutyl ether 2
5 g and 0.4 g of paratoluenesulfonic acid (monohydrate) as a curing catalyst were added and mixed and stirred. Further, 5 g of solution A and 15.0 g of a solution (solid content: 30 wt%) obtained by dissolving the acrylic resin by heating with diacetone alcohol were added, and mixed and stirred.
A coating solution for forming a heat ray / ultraviolet shielding film was obtained. The solid content in this coating solution was 19.1 wt%, and the content of LaB 6 was 0.4%.
The content of Synthetic Solution 1 was 5 wt% and 12.1 wt%.
【００６０】この熱線・紫外線遮蔽膜形成用塗布液を３
ｍｍのソーダライム系ガラス基板上にバーコーターを用
いて塗布し、常温で硬化して熱線・紫外線遮蔽膜を得
た。This coating solution for forming a heat ray / ultraviolet shielding film was
A soda lime-based glass substrate was coated using a bar coater and cured at room temperature to obtain a heat ray / ultraviolet ray shielding film.
【００６１】アクリル樹脂の添加により熱線・紫外線遮
蔽膜形成用塗布液の粘度を調整することができ、塗布性
が改良された。The viscosity of the coating solution for forming a heat ray / ultraviolet ray shielding film could be adjusted by adding an acrylic resin, and the coating property was improved.
【００６２】実施例６〜実施例８ ・・・ 実施例１の
ＬａＢ6微粒子を、ＰｒＢ6（平均粒径５３ｎｍ）、Ｎｄ
Ｂ6（平均粒径６６ｎｍ）、ＧｄＢ6（平均粒径４１ｎ
ｍ）に替えたほかは、実施例１と全く同じ手順で熱線・
紫外線遮蔽膜形成用塗布液を作製、塗布し、熱線・紫外
線遮蔽膜を得た。Example 6 to Example 8 The LaB 6 fine particles of Example 1 were replaced with PrB 6 (average particle diameter 53 nm) and Nd.
B 6 (average particle size 66 nm), GdB 6 (average particle size 41 n
m), except that the heating wire
A coating solution for forming an ultraviolet shielding film was prepared and applied to obtain a heat ray / ultraviolet shielding film.
【００６３】比較例４ ・・・ ＣｅＢ6として平均粒
径が２１２ｎｍの粗大粒子を用いたほかは実施例２と全
く同じ手順で熱線・紫外線遮蔽膜形成用塗布液を作製、
塗布し、熱線・紫外線遮蔽膜を得た。得られた膜は可視
光の散乱が強く曇りがあり、実用には向かない。Comparative Example 4 A coating solution for forming a heat ray / ultraviolet shielding film was prepared in exactly the same procedure as in Example 2 except that coarse particles having an average particle size of 212 nm were used as CeB 6 .
It was applied to obtain a heat ray / ultraviolet ray shielding film. The obtained film has strong scattering of visible light and is cloudy, and is not suitable for practical use.
【００６４】[0064]
【表１】 [Table 1]
【００６５】[0065]
【発明の効果】以上示したように、新規の硬化性紫外線
吸収剤を用い、近赤外光遮蔽材料として６ホウ化物微粒
子を添加するることで、常温で硬化し、紫外線吸収剤の
ブリードアウトが無い熱線・紫外線遮蔽膜、及びこれを
形成するための熱線・紫外線遮蔽膜形成用塗布液が提供
できた。本発明により、基材に長期間安定な熱線・紫外
線遮蔽機能を簡便な方法で付与することが可能となっ
た。As described above, by using a novel curable ultraviolet absorbent and adding hexaboride fine particles as a near-infrared light shielding material, the composition is cured at room temperature and bleed out of the ultraviolet absorbent. Thus, a heat ray / ultraviolet ray shielding film having no heat and a coating solution for forming the same were formed. ADVANTAGE OF THE INVENTION According to this invention, it became possible to give the heat ray / ultraviolet ray shielding function stable for a long time to a base material by a simple method.
フロントページの続き Ｆターム(参考） 2H048 FA04 FA05 FA07 FA12 FA18 4J038 CG141 HA216 HA446 HA476 JA33 JC32 KA04 KA06 KA20 MA14 NA19 PC03 PC08 Continued on the front page F term (reference) 2H048 FA04 FA05 FA07 FA12 FA18 4J038 CG141 HA216 HA446 HA476 JA33 JC32 KA04 KA06 KA20 MA14 NA19 PC03 PC08
Claims (5)
剤と、希釈溶媒と、硬化触媒とを含有し、常温で硬化可
能である熱線・紫外線遮蔽膜形成用塗布液であって、該
近赤外光遮蔽材料が、平均粒径２００ｎｍ以下の６ホウ
化物（ＣｅＢ 6、ＧｄＢ6、ＴｂＢ6、ＤｙＢ6、Ｈｏ
Ｂ6、ＹＢ6、ＳｍＢ6、ＥｕＢ6、ＥｒＢ6、ＴｍＢ6、Ｙ
ｂＢ6、ＬｕＢ6、ＳｒＢ6、ＣａＢ6、ＬａＢ6、Ｐｒ
Ｂ6、及びＮｄＢ6のうちの１種以上）微粒子からなり、
該硬化性紫外線吸収剤は少なくとも、２、２’、４、
４’−テトラヒドロキシベンゾフェノンとイソシアノ基
をもつアルコキシシランとを触媒の存在下で反応させて
得られた一般式（１）で示される硬化性紫外線吸収剤を
含む熱線・紫外線遮蔽膜形成用塗布液。 【化１】 但し、一般式（１）中のＸは、加水分解によってシラノ
ールを生じるアルコキシル基を示し、一般式（１）中の
Ｒは、炭素数１〜３のアルキレン鎖を示す。1. A near-infrared light shielding material and a curable ultraviolet ray absorbing material
Curing agent, diluting solvent, and curing catalyst
Coating liquid for forming a heat ray / ultraviolet ray shielding film,
The near-infrared light shielding material is made of 6
(CeB 6, GdB6, TbB6, DyB6, Ho
B6, YB6, SmB6, EuB6, ErB6, TmB6, Y
bB6, LuB6, SrB6, CaB6, LaB6, Pr
B6, And NdB6One or more of the above) fine particles,
The curable UV absorber is at least 2, 2 ', 4,
4'-tetrahydroxybenzophenone and isocyano group
With an alkoxysilane having a carboxylic acid in the presence of a catalyst
The obtained curable ultraviolet absorber represented by the general formula (1)
A coating solution for forming a heat ray / ultraviolet ray shielding film. Embedded imageHowever, X in the general formula (1) is converted to silano by hydrolysis.
And represents an alkoxyl group that generates a hydroxyl group.
R represents an alkylene chain having 1 to 3 carbon atoms.
布液に対して０．５〜５３ｗｔ％である請求項１に記載
の熱線・紫外線遮蔽膜形成用塗布液。2. The coating liquid for forming a heat ray / ultraviolet ray shielding film according to claim 1, wherein the content of the curable ultraviolet absorber is 0.5 to 53 wt% based on the coating liquid.
ｅＯＯＨのうちの１種以上からなる平均粒径１００ｎｍ
以下の微粒子の無機紫外線遮蔽成分を更に含有する、請
求項１または請求項２に記載の熱線・紫外線遮蔽膜形成
用塗布液。3. CeO 2 , ZnO, Fe 2 O 3 , and F
Average particle diameter of at least 100 nm composed of one or more of eOOH
The coating liquid for forming a heat ray / ultraviolet ray shielding film according to claim 1 or 2, further comprising an inorganic ultraviolet ray shielding component of the following fine particles.
は／及び、コロイダルシリカを含む請求項１〜請求項３
の何れかに記載の熱線・紫外線遮蔽膜形成用塗布液。4. The solid content further includes an acrylic resin and / or colloidal silica.
The coating solution for forming a heat ray / ultraviolet ray shielding film according to any one of the above.
熱線・紫外線遮蔽膜形成用塗布液を基材に塗布し、硬化
して得られる熱線・紫外線遮蔽膜。5. A heat ray / ultraviolet ray shielding film obtained by applying the heat ray / ultraviolet ray shielding film forming coating solution according to claim 1 to a substrate and curing the composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12546399A JP3760671B2 (en) | 1999-05-06 | 1999-05-06 | Heat ray / ultraviolet shielding film forming coating liquid and heat ray / ultraviolet shielding film using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12546399A JP3760671B2 (en) | 1999-05-06 | 1999-05-06 | Heat ray / ultraviolet shielding film forming coating liquid and heat ray / ultraviolet shielding film using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000319554A true JP2000319554A (en) | 2000-11-21 |
| JP3760671B2 JP3760671B2 (en) | 2006-03-29 |
Family
ID=14910722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12546399A Expired - Lifetime JP3760671B2 (en) | 1999-05-06 | 1999-05-06 | Heat ray / ultraviolet shielding film forming coating liquid and heat ray / ultraviolet shielding film using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3760671B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1319683A1 (en) * | 2001-12-11 | 2003-06-18 | Asahi Glass Co., Ltd. | Heat radiation blocking fluororesin film |
| US7258923B2 (en) | 2003-10-31 | 2007-08-21 | General Electric Company | Multilayered articles and method of manufacture thereof |
| US7399571B2 (en) | 2005-05-06 | 2008-07-15 | General Electric Company | Multilayered articles and method of manufacture thereof |
| JP2009046609A (en) * | 2007-08-21 | 2009-03-05 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming heat ray and uv ray shielding film, heat ray and uv ray shielding film, and heat ray and uv ray shielding substrate |
| US8900693B2 (en) | 2005-07-13 | 2014-12-02 | Sabic Global Technologies B.V. | Polycarbonate compositions having infrared absorbance, method of manufacture, and articles prepared therefrom |
-
1999
- 1999-05-06 JP JP12546399A patent/JP3760671B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1319683A1 (en) * | 2001-12-11 | 2003-06-18 | Asahi Glass Co., Ltd. | Heat radiation blocking fluororesin film |
| US7258923B2 (en) | 2003-10-31 | 2007-08-21 | General Electric Company | Multilayered articles and method of manufacture thereof |
| US7399571B2 (en) | 2005-05-06 | 2008-07-15 | General Electric Company | Multilayered articles and method of manufacture thereof |
| US8900693B2 (en) | 2005-07-13 | 2014-12-02 | Sabic Global Technologies B.V. | Polycarbonate compositions having infrared absorbance, method of manufacture, and articles prepared therefrom |
| JP2009046609A (en) * | 2007-08-21 | 2009-03-05 | Sumitomo Metal Mining Co Ltd | Coating liquid for forming heat ray and uv ray shielding film, heat ray and uv ray shielding film, and heat ray and uv ray shielding substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3760671B2 (en) | 2006-03-29 |
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