JP2006117526A - Complex oxide sol and film-coated base material - Google Patents
Complex oxide sol and film-coated base material Download PDFInfo
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本発明は、シリカと他の無機酸化物とからなる複合酸化物コロイド粒子が分散したゾルおよびその製造方法、ならびに、該微粒子を含有する被膜が表面に形成された基材に関するものである。 The present invention relates to a sol in which composite oxide colloidal particles composed of silica and another inorganic oxide are dispersed, a method for producing the sol, and a substrate on which a coating containing the fine particles is formed.
従来から、シリカ、アルミナ等のゾル、またはシリカ・アルミナ、シリカ・ジルコニア等の複合酸化物ゾルは公知であり、種々の用途に用いられている。これらのゾル中のコロイド粒子は、いずれも粒子内部に殆ど細孔を持たず無孔質であり、その比表面積も小さいものであった。そこで、本発明者等は先に、比表面積が大きく多孔質の微粒子が分散した複合酸化物ゾルに関する発明を行い（特開平５−１３２３０９号公報：特許文献１）、広範な用途に適用可能な複合酸化物ゾルを開示した。 Conventionally, sols such as silica and alumina or composite oxide sols such as silica / alumina and silica / zirconia are known and used in various applications. All of the colloidal particles in these sols had no pores inside the particles, were nonporous, and had a small specific surface area. Therefore, the present inventors first invented a composite oxide sol in which porous fine particles are dispersed with a large specific surface area (Japanese Patent Laid-Open No. 5-132309: Patent Document 1) and can be applied to a wide range of applications. A composite oxide sol has been disclosed.
一方、ガラス、プラスチックシート等の基材表面の反射を防止するため、その表面に反射防止膜を形成することが知られており、例えば、蒸着法、ＣＶＤ法等によって、フッ化マグネシウムのような低屈折率の物質の被膜をガラスやプラスチックの表面に形成することが行われてしている。しかし、これらの方法はコスト的に高価なものとなっている。 On the other hand, in order to prevent reflection on the surface of a substrate such as glass or plastic sheet, it is known to form an antireflection film on the surface, such as magnesium fluoride by vapor deposition or CVD. A film of a low refractive index material is formed on the surface of glass or plastic. However, these methods are costly.
また、シリカ微粒子を含む塗布液をガラス表面に塗布して、シリカ微粒子による微細で均一な凹凸をもった反射防止被膜を形成する方法も知られている。しかしながら、この方法は、シリカ微粒子により形成された凹凸面において、光の乱反射により正反射が低減されることを利用したり、微粒子間隙に生じる空気層を利用して反射防止を図るものであるが、基材表面への粒子の固定化や単層膜の形成が難しく、表面の反射率を制御することが容易ではない。
本発明は、前記従来の複合酸化物微粒子とは異なる、新規な低屈折率のコロイド粒子が分散したゾルおよびその製造方法を提供することを目的とするものである。
また、本発明はこの低屈折率の微粒子を塗布膜に利用した低反射用の基材を提供することを目的とするものである。
An object of the present invention is to provide a novel sol in which colloidal particles having a low refractive index different from the conventional composite oxide fine particles are dispersed and a method for producing the same.
Another object of the present invention is to provide a substrate for low reflection using the low refractive index fine particles as a coating film.
本発明の複合酸化物ゾルは、屈折率が１．３６〜１．４４である、シリカとシリカ以外の無機酸化物とからなる複合酸化物コロイド粒子が、水および／または有機溶媒に分散したことを特徴とするものである。 In the composite oxide sol of the present invention, the composite oxide colloidal particles composed of silica and an inorganic oxide other than silica having a refractive index of 1.36 to 1.44 are dispersed in water and / or an organic solvent. It is characterized by.
本発明の複合酸化物ゾルの製造方法は、下記第１〜第３工程よりなることを特徴とするものである。
（１）アルカリ金属、アンモニウムまたは有機塩基の珪酸塩と、アルカリ可溶の無機化合物とを、ｐＨ１０以上のアルカリ水溶液中に同時に添加して、シリカとシリカ以外の無機酸化物とからなるコロイド粒子を生成させる第１工程。
（２）該コロイド粒子中の珪素と酸素以外の元素の一部を除去する第２工程。
（３）該コロイド粒子の表面を被膜で被覆する第３工程。
The method for producing a composite oxide sol of the present invention is characterized by comprising the following first to third steps.
(1) An alkali metal, ammonium or organic base silicate and an alkali-soluble inorganic compound are simultaneously added to an alkaline aqueous solution having a pH of 10 or more to produce colloidal particles composed of silica and an inorganic oxide other than silica. The 1st process made to produce | generate.
(2) A second step of removing a part of the elements other than silicon and oxygen in the colloidal particles.
(3) A third step of coating the surface of the colloidal particles with a coating.
また、本発明の複合酸化物ゾルの別の製造方法は、下記第１〜第３工程よりなることを特徴とするものである。
（１）シード粒子が分散したｐＨ１０以上の分散液中に、アルカリ金属、アンモニウムまたは有機塩基の珪酸塩と、アルカリ可溶の無機化合物とを同時に添加し該シード粒子を核とする粒子成長を行わせて、シリカとシリカ以外の無機酸化物とからなる微粒子を生成させる第１工程。
（２）該コロイド粒子中の珪素と酸素以外の元素の一部を除去する第２工程。
（３）該コロイド粒子の表面を被膜で被覆する第３工程。
Another method for producing the composite oxide sol of the present invention is characterized by comprising the following first to third steps.
(1) In a dispersion having a pH of 10 or more in which seed particles are dispersed, alkali metal, ammonium or an organic base silicate and an alkali-soluble inorganic compound are simultaneously added to perform particle growth using the seed particles as nuclei. And a first step of generating fine particles comprising silica and an inorganic oxide other than silica.
(2) A second step of removing a part of the elements other than silicon and oxygen in the colloidal particles.
(3) A third step of coating the surface of the colloidal particles with a coating.
本発明の基材は、屈折率が１．３６〜１．４４である、シリカとシリカ以外の無機酸化物とからなる複合酸化物微粒子と、被膜形成用マトリックスとからなる被膜が表面に形成されてなることを特徴とするものである。 The base material of the present invention has a coating film formed of composite oxide fine particles composed of silica and an inorganic oxide other than silica, having a refractive index of 1.36 to 1.44, and a film forming matrix on the surface. It is characterized by.
本発明に係る複合酸化物ゾルは、従来のシリカゾル等と比べて低屈折率のコロイド粒子が分散したゾルであり、低反射用基材の表面被膜の構成成分として利用可能である。このような被膜が形成されたガラスは、陰極線管、液晶表示装置などの表示パネルを始め、低反射ガラスとして種々の用途に供し得る。また、この被膜が形成されたＰＥＴ等のプラスチックシートまたはフィルムは、低反射シートまたはフィルムとして有用である。 The composite oxide sol according to the present invention is a sol in which colloidal particles having a low refractive index are dispersed as compared with a conventional silica sol or the like, and can be used as a constituent component of a surface coating of a substrate for low reflection. The glass on which such a film is formed can be used for various applications as a low reflection glass, including display panels such as cathode ray tubes and liquid crystal display devices. Moreover, a plastic sheet or film such as PET on which this film is formed is useful as a low reflection sheet or film.
本発明に係る複合酸化物ゾルの製造方法は、ゾルの製造操作が容易で、しかも製造プロセスが簡易であるという効果を有している。 The method for producing a composite oxide sol according to the present invention has an effect that the sol production operation is easy and the production process is simple.
以下、本発明を具体的に詳述するが、始めに複合酸化物ゾルについて説明する。
〔複合酸化物ゾル〕
本発明のゾルに分散したコロイド粒子は、シリカとシリカ以外の無機酸化物、具体的には、Ａｌ2Ｏ3、Ｂ2Ｏ3、ＴｉＯ2、ＺｒＯ2、ＳｎＯ2、Ｃｅ2Ｏ3、Ｐ2Ｏ5、Ｓｂ2Ｏ3、ＭｏＯ3、ＷＯ3等との複合酸化物からなる。また、当該コロイド粒子の表面は、例えば、シリカ等の被膜で薄く被覆されており、このときの被覆処理前のコロイド粒子は多孔性の微粒子である。
Hereinafter, the present invention will be described in detail. First, the composite oxide sol will be described.
[Composite oxide sol]
The colloidal particles dispersed in the sol of the present invention are silica and inorganic oxides other than silica, specifically, Al 2 O 3 , B 2 O 3 , TiO 2 , ZrO 2 , SnO 2 , Ce 2 O 3 , P It consists of a complex oxide with 2 O 5 , Sb 2 O 3 , MoO 3 , WO 3 or the like. Further, the surface of the colloidal particles is thinly coated with a coating such as silica, for example, and the colloidal particles before the coating treatment at this time are porous fine particles.
本発明の複合酸化物ゾルは上記コロイド粒子が、水、有機溶媒または水と有機溶媒との混合溶媒に分散したゾルであるが、本発明で用いられる有機溶媒は１価または多価アルコールを始めとする従来の有機ゾルに用いられる有機溶媒が使用可能である。 The composite oxide sol of the present invention is a sol in which the colloidal particles are dispersed in water, an organic solvent or a mixed solvent of water and an organic solvent. The organic solvent used in the present invention includes monohydric or polyhydric alcohols. The organic solvent used in the conventional organic sol can be used.
また、従来のシリカゾル等のコロイド粒子の屈折率が１．４５、またはそれ以上と高いのに対して、本発明のコロイド粒子の屈折率は１．４４以下である。このコロイド粒子の屈折率は、粒子を構成するシリカと無機酸化物の割合、無機酸化物の種類または粒子内部の細孔の量を変えることにより制御することができる。 The refractive index of colloidal particles such as silica sol is as high as 1.45 or higher, whereas the refractive index of colloidal particles of the present invention is 1.44 or lower. The refractive index of the colloidal particles can be controlled by changing the ratio of silica and inorganic oxide constituting the particles, the type of inorganic oxide, or the amount of pores inside the particles.
本発明のゾル中のコロイド粒子の屈折率は、次のようにして測定する。
（１）複合酸化物ゾルをエバポレーターに採り、分散媒を蒸発させる。
（２）これを１２０℃で乾燥し、粉末とする。
（３）屈折率が既知の標準屈折液を２、３滴ガラス板上に滴下し、これに上記粉末を混合する。
（４）上記（３）の操作を種々の標準屈折液で行い、混合液が透明になったときの標準屈折液の屈折率をコロイド粒子の屈折率とする。
The refractive index of the colloidal particles in the sol of the present invention is measured as follows.
(1) Take the composite oxide sol in an evaporator and evaporate the dispersion medium.
(2) This is dried at 120 ° C. to obtain a powder.
(3) A standard refraction liquid having a known refractive index is dropped on a glass plate of a few drops, and the above powder is mixed therewith.
(4) The operation of (3) above is performed with various standard refractive liquids, and the refractive index of the standard refractive liquid when the mixed liquid becomes transparent is used as the refractive index of the colloidal particles.
〔複合酸化物ゾルの製造方法〕
次に、複合酸化物ゾルの製造方法を説明する。本発明の製造方法は、次の第１〜第３工程からなる。
[Production method of composite oxide sol]
Next, a method for producing a complex oxide sol will be described. The production method of the present invention comprises the following first to third steps.
第１工程では、予め、シリカ原料とシリカ以外の無機酸化物原料のアルカリ水溶液を個別に調製するか、または、混合水溶液を調製しておき、この水溶液を目的とする複合酸化物の複合割合に応じて、ｐＨ１０以上のアルカリ水溶液中に攪拌しながら徐々に添加する。 In the first step, a silica raw material and an alkaline aqueous solution of an inorganic oxide raw material other than silica are separately prepared in advance, or a mixed aqueous solution is prepared, and this aqueous solution is adjusted to the composite ratio of the target composite oxide. Accordingly, it is gradually added to an alkaline aqueous solution having a pH of 10 or more with stirring.
シリカ原料としては、アルカリ金属、アンモニウムまたは有機塩基の珪酸塩を用いる。
アルカリ金属の珪酸塩としては、珪酸ナトリウム（水ガラス）や珪酸カリウムが用いられる。
有機塩基としては、テトラエチルアンモニウム塩などの第４級アンモニウム塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアミン類を挙げることができ、アンモニウムの珪酸塩または有機塩基の珪酸塩には、珪酸液にアンモニア、第４級アンモニウム水酸化物、アミン化合物などを添加したアルカリ性溶液も含まれる。
As the silica raw material, alkali metal, ammonium or organic base silicate is used.
Sodium silicate (water glass) or potassium silicate is used as the alkali metal silicate.
Examples of the organic base include quaternary ammonium salts such as tetraethylammonium salt, and amines such as monoethanolamine, diethanolamine, and triethanolamine. Ammonium silicate or organic base silicate includes a silicate liquid. Also included are alkaline solutions in which ammonia, quaternary ammonium hydroxides, amine compounds and the like are added.
また、無機酸化物の原料としては、アルカリ可溶の無機化合物を用い、周期表の３Ａ族、３Ｂ族、４Ａ族、４Ｂ族、５Ａ族、５Ｂ族、６Ａ族から選ばれる金属または非金属のオキソ酸の、アルカリ金属塩またはアルカリ土類金属塩、アンモニウム塩、第４級アンモニウム塩を挙げることができ、より具体的には、アルミン酸ナトリウム、四硼酸ナトリウム、炭酸ジルコニルアンモニウム、アンチモン酸カリウム、錫酸カリウム、アルミノ珪酸ナトリウム、モリブデン酸ナトリウム、硝酸セリウムアンモニウム、燐酸ナトリウムが適当である。 Moreover, as an inorganic oxide raw material, an alkali-soluble inorganic compound is used, and a metal or non-metal selected from 3A group, 3B group, 4A group, 4B group, 5A group, 5B group, and 6A group of the periodic table is used. Mention may be made of alkali metal or alkaline earth metal salts, ammonium salts, quaternary ammonium salts of oxo acids, more specifically sodium aluminate, sodium tetraborate, zirconyl ammonium carbonate, potassium antimonate, Potassium stannate, sodium aluminosilicate, sodium molybdate, cerium ammonium nitrate and sodium phosphate are suitable.
これらの水溶液の添加と同時に混合水溶液のｐＨ値は変化するが、本発明ではこのｐＨ値を所定の範囲に制御するような操作は特に必要ない。水溶液は、最終的に、無機酸化物の種類とその混合割合とによって定まるｐＨ値に落ち着く。
ｐＨを所定の範囲に制御するとき、例えば酸を添加することがあるが、この場合、添加された酸により複合酸化物の原料の金属の塩が生成し、このためゾルの安定性が低下することがある。なお、このときの水溶液の添加速度には格別の制限はない。
Although the pH value of the mixed aqueous solution changes simultaneously with the addition of these aqueous solutions, an operation for controlling the pH value within a predetermined range is not particularly required in the present invention. The aqueous solution finally settles at a pH value determined by the type of inorganic oxide and its mixing ratio.
When the pH is controlled within a predetermined range, for example, an acid may be added. In this case, the added acid generates a metal salt of the raw material of the composite oxide, and this decreases the stability of the sol. Sometimes. In addition, there is no special restriction | limiting in the addition rate of the aqueous solution at this time.
本発明の複合酸化物ゾルの製造方法では、シード粒子の分散液を出発原料とすることも可能である。当該シード粒子としては、特に制限はないが、ＳｉＯ2、Ａｌ2Ｏ3、ＴｉＯ2またはＺｒＯ2等の無機酸化物またはこれらの複合酸化物の微粒子が用いられ、通常、これらのゾルを用いることができる。勿論、前記本発明の製造方法によって得られたゾルをシード粒子分散液としてもよい。 In the method for producing a composite oxide sol of the present invention, a dispersion of seed particles can be used as a starting material. The seed particles are not particularly limited, but inorganic oxides such as SiO 2 , Al 2 O 3 , TiO 2 or ZrO 2 or fine particles of these composite oxides are used. Usually, these sols are used. Can do. Of course, the sol obtained by the production method of the present invention may be used as a seed particle dispersion.
このｐＨ１０以上に調整したシード粒子分散液中に前記化合物の水溶液を、上記したアルカリ水溶液中に添加する方法と同様にして、攪拌しながら添加する。この場合も、分散液のｐＨ制御は行わず成り行きに任せる。このように、シード粒子を核として複合酸化物粒子を成長させると、成長粒子の粒径コントロールが容易であり、粒度の揃ったものを得ることができる。 The aqueous solution of the compound is added to the seed particle dispersion adjusted to pH 10 or higher with stirring in the same manner as in the method of adding the alkaline aqueous solution described above. In this case as well, the pH of the dispersion is not controlled and left to the future. As described above, when the composite oxide particles are grown using the seed particles as nuclei, it is easy to control the particle size of the grown particles, and particles with uniform particle sizes can be obtained.
上記したシリカ原料および無機酸化物原料はアルカリ側で高い溶解度をもっている。しかしながら、この溶解度の大きいｐＨ領域で両者を混合すると、珪酸イオンおよびアルミン酸イオンなどのオキソ酸イオンの溶解度が低下し、これらの複合物が析出して微粒子に成長したり、あるいは、シード粒子上に析出して粒子成長が起こる。従って、微粒子の析出、成長に際して、従来法のようなｐＨ制御は必ずしも行う必要がない。 The silica raw material and inorganic oxide raw material described above have high solubility on the alkali side. However, when both are mixed in this highly soluble pH region, the solubility of oxo acid ions such as silicate ions and aluminate ions decreases, and these composites precipitate and grow into fine particles, or on the seed particles. Precipitates into particles and causes particle growth. Therefore, it is not always necessary to perform pH control as in the conventional method for precipitation and growth of fine particles.
第１工程におけるシリカとシリカ以外の無機酸化物との複合割合は、無機酸化物に対するシリカのモル比が０．５〜２０の範囲内にあることが好ましい。この範囲内において、シリカの割合が少なくなる程、コロイド粒子は多孔質になり比表面積が大きくなる。しかしながら、モル比が０．５未満になると、コロイド粒子の比表面積は殆ど増加しなくなる。他方、モル比が２０を越えるようになると、細孔容積が少なくなり、比表面積も低下してくる。 The composite ratio of silica and inorganic oxide other than silica in the first step is preferably such that the molar ratio of silica to inorganic oxide is in the range of 0.5 to 20. Within this range, the smaller the silica content, the more porous the colloidal particles and the greater the specific surface area. However, when the molar ratio is less than 0.5, the specific surface area of the colloidal particles hardly increases. On the other hand, when the molar ratio exceeds 20, the pore volume decreases and the specific surface area also decreases.
第２工程では、前記複合酸化物からなるコロイド粒子から、珪素と酸素以外の元素の少なくとも一部を選択的に除去する。具体的な除去方法としては、複合酸化物中の元素を鉱酸や有機酸を用いて溶解除去したり、あるいは、陽イオン交換樹脂と接触させてイオン交換除去する。 In the second step, at least a part of elements other than silicon and oxygen is selectively removed from the colloidal particles made of the composite oxide. As a specific removal method, an element in the complex oxide is dissolved and removed using a mineral acid or an organic acid, or ion exchange is removed by contacting with an cation exchange resin.
前記第１工程で得られる複合酸化物のコロイド粒子は、珪素と無機酸化物構成元素が酸素を介して結合した網目構造の粒子である。このような複合酸化物から珪素と酸素以外の元素を除去することにより、一層多孔質で比表面積の大きいコロイド粒子が得られるのであるが、過度に除去するとコロイド粒子の強度が弱くなり、遂にはその形状を保持することができなくなる。従って、最終的な無機酸化物に対するシリカの複合割合（モル比）は、概よそ１０００以下にすることが望ましい。 The composite oxide colloidal particles obtained in the first step are particles having a network structure in which silicon and inorganic oxide constituent elements are bonded through oxygen. By removing elements other than silicon and oxygen from such a complex oxide, colloidal particles having a higher porosity and a larger specific surface area can be obtained. However, when excessively removed, the strength of the colloidal particles is weakened, and finally The shape cannot be maintained. Therefore, the composite ratio (molar ratio) of silica to the final inorganic oxide is desirably about 1000 or less.
第３工程では、このゾルに加水分解性の有機ケイ素化合物、その部分加水分解物、重縮合物またはケイ酸液等を加えることにより、コロイド粒子の表面を加水分解性有機ケイ素化合物またはケイ酸液等の重合物で被覆する。 In the third step, a hydrolyzable organosilicon compound, a partial hydrolyzate, a polycondensate or a silicic acid solution is added to the sol, so that the surface of the colloidal particles is hydrolyzable organosilicon compound or silicic acid solution. And so on.
加水分解性の有機ケイ素化合物としては、一般式ＲnＳｉ（ＯＲ′）4-n〔Ｒ、Ｒ′：アルキル基、アリール基、ビニル基、アクリル基等の炭化水素基、ｎ＝０、１、２または３〕で表されるアルコキシシランを用いることができる。特に、テトラメトキシシラン、テトラエトキシシラン、テトライソプロポキシシラン等のテトラアルコキシシランが好ましく用いられる。 The hydrolyzable organosilicon compound of the general formula R n Si (OR ') 4 -n [R, R': an alkyl group, an aryl group, a vinyl group, a hydrocarbon group such as acrylic group, n = 0, 1 2 or 3] can be used. In particular, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane are preferably used.
添加方法としては、これらのアルコキシシラン、純水、およびアルコールの混合溶液に触媒としての少量のアルカリ又は酸を添加した溶液を、前記ゾルに加え、アルコキシシランを加水分解して生成したケイ酸重合物をコロイド粒子の表面に沈着させる。このとき、アルコキシシラン、アルコール、触媒を同時にゾル中に添加してもよい。アルカリ触媒としては、アンモニア、アルカリ金属の水酸化物、アミン類を用いることができる。また、酸触媒としては、各種の無機酸と有機酸を用いることができる。 As an addition method, a solution obtained by adding a small amount of alkali or acid as a catalyst to a mixed solution of these alkoxysilanes, pure water, and alcohol is added to the sol, and hydrolyzed alkoxysilane. Deposit objects on the surface of the colloidal particles. At this time, alkoxysilane, alcohol, and catalyst may be simultaneously added to the sol. As the alkali catalyst, ammonia, an alkali metal hydroxide, or an amine can be used. As the acid catalyst, various inorganic acids and organic acids can be used.
ゾルの分散媒が水単独、または有機溶媒に対する水の比率が高い場合には、ケイ酸液による被覆処理も可能である。ケイ酸液とは、水ガラス等のアルカリ金属ケイ酸塩の水溶液をイオン交換処理して脱アルカリしたケイ酸の低重合物の水溶液である。
ケイ酸液を用いる場合には、ゾル中にケイ酸液を所定量添加し、同時にアルカリを加えてケイ酸液を重合・ゲル化させ、ケイ酸重合物をコロイド粒子表面に沈着させる。なお、ケイ酸液と上記アルコキシシランを併用して被覆処理を行うことも可能である。
有機ケイ素化合物またはケイ酸液の添加量は、コロイド粒子の表面をそれぞれの重合物が十分に被覆できる程度とする。
When the sol dispersion medium is water alone or the ratio of water to the organic solvent is high, coating treatment with a silicic acid solution is also possible. The silicic acid solution is an aqueous solution of a low silicic acid polymer obtained by dealkalizing an aqueous solution of an alkali metal silicate such as water glass by ion exchange treatment.
When a silicic acid solution is used, a predetermined amount of the silicic acid solution is added to the sol, and at the same time an alkali is added to polymerize and gel the silicic acid solution, thereby depositing the silicic acid polymer on the colloidal particle surface. In addition, it is also possible to perform a coating process by using the silicic acid solution and the alkoxysilane together.
The amount of the organosilicon compound or silicic acid solution added is such that the surface of the colloidal particles can be sufficiently covered with each polymer.
このようにして得られた複合酸化物ゾルに分散したコロイド粒子の屈折率は、従来の酸化物コロイド粒子の屈折率よりも低く、１．３６〜１．４４の範囲内となる。本発明では前述したように、まず、多孔性のコロイド粒子が分散した複合酸化物ゾルを調製し、次いで、アルコキシシラン等で該コロイド粒子の表面を被覆することにより、粒子の細孔入口が閉塞され、粒子内部の多孔性が保持される。その結果、コロイド粒子の屈折率は、従来の無孔質の酸化物コロイド粒子に比較して低くなるものと考えられる。 The refractive index of the colloidal particles dispersed in the composite oxide sol thus obtained is lower than the refractive index of the conventional oxide colloidal particles and is in the range of 1.36 to 1.44. In the present invention, as described above, first, a composite oxide sol in which porous colloidal particles are dispersed is prepared, and then the surface of the colloidal particles is covered with alkoxysilane or the like to block the pore inlets of the particles. And the porosity inside the particles is maintained. As a result, the refractive index of colloidal particles is considered to be lower than that of conventional nonporous oxide colloidal particles.
本発明のコロイド粒子の表面被覆処理は、上述のような有機ケイ素化合物、ケイ酸液のみでなく、例えば、合成樹脂等、粒子表面を薄く被覆しその細孔入口を閉塞できるものであればよい。
当該コロイド粒子の平均粒径は、調製条件によって任意のものが得られるが、一般的には５〜３００ｎｍ、好ましくは５〜１５０ｎｍとなる。
The surface coating treatment of the colloidal particles of the present invention is not limited to the above-described organosilicon compound and silicic acid solution, but may be any material that can coat the particle surface thinly and block the pore inlet, such as a synthetic resin. .
Although the average particle diameter of the colloidal particles can be obtained depending on the preparation conditions, it is generally 5 to 300 nm, preferably 5 to 150 nm.
上記複合酸化物ゾルは水を分散媒とするゾルであるが、その用途に応じて、エタノール、エチレングリコール等の１価または多価アルコール、あるいはその他の有機溶媒と溶媒置換して有機ゾルとすることも可能である。 The composite oxide sol is a sol using water as a dispersion medium. Depending on the application, the organic oxide sol is substituted with a monovalent or polyhydric alcohol such as ethanol or ethylene glycol, or another organic solvent. It is also possible.
上記コロイド粒子が分散したゾルを濃縮する場合には、予めゾル中のアルカリ金属イオン、アルカリ土類金属イオンおよびアンモニウムイオン等の一部を除去した後に濃縮した方が、安定した濃縮ゾルが得られる。除去方法としては、限外濾過等の公知の方法を採用することができる。 When concentrating the sol in which the colloidal particles are dispersed, it is possible to obtain a stable concentrated sol by concentrating after removing a part of the alkali metal ions, alkaline earth metal ions and ammonium ions in the sol in advance. . As the removal method, a known method such as ultrafiltration can be employed.
〔低反射用基材〕
次に、本発明に係る被膜付基材について説明する。この被膜付基材は、ガラス、ポリカーボネート、アクリル、ＰＥＴ、ＴＡＣ等のプラスチックシート、フィルム等の基材の表面に被膜を形成したものであり、後述する塗布液をディップ法、スプレー法、スピナー法、ロールコート法などの周知の方法で基材に塗布し、乾燥し、更に必要に応じて、焼成して得ることができる。
[Low reflective substrate]
Next, the coated substrate according to the present invention will be described. This coated substrate is formed by forming a coating on the surface of a substrate such as glass, polycarbonate, acrylic, PET, TAC, or other plastic sheet, film, and the like. It can be obtained by applying to a substrate by a known method such as a roll coating method, drying, and firing if necessary.
被膜形成用の塗布液は、前記ゾルと被膜形成用マトリックスとを混合して製造する。また、塗布液には必要に応じて有機溶媒を混合してもよい。
本発明において被膜形成用マトリックスとは、基材の表面に被膜を形成し得る成分をいい、例えば、従来から用いられているポリエステル樹脂、アクリル樹脂、ウレタン樹脂、塩化ビニル樹脂、エポキシ樹脂、メラミン樹脂、フッ素樹脂、シリコン樹脂などの塗料用樹脂、または、前記アルコキシシラン等の加水分解性有機ケイ素化合物等が挙げられる。
The coating liquid for forming a film is produced by mixing the sol and a matrix for forming a film. Moreover, you may mix an organic solvent with a coating liquid as needed.
In the present invention, the film-forming matrix refers to a component that can form a film on the surface of a substrate. For example, conventionally used polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin , A resin for coatings such as fluororesin and silicon resin, or a hydrolyzable organosilicon compound such as alkoxysilane.
マトリックスとして塗料用樹脂を用いる場合には、例えば、前記ゾルの分散媒としての水を、アルコール等の有機溶媒で置換し、この有機溶媒分散ゾルと塗料用樹脂を適当な有機溶剤で希釈して塗布液とすることができる。 When a coating resin is used as the matrix, for example, water as a dispersion medium for the sol is replaced with an organic solvent such as alcohol, and the organic solvent-dispersed sol and the coating resin are diluted with a suitable organic solvent. It can be set as a coating liquid.
一方、マトリックスとして加水分解性有機ケイ素化合物を用いる場合には、例えば、アルコキシシランとアルコールの混合液に、水および触媒としての酸またはアルカリを加えることにより、アルコキシシランの部分加水分解物を得、これに前記ゾルを混合し、必要に応じて有機溶剤で希釈して塗布液とすることができる。 On the other hand, when using a hydrolyzable organosilicon compound as a matrix, for example, by adding water and an acid or alkali as a catalyst to a mixture of alkoxysilane and alcohol, a partially hydrolyzed product of alkoxysilane is obtained, The sol can be mixed with this and diluted with an organic solvent as necessary to obtain a coating solution.
塗布液中の複合酸化物微粒子とマトリックスの重量割合は、複合酸化物微粒子：マトリックス＝９０：１〜１：９９の範囲が好ましい。複合酸化物微粒子が９０重量部を越えると被膜の強度が不足して実用性に欠ける一方、１重量部未満では当該微粒子の添加効果が現れない。
このようにして得られた被膜付基材は、ガラス、プラスチック等の基材自体より低屈折率の被膜が表面に形成されていることから、反射防止機能が優れている。
The weight ratio of the composite oxide fine particles to the matrix in the coating solution is preferably in the range of composite oxide fine particles: matrix = 90: 1 to 1:99. When the composite oxide fine particle exceeds 90 parts by weight, the strength of the coating is insufficient and the practicality is insufficient, whereas when it is less than 1 part by weight, the effect of adding the fine particle does not appear.
The base material with a coating thus obtained has an antireflection function because a coating having a lower refractive index than that of the base material itself such as glass or plastic is formed on the surface.
〔複合酸化物ゾルの製造〕
平均粒径５ｎｍ、ＳｉＯ2濃度２０重量％のシリカゾル１００ｇと純水１９００ｇの混合物を８０℃に加温した。この反応母液のｐＨは１０．５であり、同母液にＳｉＯ2として１．５重量％の珪酸ナトリウム水溶液９０００ｇとＡｌ2Ｏ3として０．５重量％のアルミン酸ナトリウム水溶液９０００ｇとを同時に添加した。その間、反応液の温度を８０℃に保持した。反応液のｐＨは添加直後、１２．５に上昇し、その後、殆ど変化しなかった。添加終了後、反応液を室温まで冷却し、限外濾過膜で洗浄して固形分濃度２０重量％のＳｉＯ2・Ａｌ2Ｏ3複合酸化物前駆体ゾル（Ａ）を得た。（第１工程）
[Production of complex oxide sol]
A mixture of 100 g of silica sol having an average particle diameter of 5 nm and a SiO 2 concentration of 20% by weight and 1900 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.5, and 9000 g of a 1.5 wt% sodium silicate aqueous solution as SiO 2 and 9000 g of a 0.5 wt% sodium aluminate aqueous solution as Al 2 O 3 were simultaneously added to the mother liquor. . Meanwhile, the temperature of the reaction solution was kept at 80 ° C. The pH of the reaction solution rose to 12.5 immediately after the addition, and hardly changed thereafter. After completion of the addition, the reaction solution was cooled to room temperature and washed with an ultrafiltration membrane to obtain a SiO 2 · Al 2 O 3 composite oxide precursor sol (A) having a solid content concentration of 20% by weight. (First step)
この前駆体ゾル（Ａ）５００ｇに純水１，７００ｇを加えて９８℃に加温し、この温度を保持しながら、ケイ酸ナトリウム水溶液を陽イオン交換樹脂で脱アルカリして得られたケイ酸液（ＳｉＯ2濃度３．５重量％）３，０００ｇを添加した。このゾルを限外濾過膜で洗浄して固形分濃度１３重量％になったゾル５００ｇに純水１，１２５ｇを加え、さらに濃塩酸（３５．５％）を滴下してｐＨ１．０とし、脱アルミニウム処理を行った。
次いで、ｐＨ３の塩酸水溶液１０Ｌと純水５Ｌを加えながら限外濾過膜で溶解したアルミニウム塩を分離し、一部のアルミニウムが除去されたＳｉＯ2・Ａｌ2Ｏ3複合酸化物前駆体ゾル（Ｂ）を得た。（第２工程）
Silica obtained by adding 1,700 g of pure water to 500 g of this precursor sol (A) and heating to 98 ° C., and maintaining the temperature while removing the alkali silicate solution with a cation exchange resin. 3,000 g of a liquid (SiO 2 concentration 3.5% by weight) was added. The sol was washed with an ultrafiltration membrane to add 1,125 g of pure water to 500 g of the sol having a solid content of 13 wt%, and concentrated hydrochloric acid (35.5%) was added dropwise to adjust the pH to 1.0. Aluminum treatment was performed.
Next, the aluminum salt dissolved in the ultrafiltration membrane was separated while adding 10 L of hydrochloric acid aqueous solution of pH 3 and 5 L of pure water, and the SiO 2 · Al 2 O 3 composite oxide precursor sol (B ) (Second step)
上記ゾル（Ｂ）１５００ｇと、純水５００ｇ、エタノール１，７５０ｇおよび２８％アンモニア水６２６ｇとの混合液を３５℃に加温した後、エチルシリケート（ＳｉＯ2２８重量％）１０４ｇを添加し、複合酸化物コロイド粒子の表面をエチルシリケートの加水分解重縮合物で被覆した。次いで、エバポレーターで固形分濃度５重量％まで濃縮した後、１５％アンモニア水を加えてｐＨ１０とし、オートクレーブで１８０℃、２時間加熱処理し、本発明の複合酸化物ゾルを得た。（第３工程） A mixture of 1500 g of the sol (B), 500 g of pure water, 1,750 g of ethanol and 626 g of 28% ammonia water was heated to 35 ° C., and then 104 g of ethyl silicate (SiO 2 28 wt%) was added. The surface of the oxide colloidal particles was coated with a hydrolyzed polycondensate of ethyl silicate. Subsequently, after concentrating to 5 weight% of solid content with an evaporator, 15% ammonia water was added to adjust to pH 10, and heat treatment was performed at 180 ° C. for 2 hours in an autoclave to obtain the composite oxide sol of the present invention. (Third step)
この複合酸化物ゾル中のコロイド粒子（Ｐ１）の平均粒径、ＳｉＯ2／ＭＯx（モル比）、および屈折率を表１に示す。ここで、平均粒径は動的光散乱法により測定し、屈折率は標準屈折液としてCARGILL 製のSeriesＡ、ＡＡを用い、前述の方法で測定した。 Table 1 shows the average particle size, SiO 2 / MO x (molar ratio), and refractive index of the colloidal particles (P1) in this composite oxide sol. Here, the average particle diameter was measured by a dynamic light scattering method, and the refractive index was measured by the above-described method using Series A and AA made by CARGILL as a standard refractive liquid.
実施例１で得られた前駆体ゾル（Ａ）１００ｇに純水１，９００ｇを加えて９５℃に加温し、この温度を保持しながら、ケイ酸ナトリウム水溶液（ＳｉＯ2として１．５ｇ重量％）２７，０００ｇおよびアルミン酸ナトリウム水溶液（Ａｌ2Ｏ3として０．５重量％）２７，０００ｇを同時に徐々に添加し、前駆体ゾル（Ａ）の微粒子を核として粒子成長を行わせた。添加終了後、室温まで冷却した後、限外濾過膜で洗浄、濃縮して、固形分濃度２０重量％の前駆体ゾル（Ｃ）を得た。（第１工程） 1,100 g of pure water was added to 100 g of the precursor sol (A) obtained in Example 1 and heated to 95 ° C., and while maintaining this temperature, an aqueous sodium silicate solution (1.5 g% as SiO 2) 27,000 g and 27,000 g of an aqueous solution of sodium aluminate (0.5% by weight as Al 2 O 3 ) were gradually added at the same time, and particle growth was performed using fine particles of the precursor sol (A) as nuclei. After completion of the addition, the mixture was cooled to room temperature, washed with an ultrafiltration membrane, and concentrated to obtain a precursor sol (C) having a solid content concentration of 20% by weight. (First step)
この前駆体ゾル（Ｃ）５００ｇを採り、実施例１と同様の方法により、第２工程の脱アルミニウム処理、および、第３工程のエチルシリケートの加水分解物による被覆処理を行い、表１に示すコロイド粒子（Ｐ２）が分散した複合酸化物ゾルを得た。 500 g of this precursor sol (C) was taken, and the dealumination treatment in the second step and the coating treatment with the hydrolyzate of ethyl silicate in the third step were performed in the same manner as in Example 1, and shown in Table 1. A composite oxide sol in which colloidal particles (P2) were dispersed was obtained.
実施例２で得られた前駆体ゾル（Ｃ）１００ｇに純水１，９００ｇを加えて９５℃に加温し、この温度を保持しながら、ケイ酸ナトリウム水溶液（ＳｉＯ2として１．５ｇ重量％）７，０００ｇおよびアルミン酸ナトリウム水溶液（Ａｌ2Ｏ3として０．５重量％）７，０００ｇを同時に徐々に添加し、粒子成長を行わせた。添加終了後、室温まで冷却した後、限外濾過膜で洗浄、濃縮して、固形分濃度２０重量％の前駆体ゾル（Ｄ）を得た。（第１工程）
この前駆体ゾル（Ｄ）５００ｇを採り、実施例１と同様の方法により、表１に示すコロイド粒子（Ｐ３）が分散した複合酸化物ゾルを得た。
1,100 g of pure water was added to 100 g of the precursor sol (C) obtained in Example 2 and heated to 95 ° C., and while maintaining this temperature, an aqueous sodium silicate solution (1.5 g% as SiO 2) ) 7,000 g and sodium aluminate aqueous solution (0.5% by weight as Al 2 O 3 ) 7,000 g were gradually added simultaneously to cause particle growth. After completion of the addition, the mixture was cooled to room temperature, washed with an ultrafiltration membrane, and concentrated to obtain a precursor sol (D) having a solid content concentration of 20% by weight. (First step)
500 g of this precursor sol (D) was taken, and a composite oxide sol in which colloidal particles (P3) shown in Table 1 were dispersed was obtained in the same manner as in Example 1.
実施例１のアルミン酸ナトリウムの代わりに、ＳｎＯ2として０．５重量％の錫酸カリウム水溶液９，０００ｇを用いた以外は、実施例１と同様の方法で、固形分濃度２０重量％のＳｉＯ2・Ａｌ2Ｏ3複合酸化物前駆体ゾルを得、更に実施例１と同様の方法で、脱Ｓｎ処理および被覆処理を行い、表１に示すコロイド粒子（Ｐ４）が分散した複合酸化物ゾルを得た。 In place of sodium aluminate of Example 1, SnO 2 was used in the same manner as in Example 1 except that 9,000 g of 0.5 wt% potassium stannate aqueous solution was used. 2 · Al 2 O 3 composite oxide precursor sol was obtained, and Sn removal treatment and coating treatment were further carried out in the same manner as in Example 1 to obtain a composite oxide sol in which colloidal particles (P4) shown in Table 1 were dispersed. Got.
実施例１の第２工程で得られた脱アルミニウム処理したＳｉＯ2・Ａｌ2Ｏ3複合酸化物前駆体ゾル（Ｂ）１，５００ｇをｐＨ１１に調整して９８℃に加温した後、ケイ酸液（ＳｉＯ2として３．５重量％）７００ｇを添加し、コロイド粒子の表面をシリカ重合物で被覆した。
次いで、限外濾過膜で洗浄、濃縮して、固形分濃度１３重量％の表１に示すコロイド粒子（Ｐ５）が分散した複合酸化物ゾルを得た。
The dealuminated SiO 2 .Al 2 O 3 composite oxide sol (B) 1,500 g obtained in the second step of Example 1 was adjusted to pH 11 and heated to 98 ° C., and then silicic acid. 700 g of a liquid (3.5% by weight as SiO 2 ) was added, and the surface of the colloidal particles was coated with a silica polymer.
Subsequently, it was washed with an ultrafiltration membrane and concentrated to obtain a composite oxide sol in which colloidal particles (P5) shown in Table 1 having a solid content concentration of 13% by weight were dispersed.
実施例１の第２工程において、濃塩酸添加による脱アルミニウム処理の条件をｐＨ１．０の代わりにｐＨ３．０で行った以外は、実施例１と同様の方法により表１に示すコロイド粒子（Ｐ６）が分散した複合酸化物ゾルを得た。 In the second step of Example 1, colloidal particles (P6) shown in Table 1 were prepared in the same manner as in Example 1 except that the condition of dealumination treatment by adding concentrated hydrochloric acid was changed to pH 3.0 instead of pH 1.0. ) Was obtained.
実施例１の第２工程において、濃塩酸添加による脱アルミニウム処理の条件をｐＨ１．０の代わりにｐＨ０．５で行った以外は、実施例１と同様の方法により表１に示すコロイド粒子（Ｐ７）が分散した複合酸化物ゾルを得た。 In the second step of Example 1, colloidal particles (P7) shown in Table 1 were prepared in the same manner as in Example 1 except that the condition of dealumination treatment by adding concentrated hydrochloric acid was changed to pH 0.5 instead of pH 1.0. ) Was obtained.
実施例１の第２工程において得られたＳｉＯ2・Ａｌ2Ｏ3複合酸化物前駆体ゾル（Ｂ）について、そのコロイド粒子（Ｐ０）の平均粒径、ＳｉＯ2／ＭＯx（モル比）、および屈折率を測定した。 About the SiO 2 · Al 2 O 3 composite oxide precursor sol (B) obtained in the second step of Example 1, the average particle diameter of the colloidal particles (P0), SiO 2 / MO x (molar ratio), And the refractive index was measured.
［表１］
微粒子 平均粒径 ＳｉＯ 2 ／ＭＯ x 屈折率
（nm） （モル比）
Ｐ０ 30 149.0 1.45
Ｐ１ 30 127.2 1.40
Ｐ２ 60 143.9 1.38
Ｐ３ 120 231.6 1.36
Ｐ４ 30 124.0 1.40
Ｐ５ 30 130.6 1.41
Ｐ６ 30 103.2 1.42
Ｐ７ 30 999.0 1.39
[Table 1]
Fine particle average particle diameter SiO 2 / MO x refractive index
( Nm ) ( molar ratio )
P0 30 149.0 1.45
P1 30 127.2 1.40
P2 60 143.9 1.38
P3 120 231.6 1.36
P4 30 124.0 1.40
P5 30 130.6 1.41
P6 30 103.2 1.42
P7 30 999.0 1.39
〔低反射フィルムの製造〕
実施例１で得られた複合酸化物ゾルを限外濾過膜に通し、分散媒の水をエタノールに置換した。このエタノールゾル（固形分濃度５重量％）５０ｇと、アクリル樹脂（ヒタロイド１００７、日立化成（株）製）３ｇおよびイソプロパノールとｎ−ブタノールの１／１（重量比）混合溶媒４７ｇとを充分に混合して塗布液を調製した。
[Manufacture of low reflection film]
The composite oxide sol obtained in Example 1 was passed through an ultrafiltration membrane, and water in the dispersion medium was replaced with ethanol. 50 g of this ethanol sol (solid content concentration 5% by weight), 3 g of acrylic resin (Hitaloid 1007, manufactured by Hitachi Chemical Co., Ltd.), and 47 g of a 1: 1 (weight ratio) mixed solvent of isopropanol and n-butanol were sufficiently mixed. Thus, a coating solution was prepared.
これをＰＥＴフィルムにバーコーター法で塗布し、８０℃、１分間乾燥させて、低反射フィルム（Ｆ８）を得た。このフィルム（Ｆ８）と、未塗布のＰＥＴフィルム（Ｆ８0）の全光線透過率、ヘイズ、および波長５５０ｎｍの光線の反射率を表２に示す。全光線透過率およびヘイズは、ヘーズメーター（スガ試験機（株）製）により、反射率は分光光度計（日本分光社、Ubest-55）により夫々測定した。 This was applied to a PET film by a bar coater method and dried at 80 ° C. for 1 minute to obtain a low reflection film (F8). Table 2 shows the total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of this film (F8) and uncoated PET film (F8 0 ). The total light transmittance and haze were measured with a haze meter (manufactured by Suga Test Instruments Co., Ltd.), and the reflectance was measured with a spectrophotometer (JASCO Corporation, Ubest-55).
〔低反射ガラスの製造〕
エチルシリケート（ＳｉＯ2濃度２８重量％）２０ｇ、エタノール４５ｇおよび純水５．３３ｇの混合溶液に少量の塩酸を添加して、エチルシリケートの部分加水分解物を含有したマトリックスを得た。このマトリックスに、実施例１で得られた複合酸化物ゾルをエタノールと溶媒置換したエタノールゾル（固形分濃度１８重量％）１６．７ｇを混合して塗布液を調製した。
[Manufacture of low reflection glass]
A small amount of hydrochloric acid was added to a mixed solution of 20 g of ethyl silicate (SiO 2 concentration 28 wt%), 45 g of ethanol and 5.33 g of pure water to obtain a matrix containing a partial hydrolyzate of ethyl silicate. To this matrix, 16.7 g of ethanol sol (solid content concentration: 18% by weight) obtained by replacing the composite oxide sol obtained in Example 1 with ethanol and a solvent was mixed to prepare a coating solution.
この塗布液を透明ガラス板の表面に５００ｒｐｍ、１０秒の条件でスピナー法により塗布した後、１６０℃で３０分間、加熱処理して低反射ガラス（Ｇ９）を得た。このガラス（Ｇ９）と、未塗布のガラス（Ｇ９0）の全光線透過率、ヘイズ、および波長５５０ｎｍの光線の反射率を表２に示す。 This coating solution was applied to the surface of the transparent glass plate by a spinner method at 500 rpm for 10 seconds, and then heat-treated at 160 ° C. for 30 minutes to obtain low reflection glass (G9). Table 2 shows the total light transmittance, haze, and reflectance of light having a wavelength of 550 nm of this glass (G9) and uncoated glass (G9 0 ).
実施例９において、複合酸化物ゾルを実施例３の複合酸化物ゾルに代えた以外は実施例９と同様にして、低反射ガラス（Ｇ１０）を得た。 In Example 9, a low reflection glass (G10) was obtained in the same manner as in Example 9, except that the complex oxide sol was replaced with the complex oxide sol of Example 3.
［表２］
基材 全光線透過率 ヘイズ 反射率
（％） （％） （％）
Ｆ８0 90.7 2.0 7.0
Ｆ８ 94.3 1.8 1.0
Ｇ９0 92.0 0.7 4.0
Ｇ９ 94.8 0.7 0.8
Ｇ１０ 95.2 0.9 0.1
[Table 2]
Substrate total light transmittance haze reflectance
( % ) ( % ) ( % )
F8 0 90.7 2.0 7.0
F8 94.3 1.8 1.0
G9 0 92.0 0.7 4.0
G9 94.8 0.7 0.8
G10 95.2 0.9 0.1
Claims (4)
A composite oxide sol in which a composite oxide colloid particle having an average particle diameter of 5 to 300 nm in the range of silica and an inorganic oxide other than silica is dispersed in water and / or an organic solvent, the colloid particle is: A part of the element constituting the inorganic oxide is removed to increase pores and the particle surface is coated with a coating, and the refractive index is in the range of 1.36 to 1.44. Complex oxide sol.
The composite oxide sol according to claim 1, wherein the coating is made of silica.
A composite oxide comprising a composite oxide fine particle having an average particle diameter of 5 to 300 nm in the range of silica and an inorganic oxide other than silica and a coating film-forming matrix formed on the surface thereof. The fine particles have pores increased by removing a part of the elements constituting the inorganic oxide, and the particle surface is coated with a film, and the refractive index is in the range of 1.36 to 1.44. A coated substrate characterized by the above.
The coated substrate according to claim 3, wherein the surface coating of the composite oxide particles is made of silica.
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| WO2016002215A1 (en) * | 2014-06-30 | 2016-01-07 | 日本板硝子株式会社 | Low-reflection coating, substrate provided with low-reflection coating, and photoelectric conversion device |
| JPWO2016002215A1 (en) * | 2014-06-30 | 2017-04-27 | 日本板硝子株式会社 | Low reflection coating, substrate with low reflection coating and photoelectric conversion device |
| US10416353B2 (en) | 2014-06-30 | 2019-09-17 | Nippon Sheet Glass Company, Limited | Low-reflection coating, low-reflection coated substrate, and photoelectric conversion device |
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