JP2009227500A - Transparent titanium oxide organosol, coating composition with the same blended, optical base material - Google Patents
Transparent titanium oxide organosol, coating composition with the same blended, optical base material Download PDFInfo
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本発明は、少なくともケイ素の水和酸化物で被覆された酸化チタンゾル粒子が有機溶媒中に分散している透明酸化チタンオルガノゾルに関する。この透明酸化チタンオルガノゾルは、バインダーと混合して基材、例えばレンズの表面に高い透明度と屈折率を有するコーティング層を形成するコーティング組成物として有用である。 The present invention relates to a transparent titanium oxide organosol in which titanium oxide sol particles coated with at least silicon hydrated oxide are dispersed in an organic solvent. This transparent titanium oxide organosol is useful as a coating composition that is mixed with a binder to form a coating layer having high transparency and refractive index on the surface of a substrate, for example, a lens.
酸化チタン系ゾルは、例えば合成樹脂製レンズやフィルムの表面に高透明かつ高屈折率なハードコートあるいは反射防止膜等を形成するための被覆組成物の成分として使用されている。 Titanium oxide-based sols are used, for example, as a component of a coating composition for forming a highly transparent and high refractive index hard coat or antireflection film on the surface of a synthetic resin lens or film.
本発明者は、特許文献１において酸化チタンゾル粒子を核とし、そのまわりをケイ素の水和酸化物で被覆し、必要であればその上にさらに他の金属水和酸化物を被覆した被覆酸化チタンヒドロゾルおよびその製造方法を開示した。また、この被覆酸化チタンヒドロゾルを有機溶媒例えばメタノールで溶媒置換した被覆酸化チタンオルガノゾルも開示している。しかし、この被覆酸化チタンオルガノゾルの溶媒はメタノールで沸点が低いため、夏場等の高温での経時安定性がよくない。 In the patent document 1, the inventor has coated titanium oxide in which titanium oxide sol particles are used as a core, and the periphery thereof is coated with a hydrated oxide of silicon and, if necessary, further coated with another metal hydrated oxide. Hydrosols and methods for their production have been disclosed. Also disclosed is a coated titanium oxide organosol obtained by replacing the coated titanium oxide hydrosol with an organic solvent such as methanol. However, since the solvent of this coated titanium oxide organosol is methanol and has a low boiling point, its stability over time at high temperatures such as in summer is not good.
酸化チタンゾル粒子をケイ素の水和酸化物等で被覆する目的は、一つにはその光触媒活性を抑制することであり、他は中性領域において安定なゾルを得るためである。本発明者が特許文献１に開示した被覆酸化チタンゾルは、中性領域で安定であり、オルガノゾルの形でバインダーと混合して高い透明度と屈折率を有するハードコート、反射防止膜等を形成するコーティング組成物に用いることができる。この用途に用いる場合、通常メタノールやエタノールを被覆チタニアゾルの媒体として使用するが、これらは沸点が低いため溶媒の蒸発が速すぎ塗膜の白化あるいはクラックが発生する。またメタノールやエタノールのような低級アルコールは極性が高いためバインダーとの混合安定性が良くないものがある。
特許文献２は高沸点溶剤であるエチレングリコール、プロピレングリコールのようなアルキレングリコールに分散した酸化チタンゾルが開示されているがアルキレングリコールの沸点は１８０℃と高く、耐熱性の低いフィルム等に塗布することはできない。
The purpose of coating the titanium oxide sol particles with a hydrated oxide of silicon or the like is to suppress the photocatalytic activity of one part and to obtain a stable sol in the neutral region. The coated titanium oxide sol disclosed in Patent Document 1 by the present inventor is stable in the neutral region, and is mixed with a binder in the form of an organosol to form a hard coat having high transparency and refractive index, an antireflection film, etc. It can be used in a composition. When used in this application, methanol or ethanol is usually used as a medium for the coated titania sol, but these have low boiling points, so that the solvent evaporates too quickly and whitening or cracking of the coating occurs. In addition, lower alcohols such as methanol and ethanol have a high polarity, so that some of them have poor mixing stability with the binder.
Patent Document 2 discloses a titanium oxide sol dispersed in an alkylene glycol such as ethylene glycol and propylene glycol, which are high-boiling solvents. The boiling point of alkylene glycol is as high as 180 ° C., and it is applied to a film having low heat resistance. I can't.
上記課題を解決するため、本発明は、分散相が少なくともケイ素の水和酸化物で被覆され、耐光性，酸化チタンゾルの安定性を向上させるためにケイ素の水和酸化物に加え、スズ、アルミニウム、ジルコニウムおよびアンチモンより選ばれた少なくとも１種の他金属水和酸化物の被覆層を持つ酸化チタンゾル粒子であり、分散媒はエチレングリコールまたはプロピレングリコールのモノ−またはジ−低級アルキルエーテルであり、分散剤はアミノ基を有し分子量５，０００〜５０，０００の高分子系分散剤であることを特徴とする透明酸化チタンオルガノゾルを提供する。さらに該透明酸化チタンオルガノゾルとバインダーを混合して形成されるコーティング組成物、そのコーティング組成物が塗布された光学基材を提供する。 In order to solve the above-mentioned problems, the present invention provides a dispersion phase coated with at least silicon hydrated oxide, tin, aluminum in addition to silicon hydrated oxide in order to improve light resistance and stability of titanium oxide sol. Titanium oxide sol particles having a coating layer of at least one other metal hydrated oxide selected from zirconium and antimony, and the dispersion medium is a mono- or di-lower alkyl ether of ethylene glycol or propylene glycol, dispersed The agent provides a transparent titanium oxide organosol having an amino group and a high molecular weight dispersant having a molecular weight of 5,000 to 50,000. Further provided are a coating composition formed by mixing the transparent titanium oxide organosol and a binder, and an optical substrate coated with the coating composition.
本発明の透明酸化チタンオルガノゾルは、被覆した酸化チタンゾル粒子と、分散媒である有機溶媒と、および分散剤の少なくとも３成分を含んでいる。
Ａ．被覆した酸化チタンゾル粒子
ケイ素の水和酸化物単独、またはケイ素の水和酸化物に加え、スズ、アルミニウムおよびジルコニウムから選ばれた水和酸化物で被覆した酸化チタンゾルおよびその製造方法は、本出願人の特開２００７−２４６３５１公報に開示されている。他の水和金属酸化物がアンチモンの水和酸化物である被覆酸化チタンゾルは本出願人の特願２００７−１０７６８３に開示されている。概略すると、含水酸化チタンを解膠して得られる酸化チタンは解膠に使用した塩酸を含んでいるため強酸性である。このためゾルへ３−グリシドキシプロピルトリメトキシシランのような水溶性シランカップリング剤を加えるか、または過酸化水素のような金属イオン錯化剤を加えてゾルをｐＨ変化に対して安定化させた後、ゾルをあらかじめアルカリを添加したケイ酸ナトリウムの水溶液へ添加する。さらにスズ、アルミニウム、ジルコニウム、アンチモン等の他の金属水和酸化物を被覆する場合は溶液をアルカリ性に保ってこれら金属の水溶性塩を添加し、添加終了後酸性ないし中性域において溶液を熟成させ、限外ろ過等によって脱塩して酸化チタンのヒドロゾルを製造する。
核となる酸化チタンの結晶形は特に限定しないが高耐光性、高屈折率を発現させるためにはルチルが好ましい。
被覆した酸化チタンの平均粒子径は１００ｎｍ以下である。１００ｎｍ以上であれば高透明な酸化チタンオルガノゾルは得られない。
酸化チタンに対する金属水和酸化物の被覆量は、ケイ素の水和酸化物がＳｉＯ２として５〜５０重量％、他の金属水和酸化物がＳｎＯ２，ＺｒＯ２，Ａｌ２Ｏ３またはＳｂ２Ｏ３として合計０〜１００重量％、全体で５〜１５０重量％であるのが好ましい。被覆量が５％以下の場合、屈折率は高くなるが酸化チタンゾルの酸性ないしは中性領域下での安定性が損なわれ、高透明な酸化チタンゾルを得ることができない。さらに被覆量が少なすぎ耐光性も低下する。
ケイ素の水和酸化物の被覆量が５０％以上ないしはトータルの被覆量が１５０％以上の場合は十分被覆されているため耐光性は良好であるが被覆物は酸化チタンより屈折率が低いため塗膜の屈折率を低下させる。
本技術は酸化チタン以外の無機酸化物ゾル、例えば酸化ジルコニウムゾル、酸化スズゾル、酸化アルミニウムゾル、酸化セリウムゾル、酸化アンチモンゾルにも応用可能である。
The transparent titanium oxide organosol of the present invention contains at least three components of coated titanium oxide sol particles, an organic solvent as a dispersion medium, and a dispersant.
A. Coated titanium oxide sol particles Silicon hydrated oxide alone or in addition to silicon hydrated oxide, titanium oxide sol coated with hydrated oxide selected from tin, aluminum and zirconium Japanese Patent Application Laid-Open No. 2007-246351. A coated titanium oxide sol in which another hydrated metal oxide is a hydrated oxide of antimony is disclosed in Japanese Patent Application No. 2007-107683 of the present applicant. In summary, titanium oxide obtained by peptizing hydrous titanium oxide is strongly acidic because it contains hydrochloric acid used for peptization. For this reason, a water-soluble silane coupling agent such as 3-glycidoxypropyltrimethoxysilane is added to the sol, or a metal ion complexing agent such as hydrogen peroxide is added to stabilize the sol against pH change. Then, the sol is added to an aqueous solution of sodium silicate to which alkali has been added in advance. Furthermore, when coating other metal hydrated oxides such as tin, aluminum, zirconium, antimony, etc., keep the solution alkaline and add a water-soluble salt of these metals. And desalting by ultrafiltration or the like to produce a titanium oxide hydrosol.
The crystal form of titanium oxide serving as a nucleus is not particularly limited, but rutile is preferable in order to exhibit high light resistance and high refractive index.
The average particle diameter of the coated titanium oxide is 100 nm or less. If it is 100 nm or more, a highly transparent titanium oxide organosol cannot be obtained.
The coverage of the hydrated metal oxide to titanium oxide, 5 to 50% by weight hydrous oxide of silicon as SiO 2, other hydrated metal oxide is SnO 2, ZrO 2, Al 2 O 3 or Sb 2 The total amount of O 3 is preferably 0 to 100% by weight, and preferably 5 to 150% by weight as a whole. When the coating amount is 5% or less, the refractive index increases, but the stability of the titanium oxide sol under the acidic or neutral region is impaired, and a highly transparent titanium oxide sol cannot be obtained. Furthermore, there is too little coating amount and light resistance also falls.
When the coating amount of the silicon hydrated oxide is 50% or more or the total coating amount is 150% or more, it is sufficiently coated and has good light resistance, but the coating has a refractive index lower than that of titanium oxide. Reduce the refractive index of the film.
The present technology can also be applied to inorganic oxide sols other than titanium oxide, such as zirconium oxide sol, tin oxide sol, aluminum oxide sol, cerium oxide sol, and antimony oxide sol.
Ｂ．分散媒
バインダーと混合してコーティング組成物とするためには、被覆酸化チタンヒドロゾルを有機溶媒で溶媒置換して得られるオルガノゾルが使用される。これまでヒドロゾルの溶媒置換に使用された有機溶媒は、メタノール、エタノールなどの低級アルカノール、エチレングリコール、プロピレングリコール等がある。
メタノール、エタノールなどの低級アルカノールは沸点が低いため溶媒の蒸発が速すぎ塗膜の白化あるいはクラックの発生が起こる。また低級アルコールは極性が高いためバインダーとの混合安定性が良くないものがある。
エチレングリコール、プロピレングリコールのようなアルキレングリコールは沸点が１８０℃以上と非常に高く耐熱性の低いフィルム等への塗布は困難である。
本発明では１００℃以上１５０℃以下の適度の沸点を有し、かつ適度の蒸発速度を有するエチレングリコールまたはプロピレングリコールのモノ−またはジ−低級アルキルエーテルを選択する。具体例としては、プロピレングリコールモノメチルエーテル（ＢＰ１２０℃）、エチレングリコールモノメチルエーテル（ＢＰ１２４℃）、エチレングリコールモノエチルエーテル（ＢＰ１３５℃）、エチレングリコールジエチルエーテル（ＢＰ１２１℃）、エチレングリコールイソプロピルエーテル（ＢＰ１４１℃）、プロピレングリコールモノエチルエーテル（ＢＰ１３２℃）などがある。特に好ましいのは沸点約１２０℃のプロピレングリコールモノメチルエーテルである。
B. In order to mix with a dispersion medium binder to form a coating composition, an organosol obtained by replacing the coated titanium oxide hydrosol with an organic solvent is used. Examples of organic solvents that have been used for solvent replacement of hydrosols so far include lower alkanols such as methanol and ethanol, ethylene glycol, and propylene glycol.
Lower alkanols such as methanol and ethanol have a low boiling point, so that the solvent evaporates too quickly and whitening or cracking of the coating occurs. Some lower alcohols have a high polarity, so that the mixing stability with the binder is not good.
Alkylene glycols such as ethylene glycol and propylene glycol have a very high boiling point of 180 ° C. or higher and are difficult to apply to films having low heat resistance.
In the present invention, a mono- or di-lower alkyl ether of ethylene glycol or propylene glycol having an appropriate boiling point of 100 ° C. to 150 ° C. and an appropriate evaporation rate is selected. Specific examples include propylene glycol monomethyl ether (BP 120 ° C.), ethylene glycol monomethyl ether (BP 124 ° C.), ethylene glycol monoethyl ether (BP 135 ° C.), ethylene glycol diethyl ether (BP 121 ° C.), ethylene glycol isopropyl ether (BP 141 ° C.). And propylene glycol monoethyl ether (BP 132 ° C.). Particularly preferred is propylene glycol monomethyl ether having a boiling point of about 120 ° C.
Ｃ．分散剤
本発明の場合、透明酸化チタンオルガノゾルの希釈安定性ならびに透明酸化チタンオルガノゾルとバインダーとを含むコーティング組成物が使用前の貯蔵時安定であるばかりでなく、コーティング液を基材に塗布し、加熱によって溶媒を除去する過程で透明性の低下、白化などが発生してはならない。そのため分散剤は多種類のバインダー樹脂と相溶性があり、高い分散能を必要とする。分散剤としては高分子系として変性ポリウレタン、変性ポリアクリレート、変性ポリエステル、ポリカルボン酸系、リン酸エステル系、アルキレンオキシド系、シリコーン系等、更にはアニオン系、カチオン系、ノニオン系の分散剤がある。この中でリン酸エステル系分散剤はヒドロゾルからエチレングリコールまたはプロピレングリコールのモノ−またはジ−低級アルキルエーテルに溶媒置換可能で固形分も１０％以上に濃縮できる。しかし、これはバインダーとの混合安定性、希釈安定性が劣っていた。バインダーとの混合安定性、希釈安定性の両方が優れている分散剤はアミノ基を有し分子量５，０００〜５０，０００の高分子系分散剤である。好ましくはアルキルアミンのアルキレンオキシド変性物で分子量５，０００〜５０，０００の高分子系分散剤である。市販品としてはソルスパース２００００（日本ルーブリゾール（株）製）、ＴＡＭＮＯ−１５（日光ケミカル（株）製）、ＢＹＫ−１６０（ビッグケミー・ジャパン（株））
ＢＹＫ−１６１（ビッグケミー・ジャパン（株））等がある。
この分散剤の使用量は、酸化チタンオルガノゾル中の酸化チタン粒子に対して３〜３０重量％が適当である。使用量が３％以下の場合、分散剤量が少なすぎオルガノゾルの安定性が損なわれる。３０％以上の場合、固形分中の分散剤配合量が増大し塗膜の屈折率および耐擦傷性を低下させる。
C. Dispersant In the case of the present invention, not only the dilution stability of the transparent titanium oxide organosol and the coating composition containing the transparent titanium oxide organosol and the binder are stable before storage, but also the coating liquid is applied to the substrate. However, the process of removing the solvent by heating should not cause a decrease in transparency or whitening. Therefore, the dispersant is compatible with many kinds of binder resins and requires high dispersibility. Examples of the dispersant include a polymer-based modified polyurethane, modified polyacrylate, modified polyester, polycarboxylic acid-based, phosphate ester-based, alkylene oxide-based, silicone-based, and the like, and anionic, cationic, and nonionic dispersants. is there. Among them, the phosphate ester dispersant can be solvent-substituted from hydrosol to ethylene glycol or propylene glycol mono- or di-lower alkyl ether, and the solid content can be concentrated to 10% or more. However, this was inferior in mixing stability and dilution stability with the binder. A dispersant having both excellent mixing stability and dilution stability with a binder is a polymeric dispersant having an amino group and a molecular weight of 5,000 to 50,000. Preferably, it is a polymer dispersant having a molecular weight of 5,000 to 50,000, which is an alkylene oxide modified product of alkylamine. Commercially available products include Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), TAMNO-15 (manufactured by Nikko Chemical Co., Ltd.), BYK-160 (Big Chemie Japan Co., Ltd.).
BYK-161 (Big Chemie Japan Co., Ltd.) and the like.
The amount of the dispersant used is suitably 3 to 30% by weight based on the titanium oxide particles in the titanium oxide organosol. When the amount used is 3% or less, the amount of the dispersant is too small and the stability of the organosol is impaired. In the case of 30% or more, the amount of the dispersant in the solid content increases and the refractive index and scratch resistance of the coating film are lowered.
本発明の透明酸化チタンオルガノゾルは、高透明なコーティング組成物を得るために透明酸化チタンオルガノゾルの透明性を高くする必要がある。透明酸化チタンオルガノゾルの透明性は固形分濃度１０重量％において光路長１０ｍｍの石英セルで測定する時ヘーズ値が５０％以下、好ましくは３０％以下である。ヘーズ値が５０％以上の場合、混合したコーティング液の透明性も低下し、コーティング組成物の透明性も低下する。 The transparent titanium oxide organosol of the present invention needs to have high transparency in order to obtain a highly transparent coating composition. The transparency of the transparent titanium oxide organosol has a haze value of 50% or less, preferably 30% or less when measured with a quartz cell having an optical path length of 10 mm at a solid content concentration of 10% by weight. When the haze value is 50% or more, the transparency of the mixed coating liquid is also lowered, and the transparency of the coating composition is also lowered.
溶媒置換は、前記分散剤を前記有機溶媒、例えばプロピレングリコールモノメチルエーテルに溶解し、この溶液を被覆した酸化チタンヒドロゾルへ加えて混合する。ロータリーエバポレーターを用いて減圧下で共沸により水が除去する。必要に応じて有機溶媒を添加しながら濃縮する。水分量が１０％以下になるまで溶媒置換し、所定の濃度になるまで濃縮する。水分量が１０％以上の場合、バインダーあるいは樹脂との混合安定性ならびに希釈安定性が低下する。
また、酸化チタンヒドロゾルを一度メタノールに溶媒置換した後、分散剤と有機溶媒を加え、同様な方法で有機溶媒に置換することも可能である。
透明酸化チタンオルガノゾルには透明性を損なわなければ粘度調整剤、有機ケイ素化合物等の添加剤を加えてもかまわない。
In the solvent replacement, the dispersant is dissolved in the organic solvent such as propylene glycol monomethyl ether, and this solution is added to the titanium oxide hydrosol coated and mixed. Water is removed azeotropically under reduced pressure using a rotary evaporator. Concentrate while adding organic solvent if necessary. The solvent is replaced until the water content becomes 10% or less, and the solution is concentrated to a predetermined concentration. When the water content is 10% or more, the mixing stability and dilution stability with the binder or resin are lowered.
It is also possible to replace the titanium oxide hydrosol with methanol once, then add a dispersant and an organic solvent, and replace with an organic solvent in the same manner.
Additives such as viscosity modifiers and organosilicon compounds may be added to the transparent titanium oxide organosol as long as the transparency is not impaired.
本発明は基材、特にレンズのような光学基材の表面に、高透明度および高屈折率を有する膜を形成するためのコーティング組成物を提供する。この組成物は、上に述べた本発明の透明酸化チタンオルガノゾルと、バインダーあるいは樹脂とを含む。前述したように、透明酸化チタンオルガノゾルが高い分散能を有する分散剤を含んでいるので、多種類のバインダーあるいは樹脂と組合せることができる。酸化チタンゾルを含んでいるコーティング組成物のバインダーあるいは樹脂は、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、シリコーン樹脂、フェノール樹脂、酢酸ビニル樹脂のような熱硬化系樹脂や非水系のＵＶ硬化型樹脂、下式で表される有機ケイ素化合物またはその部分加水分解物である。
（Ｒ）ｎ−Ｓｉ−Ｘ４−ｎ
式中、Ｒは互いに同一または異なる有機官能基（好ましくは炭化水素基）、Ｘは加水分解基であり、ｎは０〜３、好ましくは１または２である。
高透明酸化チタンオルガノゾルを配合したコーティング組成物で、膜厚1〜３μｍ、屈折率が１．６〜２．７の塗膜を作成したとき、塗膜のヘーズが０．１〜２％である。また、必要に応じて本コーティング組成物にレオロジーコントロール剤、有機ケイ素化合物等の添加剤を加えてもかまわない。本コーティング組成物を高屈折率光学基材と同じ屈折率に調整し、塗布した高屈折率光学基材は干渉縞がなく透明性の高い光学基材が得られる。
以下の実施例は限定を意図しない。これらにおいて％は特記しない限り重量基準による。
The present invention provides a coating composition for forming a film having high transparency and high refractive index on the surface of a substrate, particularly an optical substrate such as a lens. This composition contains the transparent titanium oxide organosol of the present invention described above and a binder or resin. As described above, since the transparent titanium oxide organosol contains a dispersant having a high dispersibility, it can be combined with many kinds of binders or resins. The binder or resin of the coating composition containing the titanium oxide sol is a heat such as polyester resin, acrylic resin, urethane resin, vinyl chloride resin, epoxy resin, melamine resin, fluorine resin, silicone resin, phenol resin, vinyl acetate resin. A curable resin, a non-aqueous UV curable resin, an organosilicon compound represented by the following formula, or a partial hydrolyzate thereof.
(R) n -Si-X 4-n
In the formula, R is the same or different organic functional group (preferably a hydrocarbon group), X is a hydrolyzable group, and n is 0 to 3, preferably 1 or 2.
A coating composition containing a highly transparent titanium oxide organosol. When a coating film having a film thickness of 1 to 3 μm and a refractive index of 1.6 to 2.7 is prepared, the haze of the coating film is 0.1 to 2%. is there. Moreover, you may add additives, such as a rheology control agent and an organosilicon compound, to this coating composition as needed. The coating composition is adjusted to have the same refractive index as that of the high refractive index optical substrate, and the applied high refractive index optical substrate is free from interference fringes and a highly transparent optical substrate is obtained.
The following examples are not intended to be limiting. In these,% is based on weight unless otherwise specified.
透明酸化チタンオルガノゾル
実施例１
第１部 ルチル形酸化チタンヒドロゾル（Ａ液）
１Ｌのガラスビーカーに、ＴｉＯ２濃度２５％のオキシ塩化チタン水溶液２４０ｇ（ＴｉＯ２として６０ｇ）と、ＺｒＯ２濃度３５％のオキシ塩化ジルコニウム粉末５ｇ（ＺｒＯ２として１．８ｇ）を入れ、水で全量を１Ｌとし、溶解を確認した。
攪拌手段および還流冷却器を備えた２Ｌフラスコに、水１ｋｇと、ＳｎＯ２濃度３０％の塩化第二スズ水溶液２０ｇ（ＳｎＯ２として６ｇ）と、３６％塩酸１６ｇを仕込み、攪拌しながら６０℃へ加熱した。この温度を維持しながら上のオキシ塩化チタン・オキシ塩化ジルコニウム水溶液１Ｌを１５分間要して滴下し、滴下終了後沸騰温度まで加熱し、３時間沸騰状態で加熱還流した。加熱停止後４０℃まで冷却し、限外濾過モジュール（旭化成ケミカルズ（株）製マイクローザＳＬＰ−１０５３）にろ液量と同量のイオン交換水を補給しながら通液し、ＴｉＯ２濃度１０％で電気伝導度が１０，０００μＳ／ｃｍになるまで電解質成分を除去し、ＴｉＯ２濃度２０％まで濃縮し、ｐＨ１．３の酸化チタンゾル（Ａ液）３００ｇを得た。
Ａ液を１００℃で乾燥した粉末のＸ線回折は結晶形がルチル形であることを示した。
Transparent titanium oxide organosol Example 1
Part 1 Rutile-type titanium oxide hydrosol (liquid A)
In a 1 L glass beaker, 240 g of titanium oxychloride aqueous solution with a TiO 2 concentration of 25% (60 g as TiO 2 ) and 5 g of zirconium oxychloride powder with a ZrO 2 concentration of 35% (1.8 g as ZrO 2 ) were added, and the whole amount was added with water. Was 1 L, and dissolution was confirmed.
A 2 L flask equipped with a stirring means and a reflux condenser was charged with 1 kg of water, 20 g of a stannic chloride aqueous solution having a SnO 2 concentration of 30% (6 g as SnO 2 ), and 16 g of 36% hydrochloric acid, and the mixture was heated to 60 ° C. with stirring. Heated. While maintaining this temperature, 1 L of the above aqueous titanium oxychloride / zirconium oxychloride solution was added dropwise over 15 minutes, heated to the boiling temperature after completion of the addition, and heated to reflux for 3 hours in a boiling state. After stopping the heating, it was cooled to 40 ° C. and passed through an ultrafiltration module (Microsa SLP-1053 manufactured by Asahi Kasei Chemicals Co., Ltd.) while replenishing the same amount of ion-exchanged water as the filtrate, and a TiO 2 concentration of 10%. Then, the electrolyte component was removed until the electric conductivity reached 10,000 μS / cm and concentrated to a TiO 2 concentration of 20% to obtain 300 g of a titanium oxide sol (liquid A) having a pH of 1.3.
X-ray diffraction of the powder obtained by drying solution A at 100 ° C. showed that the crystal form was rutile.
第２部 シランカップリング剤処理酸化チタンヒドロゾル（Ｂ液）
２ＬガラスビーカーにＴｉＯ２濃度２０％のルチル形酸化チタンゾル（Ａ液）２００ｇ（ＴｉＯ２として４０ｇ）を取り、イオン交換水でＴｉＯ２濃度４％に希釈し、攪拌しながら３−グリシドキシプロピルトリメトキシシラン（信越化学工業（株）製ＫＢＭ−４０３）５．２ｇを１０分間要して滴下し、シランカップリング剤処理酸化チタンヒドロゾル（Ｂ液）を得た。
Part 2 Silane coupling agent treated titanium oxide hydrosol (liquid B)
In a 2 L glass beaker, take 200 g of rutile-type titanium oxide sol (liquid A) of 20% TiO 2 concentration (40 g as TiO 2 ), dilute to 4% TiO 2 concentration with ion-exchanged water, and add 3-glycidoxypropyl with stirring. Trimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-403) 5.2 g was added dropwise over 10 minutes to obtain a silane coupling agent-treated titanium oxide hydrosol (liquid B).
第３部 酸化チタンヒドロゾルの被覆処理
５Ｌガラスビーカーに、ＳｉＯ２濃度１０％のケイ酸ナトリウム水溶液６０ｇ（ＳｉＯ２として６ｇ）と、４８％水酸化ナトリウム水溶液２ｇを入れ、イオン交換水を加えて全量を１２００ｇとした。この液に攪拌しながらＢ液全量（ＴｉＯ２として４０ｇ）を１５分間要して添加した。添加終了時のｐＨは１０であった。
次にこの反応液を８０℃へ加熱した後、１％塩酸を１２０分間間要して添加し、ｐＨ８に調節した。この液を２０℃に冷却し、１０％クエン酸水溶液でｐＨ３に調節した。この液を限外濾過モジュール（旭化成ケミカルズ（株）製マイクローザＳＬＰ−１０５３）に、ろ液量と同量のイオン交換水を補水しながら通液し、ＴｉＯ２濃度１０％で、電気伝導度が１０００μＳ／ｃｍ以下になるまで電解質成分を低減させた。
The coating process 5L glass beaker Part 3 titanium oxide hydrosol, a SiO 2 concentration of 10% aqueous sodium silicate solution 60 g (6 g as SiO 2), placed in a 48% aqueous solution of sodium hydroxide 2g, by adding ion-exchanged water The total amount was 1200 g. While stirring this solution, the entire amount of solution B (40 g as TiO 2 ) was added over 15 minutes. The pH at the end of the addition was 10.
Next, after heating this reaction liquid to 80 degreeC, 1% hydrochloric acid was added for 120 minutes, and it adjusted to pH8. The solution was cooled to 20 ° C. and adjusted to pH 3 with a 10% aqueous citric acid solution. This solution was passed through an ultrafiltration module (Microza SLP-1053 manufactured by Asahi Kasei Chemicals Corporation) while replenishing the same amount of ion-exchanged water as the amount of the filtrate, with a TiO 2 concentration of 10% and electrical conductivity. The electrolyte component was reduced until the value became 1000 μS / cm or less.
第４部 溶媒置換
2Ｌのガラスビーカーに第3部で作成したゾル４００ｇ（ＴｉＯ２として４０ｇ）に分散剤（日本ルーブリゾール（株）製 ソルスパース２００００） ８ｇを配合したプロピレングリコールモノメチルエーテル８００ｇを加え、室温で熟成した。熟成後、ロータリーエバポレーターを用いて減圧下で２００ｇまで濃縮した。
Part 4 Solvent replacement
To a 2 L glass beaker, 800 g of propylene glycol monomethyl ether containing 8 g of a dispersant (Solsperse 20000 manufactured by Nippon Lubrizol Co., Ltd.) was added to 400 g of the sol prepared in Part 3 (40 g as TiO 2 ), and the mixture was aged at room temperature. After aging, the mixture was concentrated to 200 g under reduced pressure using a rotary evaporator.
実施例２
実施例1の第３部で１０％のケイ酸ナトリウム水溶液を３２ｇ（ＳｉＯ２として３．２ｇ）に変更したことを除き、実施例１の操作を繰り返して固形分２０％のプロピレングリコールモノメチルエーテル分散酸化チタンゾルを作成した。
Example 2
The procedure of Example 1 was repeated except that the 10% sodium silicate aqueous solution was changed to 32 g (3.2 g as SiO 2 ) in the third part of Example 1, and propylene glycol monomethyl ether dispersion having a solid content of 20% was repeated. A titanium oxide sol was prepared.
実施例３
実施例1の第３部でＢ液添加後、ＳｎＯ２濃度３０％の塩化第二スズ水溶液２０ｇ（ＳｎＯ２として６ｇ）を１０％水酸化ナトリウム水溶液と同時にｐＨ１０を保持しながら、３０分間を要して添加したことを除き、実施例１の操作を繰り返して固形分２０％のプロピレングリコールモノメチルエーテル分散酸化チタンゾルを作成した。
Example 3
After adding solution B in Part 3 of Example 1, 30 g of SnO 2 concentration 30% stannic chloride aqueous solution (6 g as SnO 2 ) was required for 30 minutes while maintaining pH 10 simultaneously with 10% sodium hydroxide aqueous solution. The propylene glycol monomethyl ether-dispersed titanium oxide sol having a solid content of 20% was prepared by repeating the procedure of Example 1 except that the titanium oxide sol was added.
実施例４
実施例1の第３部でＢ液添加後、Ａｌ２Ｏ３濃度１０％のアルミン酸ナトリウム水溶液２０ｇ（Ａｌ２Ｏ３として２ｇ）を１０％塩酸と同時にｐＨ１０を保持しながら、３０分間を要して添加したことを除き、実施例１の操作を繰り返して固形分２０％のプロピレングリコールモノメチルエーテル分散酸化チタンゾルを作成した。
Example 4
After adding solution B in Part 3 of Example 1, 30 minutes was required while maintaining pH 10 at the same time with 10% hydrochloric acid in 20 g of an aqueous solution of sodium aluminate having an Al 2 O 3 concentration of 10% ( 2 g as Al 2 O 3 ). The propylene glycol monomethyl ether-dispersed titanium oxide sol having a solid content of 20% was prepared by repeating the procedure of Example 1 except that the titanium oxide sol was added.
実施例５
実施例1の第３部でＢ液添加後、ＺｒＯ２濃度１０％のオキシ塩化ジルコニウム水溶液２０ｇ（ＺｒＯ２として２ｇ）を１０％水酸化ナトリウム水溶液と同時にｐＨ１０を保持しながら、３０分間を要して添加したことを除き、実施例１の操作を繰り返して固形分２０％のプロピレングリコールモノメチルエーテル分散酸化チタンゾルを作成した。
Example 5
After adding the B solution in the third part of Example 1, 30 g of ZrO 2 concentration 10% zirconium oxychloride aqueous solution 20 g ( 2 g as ZrO 2 ) was maintained while maintaining the pH 10 simultaneously with the 10% sodium hydroxide aqueous solution. The propylene glycol monomethyl ether-dispersed titanium oxide sol having a solid content of 20% was prepared by repeating the operation of Example 1 except that the titanium oxide sol was added.
実施例６
２Ｌガラスビーカーに、三酸化アンチモン（日本精鉱（株）ＰＡＴＡＸ−ＣＦ）２００ｇと、３０％過酸化水素水１４６．６７ｇ（Ｈ２Ｏ２として４４ｇ）を仕込み、水を加えて２０００ｇとした。この懸濁液を還流冷却器つきフラスコに入れ、１時間沸騰温度で還流下反応させた。４０℃以下に冷却後、反応液を希釈、ジイソプロピルアミンでｐＨ７．５に調節し、Ｓｂ２Ｏ５ １０％の五酸化アンチモンゾルを得た。実施例1の第３部でＢ液添加後、五酸化アンチモンゾル２０ｇ（Ｓｂ２Ｏ５として２ｇ）を添加したことを除き、実施例１の操作を繰り返して固形分２０％のプロピレングリコールモノメチルエーテル分散酸化チタンゾルを作成した。
Example 6
A 2 L glass beaker was charged with 200 g of antimony trioxide (Nippon Seiko Co., Ltd. PATAX-CF) and 146.67 g of 30% hydrogen peroxide (44 g as H 2 O 2 ), and water was added to make 2000 g. This suspension was placed in a flask equipped with a reflux condenser and reacted at reflux at the boiling temperature for 1 hour. After cooling to 40 ° C. or lower, the reaction solution was diluted and adjusted to pH 7.5 with diisopropylamine to obtain Sb 2 O 5 10% antimony pentoxide sol. After the addition of solution B in Part 3 of Example 1, the procedure of Example 1 was repeated except that 20 g of antimony pentoxide sol ( 2 g as Sb 2 O 5 ) was added, and propylene glycol monomethyl ether having a solid content of 20%. A dispersed titanium oxide sol was prepared.
実施例７
実施例１の第3部で作成したゾルを２％に希釈し、２００℃−１０時間の条件で水熱処理を行った。処理後、室温に冷却し、ＴｉＯ２濃度１０％まで限外ろ過にて濃縮した。その濃縮液６６７ｇ（ＴｉＯ２として４０ｇ）に分散剤（日本ルーブリゾール（株）製 ソルスパース２００００） ８ｇ（ＴｉＯ２に対して２０％）を配合したプロピレングリコールモノメチルエーテル８００ｇを加え、室温で熟成した。熟成後、ロータリーエバポレーターを用いて減圧下で２００ｇまで濃縮した。さらにプロピレングリコールモノメチルエーテル８００ｇを加え、固形分が２０％になるまでロータリーエバポレーターを用いて減圧下で濃縮した。
Example 7
The sol prepared in Part 3 of Example 1 was diluted to 2% and hydrothermally treated under the conditions of 200 ° C. for 10 hours. After the treatment, it was cooled to room temperature and concentrated by ultrafiltration to a TiO 2 concentration of 10%. To the concentrated solution 667 g (40 g as TiO 2 ), 800 g of propylene glycol monomethyl ether containing 8 g (20% with respect to TiO 2 ) of a dispersant (Solsperse 20000 manufactured by Nippon Lubrizol Co., Ltd.) was added and aged at room temperature. After aging, the mixture was concentrated to 200 g under reduced pressure using a rotary evaporator. Further, 800 g of propylene glycol monomethyl ether was added, and the mixture was concentrated under reduced pressure using a rotary evaporator until the solid content became 20%.
実施例８
実施例７で分散剤を２ｇ（ＴｉＯ２に対して５％）に変更したことを除き、実施例７の操作を繰り返して固形分２０％のプロピレングリコールモノメチルエーテル分散酸化チタンゾルを作成した。
Example 8
Except that the dispersant was changed to 2 g (5% with respect to TiO 2 ) in Example 7, the procedure of Example 7 was repeated to prepare a propylene glycol monomethyl ether-dispersed titanium oxide sol having a solid content of 20%.
実施例９
実施例１ 第４部の溶媒をエチレングリコールジエチルエーテルに変更したことを除き、実施例１の操作を繰り返して固形分２０％のエチレングリコールジエチルエーテル分散チタニアゾルを作成した。
Example 9
Example 1 An ethylene glycol diethyl ether-dispersed titania sol having a solid content of 20% was prepared by repeating the procedure of Example 1 except that the solvent in Part 4 was changed to ethylene glycol diethyl ether.
比較例１
実施例１ 第４部において分散剤を添加せず、実施例１の操作を行ったが、プロピレングリコールモノメチルエーテル分散酸化チタンゾルは増粘し溶媒置換できなかった。
Comparative Example 1
Example 1 The operation of Example 1 was carried out without adding a dispersant in Part 4. However, the propylene glycol monomethyl ether-dispersed titanium oxide sol was thickened and could not be replaced with a solvent.
比較例２
実施例１で分散剤を４０ｇ（ＴｉＯ２に対して１００％）に変更したことを除き、実施例１の操作を繰り返して固形分２０％のプロピレングリコールモノメチルエーテル分散酸化チタンゾルを作成した。
比較例３
実施例１ 第３部の酸化チタンヒドロゾルをジイソプロピルアミンで液のｐＨを６に調節し、メタノールでＴｉＯ２濃度５％に希釈し、限外濾過モジュール（旭化成ケミカルズ（株）製マイクローザＳＬＰ−１０５３）に、濾液量と同量のメタノールを補給しながら通液し、メタノールに溶媒置換した。
Comparative Example 2
Except that the dispersant was changed to 40 g (100% with respect to TiO 2 ) in Example 1, the procedure of Example 1 was repeated to prepare a propylene glycol monomethyl ether-dispersed titanium oxide sol having a solid content of 20%.
Comparative Example 3
Example 1 Titanium oxide hydrosol of Part 3 was adjusted to pH 6 with diisopropylamine, diluted with methanol to a TiO 2 concentration of 5%, and ultrafiltration module (Microsa SLP-manufactured by Asahi Kasei Chemicals Corporation) 1053) was passed through while supplying methanol in the same amount as the filtrate, and the solvent was replaced with methanol.
コーティング剤の実施例
コーティング剤（その１）
実施例１０〜１８、比較例４，５
ポリエステル樹脂（大日本インキ化学工業（株）製 ベッコライトＭ６４０１−５０） ３２．６ｇとメラミン樹脂（大日本インキ化学工業（株）製 スーパーベッカミンＪ８２０−５０） ４．８ｇを混合し、バインダーを作成した。次に実施例１〜９および比較例２，３で製造した固形分２０％の酸化チタンゾル １００．０ｇ、溶媒 ５０．０ｇ、バインダー ３３．３ｇを混合し、熱硬化性樹脂を用いたコーティング剤を作成した。
Examples of coating agents
Coating agent (part 1)
Examples 10 to 18, Comparative Examples 4 and 5
32.6 g of polyester resin (Beckolite M6401-50, manufactured by Dainippon Ink and Chemicals Co., Ltd.) and 4.8 g of melamine resin (Super Becamine J820-50, manufactured by Dainippon Ink and Chemicals Co., Ltd.) were mixed and a binder was added. Created. Next, 100.0 g of a 20% solid content titanium oxide sol produced in Examples 1 to 9 and Comparative Examples 2 and 3, 50.0 g of a solvent, and 33.3 g of a binder were mixed, and a coating agent using a thermosetting resin was prepared. Created.
コーティング剤（その２）
実施例１９〜２７、比較例６，７
ＵＶ硬化樹脂（日本合成化学工業（株）製紫光ＵＶ−７６０５Ｂ）１６．７ｇを酸化チタンゾルの溶媒９．０ｇに溶解する。開始剤２種類（チバスペシャリティ・ケミカルズ（株）製イルガキュア１８４及び８１９） 各０．３ｇを酸化チタンゾルの溶媒７．０ｇに溶解する。酸化チタンゾルの溶媒に溶解したＵＶ硬化樹脂 ２５．７ｇと酸化チタンゾルの溶媒に溶解した開始剤７．６ｇを混合し、バインダーを作成した。次に実施例１〜９および比較例２，３で製造した固形分２０％の酸化チタンゾル １００．０ｇ、溶媒 ５０．０ｇ、バインダー ３３．３ｇを混合し、ＵＶ硬化性樹脂を用いたコーティング剤を作成した。
Coating agent (2)
Examples 19 to 27, Comparative Examples 6 and 7
16.7 g of a UV curable resin (purple light UV-7605B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) is dissolved in 9.0 g of a titanium oxide sol solvent. Two types of initiators (Irgacure 184 and 819 manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 g of each is dissolved in 7.0 g of a solvent of titanium oxide sol. A binder was prepared by mixing 25.7 g of a UV curable resin dissolved in a solvent of titanium oxide sol and 7.6 g of an initiator dissolved in a solvent of titanium oxide sol. Next, 100.0 g of a 20% solid content titanium oxide sol produced in Examples 1 to 9 and Comparative Examples 2 and 3, 50.0 g of a solvent, and 33.3 g of a binder were mixed, and a coating agent using a UV curable resin was mixed. Created.
コーティング剤（その３）
実施例２８〜３６、比較例８，９
３−グリシドキシプロピルトリメトキシシラン（信越化学工業（株）ＫＢＭ−４０３）２７．０ｇに、０．０１Ｎ塩酸７．０ｇを加えて２４時間攪拌し、バインダーを作成した。実施例１〜９および比較例２，３で製造した固形分２０％の酸化チタンゾル１００．０ｇ、酸化チタンゾルの溶媒 ６７ｇ、バインダー ２７．０ｇ 硬化剤（アルミニウムアセチルアセトナート）少量、レベリング剤（東レ・ダウコーニング（株）製Ｌ−７００１）少量を加え、攪拌してハードコート用のコーティング剤を作成した。
Coating agent (3)
Examples 28 to 36, Comparative Examples 8 and 9
7.0 g of 0.01N hydrochloric acid was added to 27.0 g of 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM-403) and stirred for 24 hours to prepare a binder. 100.0 g of titanium oxide sol having a solid content of 20% produced in Examples 1 to 9 and Comparative Examples 2 and 3, 67 g of solvent of titanium oxide sol, 27.0 g of binder, a small amount of curing agent (aluminum acetylacetonate), leveling agent (Toray A small amount of L-7001 manufactured by Dow Corning Co., Ltd. was added and stirred to prepare a coating agent for hard coating.
光学部材（その１）
実施例３７〜４５および比較例１０，１１
実施例１０〜１８および比較例４，５のコーティング剤を温度３０℃、湿度７０％の環境下で５００ｒｐｍ、３秒で松浪ガラス工業（株）製ミクロスライドガラスプレート（７０×５５×１．３ｍｍ）にスピンコートし、２５℃で１５分、１１０℃で６０分乾燥して膜厚２μｍの塗膜を形成した。
Optical member (1)
Examples 37 to 45 and Comparative Examples 10 and 11
The coating agents of Examples 10 to 18 and Comparative Examples 4 and 5 were microslide glass plates (70 × 55 × 1.3 mm) manufactured by Matsunami Glass Industry Co., Ltd. in an environment of 30 ° C. and 70% humidity at 500 rpm for 3 seconds. And spin-coated at 25 ° C. for 15 minutes and at 110 ° C. for 60 minutes to form a coating film having a thickness of 2 μm.
光学部材（その２）
実施例４６〜５４および比較例１２，１３
実施例１９〜２７および比較例６，７のコーティング剤を温度３０℃、湿度７０％の環境下で５００ｒｐｍ、３秒で松浪ガラス工業（株）製ミクロスライドガラスプレート（７０×５５×１．３ｍｍ）にスピンコートし、８０℃で３０分乾燥後、 ５８０ｍＪ／ｃｍ２の紫外線を照射して膜厚２μｍの塗膜を作成した。
Optical member (2)
Examples 46 to 54 and Comparative Examples 12 and 13
A micro slide glass plate (70 × 55 × 1.3 mm) manufactured by Matsunami Glass Industry Co., Ltd. was applied in an environment of 30 ° C. and 70% humidity at 500 rpm for 3 seconds in the coating agents of Examples 19 to 27 and Comparative Examples 6 and 7. ), And dried at 80 ° C. for 30 minutes, and then irradiated with 580 mJ / cm 2 of ultraviolet rays to form a coating film having a thickness of 2 μm.
光学部材（その３）
実施例５５〜６３および比較例１４，１５
屈折率１．６７のチオウレタン系の樹脂レンズを濃度１３％のＮａＯＨ水溶液中に5分間浸漬した後、充分に水洗し、乾燥した。実施例２８〜３６、比較例８，９のコーティング剤を温度３０℃、湿度７０％の環境下でディッピング法（引き上げ速度１６．５ｍｍ／秒 マイクロディップコーターＮＤ０４０８ （株）ＳＤＩ製）にて塗布し、２５℃−１５分、８０℃−３０分、１２０℃−６０分乾燥して膜厚２μｍの塗膜を作成した。
Optical member (3)
Examples 55-63 and Comparative Examples 14, 15
A thiourethane resin lens having a refractive index of 1.67 was immersed in an aqueous NaOH solution having a concentration of 13% for 5 minutes, washed thoroughly with water and dried. The coating agents of Examples 28 to 36 and Comparative Examples 8 and 9 were applied by the dipping method (pickup speed 16.5 mm / sec, Micro Dip Coater ND0408, manufactured by SDI Corporation) in an environment of a temperature of 30 ° C. and a humidity of 70%. The film was dried at 25 ° C. for 15 minutes, 80 ° C. for 30 minutes, and 120 ° C. for 60 minutes to form a coating film having a thickness of 2 μm.
酸化チタンゾルの評価
透明性（ヘーズ）
酸化チタンゾルを分散溶媒にて固形分１０％に希釈し、光路長１０ｍｍの石英セルに入れ、ヘーズメーター（日本電色工業（株）ヘーズメーターＮＨＤ−２０００）でヘーズ値を測定した。ヘーズ値が小さいほど透明性は高い。
Evaluation of titanium oxide sol
Transparency (haze)
The titanium oxide sol was diluted with a dispersion solvent to a solid content of 10%, put in a quartz cell having an optical path length of 10 mm, and the haze value was measured with a haze meter (Nippon Denshoku Industries Co., Ltd. Haze Meter NHD-2000). The smaller the haze value, the higher the transparency.
経時安定性
酸化チタンゾルを１ヶ月間 ４０℃の恒温室に保管したときの状態を目視観察した。
○・・・変化なし
△・・・増粘
×・・・ゲル化あるいは凝集
結果を表１に示す。
The time-stable titanium oxide sol was visually observed for one month when stored in a constant temperature room at 40 ° C.
○: No change Δ: Thickening ×: Gelation or aggregation results are shown in Table 1.
コーティング剤および塗膜の評価
コーティング剤の安定性
コーティング剤作成直後および1週間室温で静置したときの状態を目視評価した。実施例１０ないし３６のコーティング剤は作成直後および室温で１週間放置後凝集、増粘などの安定性を示す状態の変化がなかったが、比較例５のコーティング剤はコーティング剤作成直後、凝集した。
塗膜の評価は光学部材に形成した塗膜について行った。
Evaluation of coating agents and coatings
Stability of coating agent Immediately after the preparation of the coating agent and after standing for 1 week at room temperature, the state was visually evaluated. The coating agents of Examples 10 to 36 did not change in the state of stability such as aggregation and thickening immediately after the preparation and after standing for 1 week at room temperature, but the coating agent of Comparative Example 5 aggregated immediately after the preparation of the coating agent. .
The evaluation of the coating film was performed on the coating film formed on the optical member.
塗膜の透明性
塗膜をヘーズメーター（日本電色工業（株）ヘーズメーターＮＨＤ−２０００）でヘーズ値を測定した。ヘーズ値が小さいほど透明性は高い。
The haze value of the transparent coating film of the coating film was measured with a haze meter (Nippon Denshoku Industries Co., Ltd. Haze Meter NHD-2000). The smaller the haze value, the higher the transparency.
塗膜の屈折率
塗膜をエリプソメーター（（株）溝尻光学研究所ＤＶＡ−ＦＬ３Ｇ）で６３３ｎｍの波長における屈折率を測定した。
Refractive index of the coating film The refractive index of the coating film at a wavelength of 633 nm was measured with an ellipsometer (Mizoji Optical Laboratory DVA-FL3G).
塗膜の耐擦傷性
実施例５５〜６３および比較例１４の光学部材を日本スチールウール（株）製スチールウール 番手００００で塗膜表面を荷重３００ｇで１０回擦り、傷の付き方を目視評価した。
○ ： 傷僅少
× ： 全面傷あり
結果を表２に示す。
Scratch resistance of coating film The optical members of Examples 55 to 63 and Comparative Example 14 were rubbed 10 times with a load of 300 g of steel wool with a steel wool number 0000 manufactured by Nippon Steel Wool Co., Ltd., and the scratching was visually evaluated. .
○: Slightly scratched ×: Table 2 shows the results with full scratches.
Claims (15)
（Ｒ）ｎ−Ｓｉ−Ｘ４−ｎまたは
式中、Ｒは互いに同一または異なる有機官能基、Ｘは加水分解基であり、ｎは０〜３である。 The coating composition according to claim 10, wherein the binder is an organosilicon compound represented by the following general formula or a partial hydrolyzate thereof:
(R) n -Si-X 4-n or wherein R is the same or different organic functional group, X is a hydrolyzable group, and n is 0-3.
An optical substrate coated with the coating composition according to claim 10.
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| JP2011148668A (en) * | 2010-01-25 | 2011-08-04 | Jsr Corp | Metal oxide particle dispersion, metal oxide particle-containing composition and film formed using the same, and photoelectric conversion element |
| JP2014063125A (en) * | 2012-08-31 | 2014-04-10 | Fujifilm Corp | Low refractive index film, curable composition for forming low refractive index film, optical member and solid-state imaging device using the same |
| JP2016108189A (en) * | 2014-12-08 | 2016-06-20 | 多木化学株式会社 | Coated titanium oxide sol |
| JP2020105274A (en) * | 2018-12-26 | 2020-07-09 | 長野県 | Hydrophilic coating agent and coating film thereof |
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