JPWO2006057119A1 - INORGANIC COATING COMPOSITION, LOW REFRACTIVE FILM COATING METHOD, AND METHOD FOR FORMING LOW REFRACTIVE FILM - Google Patents

INORGANIC COATING COMPOSITION, LOW REFRACTIVE FILM COATING METHOD, AND METHOD FOR FORMING LOW REFRACTIVE FILM Download PDF

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JPWO2006057119A1
JPWO2006057119A1 JP2006547675A JP2006547675A JPWO2006057119A1 JP WO2006057119 A1 JPWO2006057119 A1 JP WO2006057119A1 JP 2006547675 A JP2006547675 A JP 2006547675A JP 2006547675 A JP2006547675 A JP 2006547675A JP WO2006057119 A1 JPWO2006057119 A1 JP WO2006057119A1
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coating film
coating composition
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洋平 河合
洋平 河合
米田 貴重
貴重 米田
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Abstract

高い透明性を有し、有機基材との密着性に優れた低屈折率性塗膜を形成できる無機塗料組成物。有機基材上に低屈折率性塗膜を形成できる下記組成の無機塗料組成物、平均粒子径5〜3000nmの中空状シリカ粒子:0.1〜20質量%、有機基材を膨潤又は溶解でき、かつ、気圧0.1MPaの状態で沸点130℃以上の、水に混和しうる有機溶剤:1〜20質量%、有機基材を実質上膨潤又は溶解させず、かつ、気圧0.1MPaの状態で沸点50〜120℃の、水に混和しうる有機溶剤及び水:60〜98.9質量%。An inorganic coating composition that can form a low refractive index coating film having high transparency and excellent adhesion to an organic substrate. An inorganic coating composition having the following composition capable of forming a low refractive index coating film on an organic substrate, hollow silica particles having an average particle size of 5 to 3000 nm: 0.1 to 20% by mass, and an organic substrate can be swollen or dissolved In addition, an organic solvent miscible with water having a boiling point of 130 ° C. or higher at a pressure of 0.1 MPa: 1 to 20% by mass, a state in which the organic base material is not substantially swollen or dissolved, and a pressure of 0.1 MPa And a water-miscible organic solvent having a boiling point of 50 to 120 ° C. and water: 60 to 98.9% by mass.

Description

本発明は、透明性の高い低屈折率性塗膜を形成できる無機塗料組成物、低屈折率性塗膜及び低屈折率性塗膜を形成する方法に関する。   The present invention relates to an inorganic coating composition capable of forming a highly transparent low refractive index coating film, a low refractive index coating film, and a method for forming a low refractive index coating film.

従来より、ディスプレイパネルのカバー材料や、光学レンズ、光学フィルタ、偏光フィルム等の有機基材に対して、反射率の低減等を目的として、低屈折率性塗膜を形成する様々な方法が検討されている。この検討の一環として、スパッタやCVD等の蒸着法が挙げられるが、有機基材の場合、高温に加熱することができず、有機基材と塗膜の密着性が充分なものが得られないという問題がある。また、上記蒸着法は一般に、膨大な設備投資がかかりコストが高くなる他、大面積の基材に対しては生産技術的に難しいという問題も挙げられる。このため、簡易な装置で安価に生産できることから、例えば、多孔質シリカ微粒子とバインダを含有した塗布液を塗工して、低屈折率性塗膜を形成する湿式による方法が挙げられる(特許文献1)。しかし、この湿式による方法では、バインダを必須とするため、このバインダの影響により得られる塗膜の反射率がそれほど下がるものは得られてない。また、有機基材上にシリカ等の無機粒子を形成する際には有機基材と無機粒子の密着性を向上させるためにプライマー層やハードコート層が中間層として必要となる場合があり、コストが高くなるという問題がある。   Conventionally, various methods for forming low-refractive-index coatings for display panel cover materials and organic substrates such as optical lenses, optical filters, and polarizing films have been studied for the purpose of reducing reflectivity. Has been. As part of this study, vapor deposition methods such as sputtering and CVD can be mentioned. However, in the case of an organic base material, it cannot be heated to a high temperature, and an organic base material and a coating film with sufficient adhesion cannot be obtained. There is a problem. In addition, the above-described vapor deposition method generally requires a large amount of capital investment and increases the cost, and there is also a problem that it is difficult in terms of production technology for a large-area substrate. For this reason, since it can be produced inexpensively with a simple apparatus, for example, a wet method of forming a low refractive index coating film by applying a coating liquid containing porous silica fine particles and a binder is mentioned (Patent Document). 1). However, in this wet method, since a binder is indispensable, a coating film obtained by the influence of the binder that has a low reflectivity is not obtained. In addition, when forming inorganic particles such as silica on an organic substrate, a primer layer or a hard coat layer may be required as an intermediate layer in order to improve the adhesion between the organic substrate and the inorganic particles. There is a problem that becomes high.

また、ポリカーボネート等の有機基材に強固なシリカ膜を形成する方法として、疎水処理されたシリカ、水、及び有機基材に対して溶解性のあるセロソルブアセテート等の有機溶剤を含んだ塗料が開示されている(特許文献2)。しかし、この方法では、有機基材に対して溶解性のある有機溶剤を大量に含むことから有機基材への侵食がかなり進み、得られた塗膜品が白濁しやすいという問題がある。   Also, as a method for forming a strong silica film on an organic substrate such as polycarbonate, a paint containing hydrophobically treated silica, water, and an organic solvent such as cellosolve acetate that is soluble in the organic substrate is disclosed. (Patent Document 2). However, this method has a problem that since the organic base material contains a large amount of an organic solvent that is soluble in the organic base material, the erosion of the organic base material is considerably advanced, and the obtained coating film product tends to become cloudy.

特開平7−48527号公報JP 7-48527 A 米国特許第4413088号明細書US Pat. No. 4,413,088

本発明は、高い透明性を有し、有機基材との密着性に優れた低屈折率性塗膜を形成できる無機塗料組成物、低屈折率性塗膜及び低屈折率性塗膜を形成する方法を提供することを目的とする。   The present invention forms an inorganic coating composition, a low refractive index coating film and a low refractive index coating film that can form a low refractive index coating film having high transparency and excellent adhesion to an organic substrate. It aims to provide a way to do.

本発明は下記を特徴とする要旨を有する。
(1)(a)平均粒子径5〜3000nmの中空状シリカ粒子を0.1〜20質量%;(b)有機基材を膨潤又は溶解することができ、かつ、気圧0.1MPaの状態で沸点130℃以上の、水に混和しうる有機溶剤Aを1〜20質量%;(c)有機基材を実質上膨潤又は溶解させることなく、かつ、気圧0.1MPaの状態で沸点50〜120℃の、水に混和しうる有機溶剤B及び/又は(d)水を60〜98.9質量%を含有し、有機基材上に低屈折率性塗膜を形成することのできる無機塗料組成物。
(2)前記有機基材がポリカーボネート又はアクリル樹脂からなる上記(1)に記載の無機塗料組成物。
(3)前記有機溶剤Aが、ジグライム、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、アセト酢酸エチル、N−メチル−2−ピロリジノン、2−ピロリジノン、1,3−ジメチル−2−イミダゾリジノン及びジメチルスルホキシドからなる群より選ばれる少なくとも1種である上記(1)又は(2)に記載の無機塗料組成物。
(4)前記有機基材を実質上膨潤又は溶解させることなく、かつ、気圧0.1MPaの状態で沸点50〜120℃の、水に混和しうる有機溶剤が、メタノール、エタノール、n−プロパノール、イソプロパノール、n−ブタノール、イソブタノール、sec−ブタノール及びt−ブタノールからなる群より選ばれる少なくとも1種である上記(1)〜(3)のいずれかに記載の無機塗料組成物。
(5)上記(1)〜(4)のいずれかに記載の無機塗料組成物を有機基材に塗布することにより得られる低屈折率性塗膜。
(6)前記低屈折率性塗膜のJIS K−7150の規格に則ったヘイズが1%以下である上記(5)に記載の低屈折率性塗膜。
(7)前記低屈折率性塗膜の屈折率が1.1〜1.4である上記(5)又は(6)に記載の低屈折率性塗膜。
(8)(a)平均粒子径5〜3000nmの中空状シリカ粒子を0.1〜20質量%;(b)有機基材を膨潤又は溶解することができ、かつ、気圧0.1MPaの状態で沸点130℃以上の、水に混和しうる有機溶剤Aを1〜20質量%;(c)有機基材を実質上膨潤又は溶解させることなく、かつ、気圧0.1MPaの状態で沸点50〜120℃の、水に混和しうる有機溶剤B及び/又は(d)水を60〜98.9質量%;を含有する無機塗料組成物を調製する工程、及び該無機塗料組成物を有機基材上に塗布、乾燥することにより低屈折率性塗膜を形成する工程、を経る低屈折率性塗膜の形成方法。
The present invention has the gist characterized by the following.
(1) (a) 0.1 to 20% by mass of hollow silica particles having an average particle diameter of 5 to 3000 nm; (b) an organic base material can be swollen or dissolved, and at a pressure of 0.1 MPa. 1 to 20% by mass of water-miscible organic solvent A having a boiling point of 130 ° C. or higher; (c) a boiling point of 50 to 120 without substantially swelling or dissolving the organic base material and at a pressure of 0.1 MPa. Inorganic coating composition containing 60-98.9% by mass of organic solvent B and / or (d) water that is miscible with water and capable of forming a low refractive index coating film on an organic substrate. object.
(2) The inorganic coating composition according to the above (1), wherein the organic substrate is made of polycarbonate or acrylic resin.
(3) The organic solvent A is diglyme, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetoacetate, N-methyl-2-pyrrolidinone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazo The inorganic coating composition according to the above (1) or (2), which is at least one selected from the group consisting of lysinone and dimethyl sulfoxide.
(4) An organic solvent miscible with water having a boiling point of 50 to 120 ° C. in a state of atmospheric pressure of 0.1 MPa without substantially swelling or dissolving the organic base material is methanol, ethanol, n-propanol, The inorganic coating composition according to any one of (1) to (3), which is at least one selected from the group consisting of isopropanol, n-butanol, isobutanol, sec-butanol, and t-butanol.
(5) A low refractive index coating film obtained by applying the inorganic coating composition according to any one of (1) to (4) to an organic substrate.
(6) The low refractive index coating film according to the above (5), wherein the low refractive index coating film has a haze of 1% or less in accordance with JIS K-7150 standards.
(7) The low refractive index coating film according to (5) or (6) above, wherein the low refractive index coating film has a refractive index of 1.1 to 1.4.
(8) (a) 0.1 to 20% by mass of hollow silica particles having an average particle diameter of 5 to 3000 nm; (b) the organic base material can be swollen or dissolved, and the atmospheric pressure is 0.1 MPa. 1 to 20% by mass of water-miscible organic solvent A having a boiling point of 130 ° C. or higher; (c) a boiling point of 50 to 120 without substantially swelling or dissolving the organic base material and at a pressure of 0.1 MPa. A step of preparing an inorganic coating composition containing an organic solvent B miscible with water and / or (d) 60 to 98.9% by mass of water, and the inorganic coating composition on an organic substrate A method for forming a low refractive index coating film, comprising: applying and drying to form a low refractive index coating film.

本発明により、高い透明性を有し、有機基材との密着性に優れた低屈折率性塗膜を形成できる無機塗料組成物及び低屈折率性塗膜を得ることができる。また、本発明により、簡易で、安価な低屈折率性塗膜の形成方法も提供することができる。   According to the present invention, it is possible to obtain an inorganic coating composition and a low refractive index coating film which can form a low refractive index coating film having high transparency and excellent adhesion to an organic substrate. The present invention can also provide a simple and inexpensive method for forming a low refractive index coating film.

本発明の無機塗料組成物は、(a)中空シリカ粒子、(b)有機溶剤Aと、(c)有機溶剤B及び/又は(d)水とを含有する。   The inorganic coating composition of the present invention contains (a) hollow silica particles, (b) an organic solvent A, and (c) an organic solvent B and / or (d) water.

本発明において、(a)中空シリカ粒子は平均粒子径5〜3000nmであることが必要である。平均粒子径5nm未満であると、無機塗料組成物中で中空シリカ粒子が不安定となり、凝集して粒子が大きくなりすぎるため沈殿するおそれがあるので好ましくなく、平均粒子径3000nm超であると、塗膜を形成した際、有機基材への埋め込みが困難となり、密着性が低下するおそれがあるので好ましくない。中空シリカ粒子は、得られる塗膜が透明性に優れることから、平均粒子径5〜200nmであることが特に好ましく、平均粒子径5〜100nmであることが最も好ましい。なお、本明細書において、中空シリカ粒子の平均粒子径は質量基準のものである。   In the present invention, (a) the hollow silica particles are required to have an average particle diameter of 5 to 3000 nm. If the average particle size is less than 5 nm, the hollow silica particles become unstable in the inorganic coating composition, and it is not preferable because the particles may be aggregated and become too large, and the average particle size is more than 3000 nm. When a coating film is formed, it is difficult to embed it in an organic base material, and the adhesion may be lowered. The hollow silica particles preferably have an average particle size of 5 to 200 nm, and most preferably an average particle size of 5 to 100 nm, because the resulting coating film is excellent in transparency. In the present specification, the average particle diameter of the hollow silica particles is based on mass.

中空シリカ粒子は、屈折率1.2〜1.5であることが好ましい。これにより、低屈折率性塗膜が得られるので好ましい。中空シリカ粒子の屈折率は、例えば、特開2001−233611号公報に記載されている方法により測定することが好ましい。具体的には、屈折率が既知の種々の標準液について、2、3滴ガラス板上に滴下し、これに中空シリカ粒子を混合して、混合液が透明になったときの標準液の屈折率を中空シリカ粒子の屈折率とする方法が挙げられる。中空シリカ粒子が分散液中に含有される場合は、分散液中の分散媒を蒸発させた後、乾燥して、粉末にして使用することが好ましい。中空シリカ粒子は、屈折率1.3〜1.4であることが特に好ましい。
なお、本明細書において、中空シリカ粒子とは、粒子内部に空孔のあるシリカ粒子であり、空孔以外の外殻の部分は多孔質でも無孔質のものでもよく、従来より公知のものを適宜必要に応じて使用することができる。中空シリカ粒子の製造方法としては、例えば、多孔質の無機粒子を核粒子として使用し、この核粒子の周りにケイ酸アルカリ等を使用してシリカで被覆した後、酸で核粒子を溶解して中空粒子を得る方法が挙げられる。中空シリカ粒子は、空孔径が粒子径の1/3〜2/3であるものが好ましい。
The hollow silica particles preferably have a refractive index of 1.2 to 1.5. This is preferable because a low refractive index coating film can be obtained. The refractive index of the hollow silica particles is preferably measured, for example, by the method described in JP-A No. 2001-233611. Specifically, with respect to various standard solutions with known refractive indexes, a few drops are dropped onto a glass plate, and hollow silica particles are mixed with this to refract the standard solution when the mixture becomes transparent. And a method in which the refractive index is the refractive index of the hollow silica particles. When the hollow silica particles are contained in the dispersion, it is preferable to evaporate the dispersion medium in the dispersion and then dry and use it as a powder. It is particularly preferable that the hollow silica particles have a refractive index of 1.3 to 1.4.
In the present specification, the hollow silica particles are silica particles having pores inside the particles, and the outer shell portion other than the pores may be porous or nonporous, and conventionally known ones. Can be used as needed. As a method for producing hollow silica particles, for example, porous inorganic particles are used as core particles, and the core particles are coated with silica using alkali silicate around the core particles, and then the core particles are dissolved with an acid. And a method of obtaining hollow particles. The hollow silica particles preferably have a pore diameter of 1/3 to 2/3 of the particle diameter.

本発明では、無機塗料組成物中に有機溶剤Aを含有する。これにより、得られる塗膜の密着性を向上させることができる。有機溶剤Aを含有することにより、有機基材との密着性が向上する機構については解明できていないが、有機溶剤Aが有機基材を膨潤又は溶解させることにより、有機基材表面にミクロな欠陥部位を作り出し、そのミクロな欠陥部位に中空シリカ粒子が浸入した後、有機溶剤Aが揮発することで有機基材の表面部位で樹脂の収縮が起こり中空シリカ粒子が有機基材中に埋め込まれた状態で固定化されるものと考えられる。   In the present invention, the organic solvent A is contained in the inorganic coating composition. Thereby, the adhesiveness of the coating film obtained can be improved. Although the mechanism by which the adhesion with the organic base material is improved by containing the organic solvent A has not been elucidated, the organic solvent A swells or dissolves the organic base material, so that the surface of the organic base material is microscopic. After creating a defect site and the hollow silica particles infiltrate into the micro defect site, the organic solvent A volatilizes, causing the resin to shrink at the surface of the organic substrate, and the hollow silica particles are embedded in the organic substrate. It is thought that it is fixed in the state.

有機溶剤Aは、有機基材を膨潤又は溶解することができ、かつ、気圧0.1MPaの状態で沸点130℃以上を有する。有機溶剤Aは、無機塗料組成物を調製する際、無機塗料組成物中の水と混和して無機塗料組成物が相分離を起こさないものであることが必要である。このため、有機溶剤Aは、水に対する溶解度が2以上であることが好ましい。なお、本発明において、水に対する溶解度とは温度20℃で水100gに溶解する有機溶剤Aの量(g)をいう。   The organic solvent A can swell or dissolve the organic base material, and has a boiling point of 130 ° C. or higher under a pressure of 0.1 MPa. When preparing the inorganic coating composition, the organic solvent A needs to be mixed with water in the inorganic coating composition so that the inorganic coating composition does not cause phase separation. For this reason, it is preferable that the organic solvent A has a solubility in water of 2 or more. In the present invention, the solubility in water means the amount (g) of the organic solvent A dissolved in 100 g of water at a temperature of 20 ° C.

また、有機溶剤Aが気圧0.1MPaの状態で沸点130℃以上であることにより、無機塗料組成物中において、有機溶剤B、水に比べて最後まで残存することができ、上述のような効果を示すことができる。有機溶剤Aは、気圧0.1MPaの状態で、沸点160〜300℃であることが特に好ましい。なお、本発明で、「気圧」とは、絶対圧を意味する。
有機溶剤Aは、ジグライム、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、アセト酢酸エチル、N−メチル−2−ピロリジノン、2−ピロリジノン、1,3−ジメチル−2−イミダゾリジノン及びジメチルスルホキシドからなる群より選ばれるいずれかのものが好ましい。
In addition, when the organic solvent A has a boiling point of 130 ° C. or higher in a state where the atmospheric pressure is 0.1 MPa, the organic solvent A can remain in the inorganic coating composition as compared with the organic solvent B and water. Can be shown. The organic solvent A particularly preferably has a boiling point of 160 to 300 ° C. under a pressure of 0.1 MPa. In the present invention, “atmospheric pressure” means absolute pressure.
Organic solvent A is diglyme, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetoacetate, N-methyl-2-pyrrolidinone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone and dimethyl Any one selected from the group consisting of sulfoxides is preferred.

また、本発明の無機塗料組成物は、有機溶剤B及び/又は水を含有する。有機溶剤Bも有機溶剤Aと同様、無機塗料組成物を調製する際、無機塗料組成物中の水と混和して無機塗料組成物が相分離を起こさないものであることが必要である。このため、有機溶剤Bも水に対する溶解度が2以上であることが好ましい。有機溶剤B及び水は、任意の割合で配合したものが使用でき、後述のとおり、それぞれ、単独で使用してもよい。
有機溶剤B及び水は、無機塗料組成物において、中空シリカ粒子を安定して分散させる役割をする。また、有機溶剤Bは、無機塗料組成物の塗布性を向上させる役割もするので特に好ましい。この有機溶剤B及び水を含有することにより、無機塗料組成物を塗布して、乾燥する際、有機溶剤Aより早く蒸発するために、乾燥の最終段階で有機基材Aが有機基材表面に均一に残り、有機基材を均一に膨潤又は溶解することができるので好ましい。 有機溶剤Bは、有機基材を実質上膨潤又は溶解させることなく、かつ、気圧0.1MPaの状態で沸点50〜120℃であることが必要である。有機溶剤Bの沸点が50℃未満であると、常温で揮発しやすく、無機塗料組成物の取り扱いが難しくなるので好ましくなく、沸点が120℃超であると、揮発せずに残存し、有機基材と中空シリカ粒子との密着性を阻害するおそれがあるので好ましくない。有機溶剤Bは気圧0.1MPaの状態で沸点が有機溶剤Aの沸点に対して50〜80℃程度低いものを使用することが好ましい。
有機溶剤Bとしては、例えば、メタノール、エタノール、n−プロパノール、イソプロパノール、n−ブタノール、イソブタノール、sec−ブタノール及びt−ブタノールからなる群より選ばれるいずれかのものが好ましい。
Moreover, the inorganic coating composition of this invention contains the organic solvent B and / or water. Similarly to the organic solvent A, the organic solvent B needs to be mixed with water in the inorganic coating composition so that the inorganic coating composition does not cause phase separation when preparing the inorganic coating composition. For this reason, it is preferable that the organic solvent B has a solubility in water of 2 or more. The organic solvent B and water can be used in an arbitrary ratio, and each may be used alone as described later.
The organic solvent B and water serve to stably disperse the hollow silica particles in the inorganic coating composition. Moreover, the organic solvent B is particularly preferable because it also serves to improve the coating property of the inorganic coating composition. By containing the organic solvent B and water, when the inorganic coating composition is applied and dried, the organic substrate A evaporates faster than the organic solvent A. This is preferable because it remains uniformly and the organic substrate can be uniformly swollen or dissolved. The organic solvent B needs to have a boiling point of 50 to 120 ° C. without substantially swelling or dissolving the organic base material and at a pressure of 0.1 MPa. If the boiling point of the organic solvent B is less than 50 ° C., it is not preferable because it tends to volatilize at room temperature and the handling of the inorganic coating composition becomes difficult. If the boiling point exceeds 120 ° C., the organic solvent B remains without volatilization. This is not preferable because the adhesion between the material and the hollow silica particles may be hindered. It is preferable to use an organic solvent B having a boiling point of about 50 to 80 ° C. lower than the boiling point of the organic solvent A at a pressure of 0.1 MPa.
As the organic solvent B, for example, any one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and t-butanol is preferable.

本発明の無機塗料組成物は、適宜必要に応じて、界面活性剤を含有することができる。界面活性剤としては、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤のいずれのものも使用できる。界面活性剤を含有することにより、有機基材に対して優れた濡れ性を有するので好ましい。界面活性剤としては、−CHCHO−、−SO−、−NR−(Rは水素原子又は有機基)、−NH、−SOY、又は−COOY(Yは水素原子、ナトリウム原子、カリウム原子又はアンモニウムイオン)の構造単位を有するノニオン性界面活性剤が好ましい。なかでも、無機塗料組成物の保存安定性を損なうおそれのないことから、−CHCHO−の構造単位をもつノニオン系の界面活性剤が特に好ましい。
ノニオン系の界面活性剤としては、例えば、アルキルポリオキシエチレンエーテル、アルキルポリオキシエチレン−ポリプロピレンエーテル、脂肪酸ポリオキシエチレンエステル、脂肪酸ポリオキシエチレンソルビタンエステル、脂肪酸ポリオキシエチレンソルビトールエステル、アルキルポリオキシエチレンアミン、アルキルポリオキシエチレンアミド、ポリエーテル変性のシリコーン系界面活性剤等が挙げられる。
The inorganic coating composition of the present invention can contain a surfactant as necessary. As the surfactant, any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used. It is preferable to contain a surfactant because it has excellent wettability with respect to the organic substrate. As the surfactant, —CH 2 CH 2 O—, —SO 2 —, —NR— (R is a hydrogen atom or an organic group), —NH 2 , —SO 3 Y, or —COOY (Y is a hydrogen atom, Nonionic surfactants having a structural unit of sodium atom, potassium atom or ammonium ion are preferred. Among these, nonionic surfactants having a structural unit of —CH 2 CH 2 O— are particularly preferred because they do not impair the storage stability of the inorganic coating composition.
Nonionic surfactants include, for example, alkyl polyoxyethylene ether, alkyl polyoxyethylene-polypropylene ether, fatty acid polyoxyethylene ester, fatty acid polyoxyethylene sorbitan ester, fatty acid polyoxyethylene sorbitol ester, alkyl polyoxyethylene amine , Alkyl polyoxyethylene amide, polyether-modified silicone surfactants, and the like.

また、本発明の無機塗料組成物は、適宜必要に応じて、着色用染料、顔料、紫外線吸収剤、酸化防止剤等の添加剤を含有することができる。   Moreover, the inorganic coating composition of this invention can contain additives, such as coloring dye, a pigment, a ultraviolet absorber, antioxidant, as needed suitably.

有機溶剤Aの含有量は、無機塗料組成物の1〜20質量%であることが必要である。有機溶剤Aは上述のとおり、有機基材を膨潤又は溶解させることにより中空シリカ粒子を基材中に埋め込ませる働きをすると考えられる。したがって、有機溶剤Aは有機基材の表面を覆う量だけ存在すればよく、無機塗料組成物において、固形分でなく全体の濃度に依存する。有機溶剤Aの含有量が1質量%未満であると、得られる塗膜の有機基材への密着性が低下するおそれがあるので好ましくない。また、有機溶剤Aの含有量が20質量%超であると、有機基材への侵食の影響が大きくなり、表面の平滑性が損なわれ、塗膜の透明性が低下するおそれがあり、さらに、塗膜の外観が悪くなるおそれがあるので好ましくない。有機溶剤Aの含有量は3〜10質量%であることが特に好ましい。   The content of the organic solvent A needs to be 1 to 20% by mass of the inorganic coating composition. As described above, the organic solvent A is considered to function to embed the hollow silica particles in the substrate by swelling or dissolving the organic substrate. Accordingly, the organic solvent A only needs to be present in an amount that covers the surface of the organic substrate, and depends on the overall concentration, not the solid content, in the inorganic coating composition. If the content of the organic solvent A is less than 1% by mass, the adhesion of the resulting coating film to the organic substrate may be reduced, such being undesirable. Further, when the content of the organic solvent A is more than 20% by mass, the influence of erosion on the organic base material is increased, the smoothness of the surface is impaired, and the transparency of the coating film may be reduced. Since the appearance of the coating film may be deteriorated, it is not preferable. The content of the organic solvent A is particularly preferably 3 to 10% by mass.

有機溶剤B及び水の含有量は、無機塗料組成物の60〜98.9質量%であることが必要である。有機溶剤B及び水の含有量が60質量%未満であると、中空シリカ粒子又は有機溶剤Aが所定の範囲を超えるので好ましくなく、98.9質量%超であると、有機溶剤Aの量が少なくなるため有機基材への低屈折率性塗膜の密着力が低下するおそれがあるので好ましくない。なお、有機溶剤B及び水は、任意の割合で配合された場合でも、単独で使用された場合でも、その総量が60〜98.9質量%含有されればよい。すなわち、本発明の無機塗料組成物においては、有機溶剤B又は水のいずれかを全く含まなくてもよい。有機溶剤B及び水の含有量は80〜97質量%であることが特に好ましい。   The content of the organic solvent B and water needs to be 60 to 98.9% by mass of the inorganic coating composition. When the content of the organic solvent B and water is less than 60% by mass, the hollow silica particles or the organic solvent A is not preferable because it exceeds the predetermined range, and when it exceeds 98.9% by mass, the amount of the organic solvent A is Since it decreases, there is a possibility that the adhesion of the low refractive index coating film to the organic substrate may decrease, which is not preferable. In addition, the organic solvent B and water should just contain 60-98.9 mass% of the total amount, even when mix | blended in arbitrary ratios, or when used alone. That is, the inorganic coating composition of the present invention may not contain any of the organic solvent B or water. The content of the organic solvent B and water is particularly preferably 80 to 97% by mass.

本発明の無機塗料組成物の固形分含有量は0.1〜20質量%であることが必要である。固形分含有量が0.1質量%未満であると、無機塗料組成物を塗布した際、ムラが発生しやすくなるので好ましくなく、固形分含有量が20質量%超であると、塗布する際の作業性が悪くなるおそれがあるので好ましくない。無機塗料組成物の固形分含有量は0.1〜10質量%であることが特に好ましい。   The solid content of the inorganic coating composition of the present invention is required to be 0.1 to 20% by mass. When the solid content is less than 0.1% by mass, unevenness is likely to occur when the inorganic coating composition is applied, and this is not preferable. When the solid content is more than 20% by mass, the solid content is more than 20% by mass. This is not preferable because the workability may be deteriorated. The solid content of the inorganic coating composition is particularly preferably 0.1 to 10% by mass.

本発明の無機塗料組成物において、界面活性剤は1〜500ppmであることが好ましい。界面活性剤が1ppm未満であると、無機塗料組成物の濡れ性が低下するため塗布する際の作業性が悪くなるおそれがあるので好ましくなく、界面活性剤が500ppm超であると、得られる塗膜の外観の品質が低下するおそれがあるので好ましくない。界面活性剤は10〜400ppmであることが特に好ましい。   In the inorganic coating composition of the present invention, the surfactant is preferably 1 to 500 ppm. If the surfactant is less than 1 ppm, the wettability of the inorganic coating composition is lowered, so that the workability at the time of application may be deteriorated, which is not preferred, and if the surfactant is more than 500 ppm, the resulting coating is obtained. This is not preferable because the quality of the appearance of the film may be deteriorated. The surfactant is particularly preferably 10 to 400 ppm.

本発明の無機塗料組成物は、適宜必要に応じて、中空シリカ粒子100質量部に対して、ケイ酸オリゴマーを固形分換算で1〜50質量部含有することが好ましい。これにより、得られる塗膜の強度を向上させることができるので好ましい。ケイ酸オリゴマーの含有量が1質量部未満であると、塗膜の強度を向上させる効果がほとんどないことから好ましくなく、含有量が50質量部超であると、得られる塗膜の屈折率が上がるおそれがあるので好ましくない。ケイ酸オリゴマーの含有量は1〜30質量部であることが特に好ましい。   The inorganic coating composition of the present invention preferably contains 1 to 50 parts by mass of silicic acid oligomer in terms of solid content with respect to 100 parts by mass of the hollow silica particles as necessary. Thereby, since the intensity | strength of the coating film obtained can be improved, it is preferable. When the content of the silicic acid oligomer is less than 1 part by mass, it is not preferable because there is almost no effect of improving the strength of the coating film, and when the content exceeds 50 parts by mass, the refractive index of the obtained coating film is It is not preferable because it may increase. The content of the silicic acid oligomer is particularly preferably 1 to 30 parts by mass.

ケイ酸オリゴマーとしては、ケイ酸エチル等のケイ酸アルコキサイドを加水分解する方法、アルカリ金属ケイ酸塩を酸で分解した後、透析する方法、アルカリ金属ケイ酸塩を解膠する方法、アルカリ金属ケイ酸塩を酸型のカチオン交換樹脂と接触させる方法等により得られるものが好ましい。なかでも、アルカリ金属ケイ酸塩を酸型のカチオン交換樹脂と接触させる方法により得られるケイ酸オリゴマーが純度の高いものが得られ、塗膜を形成した際、バインダ力の強いことから特に好ましい。
ケイ酸アルカリ金属塩としては、ケイ酸ナトリウム、ケイ酸カリウム、ケイ酸リチウム等が好ましい。イオン交換樹脂としては、従来より公知のものが使用でき、例えば、−SOH基、−COOH基等を有する陽イオン交換樹脂を使用することが好ましい。使用する陽イオン交換樹脂の量、接触時間、接触方法等を制御することで、除去するアルカリ金属イオンの量を調節できる。なお、本明細書において、ケイ酸オリゴマーとは分散媒中でSiO分子が2〜20程度重合したものをいう。ケイ酸オリゴマーにおいて、アルカリ金属の95%以上が除去されたものであることが好ましい。これにより、耐候性に優れた低屈折率性塗膜品が得られるので好ましい。
Silicate oligomers include hydrolyzing alkoxides such as ethyl silicate, dialysis after alkali metal silicate decomposition with acid, peptizing alkali metal silicate, alkali metal silica What is obtained by the method etc. which contact an acid salt with an acid type cation exchange resin is preferable. Among them, a silicate oligomer obtained by a method in which an alkali metal silicate is brought into contact with an acid-type cation exchange resin has a high purity, and is particularly preferable since a binder force is strong when a coating film is formed.
As the alkali metal silicate, sodium silicate, potassium silicate, lithium silicate and the like are preferable. As the ion exchange resin, conventionally known ones can be used. For example, it is preferable to use a cation exchange resin having a —SO 3 H group, a —COOH group or the like. The amount of alkali metal ions to be removed can be adjusted by controlling the amount of cation exchange resin used, the contact time, the contact method, and the like. In the present specification, the silicic acid oligomer refers to a polymer in which about 2 to 20 SiO 2 molecules are polymerized in a dispersion medium. In the silicic acid oligomer, 95% or more of the alkali metal is preferably removed. This is preferable because a low refractive index coated product having excellent weather resistance can be obtained.

ケイ酸オリゴマーは適宜必要に応じて、水の他、メタノール、エタノール、イソプロパノール等の有機溶剤に分散させて分散液として使用することが好ましい。分散液中のケイ酸オリゴマーの含有量は1〜10質量%であることが好ましい。   The silicic acid oligomer is preferably used as a dispersion by dispersing it in water or an organic solvent such as methanol, ethanol or isopropanol as needed. The content of the silicic acid oligomer in the dispersion is preferably 1 to 10% by mass.

本発明の無機塗料組成物は、有機基材に塗布することにより、低屈折率性塗膜を形成することができる。得られる塗膜は屈折率1.1〜1.4であるのが好適である。有機基材としては、適宜必要に応じて、様々なものが使用することができるが、ポリカーボネート又はアクリル樹脂からなる基板を使用することが好ましい。また、基材の形状は平板に限らず、全面又は一部に曲率を有していてもよい。   The inorganic coating composition of the present invention can form a low refractive index coating film by applying it to an organic substrate. The resulting coating film preferably has a refractive index of 1.1 to 1.4. As the organic base material, various materials can be used as appropriate, but it is preferable to use a substrate made of polycarbonate or acrylic resin. Further, the shape of the substrate is not limited to a flat plate, and may have a curvature on the entire surface or a part thereof.

本発明により得られる塗膜は、波長380〜780nmの領域において、反射率の極小値が1%以下であることが好ましい。反射率は分光光度計で測定することが好ましい。反射率の極小値が1%超であると、低屈折率性塗膜としての機能が不充分となるおそれがあることから好ましくない。本発明により得られる塗膜は、波長550nmでの反射率が極小値をとるように膜厚を調整することが好ましい。なお、膜厚の調整は、式λ/4n=138/n(ただし、λは光の波長、nは膜の屈折率)により行うことができる。   The coating film obtained by the present invention preferably has a minimum reflectance of 1% or less in a wavelength range of 380 to 780 nm. The reflectance is preferably measured with a spectrophotometer. If the minimum value of the reflectance is more than 1%, the function as a low refractive index coating film may be insufficient, which is not preferable. The thickness of the coating film obtained by the present invention is preferably adjusted so that the reflectance at a wavelength of 550 nm takes a minimum value. The film thickness can be adjusted by the formula λ / 4n = 138 / n (where λ is the wavelength of light and n is the refractive index of the film).

また、本発明の無機塗料組成物を塗布することにより得られる低屈折率性塗膜は、透明性に優れたものが得られるので、特に有機基材が透明である場合に使用に適している。透明性については、JIS K7150の規格に則り、ヘイズ値で評価することが好ましい。得られた低屈折率性塗膜は、ヘイズ値は1%以下であることが好ましい。ヘイズ値が1%超であると、塗膜の透明性が悪くなり、透過率が低下するので好ましくない。得られる塗膜のヘイズ値は0.5%以下であることが特に好ましい。   Moreover, since the low refractive index coating film obtained by applying the inorganic coating composition of the present invention is excellent in transparency, it is particularly suitable for use when the organic substrate is transparent. . About transparency, it is preferable to evaluate by a haze value according to the specification of JIS K7150. The obtained low refractive index coating film preferably has a haze value of 1% or less. When the haze value is more than 1%, the transparency of the coating film is deteriorated and the transmittance is lowered, which is not preferable. The haze value of the obtained coating film is particularly preferably 0.5% or less.

本発明では、中空シリカ粒子を0.1〜20質量%、有機溶剤Aを1〜20質量%、有機溶剤B及び水を60〜98.9質量%含有する無機塗料組成物を調整する工程、及び、無機塗料組成物を有機基材上に塗布、乾燥することにより低屈折率性塗膜を形成する工程、を経ることにより低折率性塗膜を形成することができるので好ましい。   In the present invention, a step of adjusting an inorganic coating composition containing 0.1 to 20% by mass of hollow silica particles, 1 to 20% by mass of organic solvent A, 60 to 98.9% by mass of organic solvent B and water, And since a low-refractive-index coating film can be formed by passing through the process of forming a low-refractive-index coating film by apply | coating and drying an inorganic coating composition on an organic base material, it is preferable.

本発明の無機塗料組成物は、公知の方法で塗布することができる。例えば、はけ塗り、ローラー塗布、手塗り、回転塗布、浸漬塗布、各種印刷方式による塗布、カーテンフロー、ダイコート、グラビアコート、リバースコート、ロールコート、フローコート、スプレーコート、ディップコート等が挙げられる。また、塗膜の機械的強度を高める目的で、必要に応じて、加熱や紫外線や電子線等による照射を行ってもよい。加熱は有機基材の耐熱性を加味して決定すればよいが、60〜100℃が好ましい。本発明の無機塗料組成物を塗布するにあたり、有機基材に対して特に前処理は必要としないが、塗膜の密着性をより高める目的で、プラズマ処理、コロナ処理、UV処理、オゾン処理等の放電処理、水、酸やアルカリ等の化学処理、又は研磨剤を用いた物理的処理を施すことができる。   The inorganic coating composition of the present invention can be applied by a known method. Examples include brush coating, roller coating, hand coating, spin coating, dip coating, coating by various printing methods, curtain flow, die coating, gravure coating, reverse coating, roll coating, flow coating, spray coating, dip coating, and the like. . Moreover, you may perform irradiation by a heating, an ultraviolet-ray, an electron beam, etc. as needed in order to raise the mechanical strength of a coating film. The heating may be determined in consideration of the heat resistance of the organic base material, but is preferably 60 to 100 ° C. When applying the inorganic coating composition of the present invention, no pretreatment is required for the organic substrate, but for the purpose of further improving the adhesion of the coating film, plasma treatment, corona treatment, UV treatment, ozone treatment, etc. Discharge treatment, chemical treatment such as water, acid or alkali, or physical treatment using an abrasive.

本発明において、得られる塗膜の厚さは30〜3000nmであることが好ましい。塗膜の膜さが30nm未満であると、低屈折率性塗膜としての機能が不充分となるおそれがあるので好ましくなく、塗膜の膜さが3000nm超であると、クラックが入りやすくなったり、干渉縞が発生したり、傷が目立ちやすくなるおそれがあるので好ましくない。塗膜は膜さ50〜1000nmであることが特に好ましい。   In this invention, it is preferable that the thickness of the coating film obtained is 30-3000 nm. If the coating film thickness is less than 30 nm, the function as a low refractive index coating film may be insufficient, which is not preferable. If the coating film thickness exceeds 3000 nm, cracks tend to occur. Or interference fringes may occur or scratches may be noticeable. It is particularly preferable that the coating film has a film thickness of 50 to 1000 nm.

以下に、実施例として、例1、2、5、6を示す。また、比較例として、例3、4を示す。以下、質量%を単に%で示す。なお、中空状シリカ粒子の屈折率については、以下の方法により行う。すなわち、中空状シリカ微粒子分散ゾルから分散媒をエバポレーターにより蒸発させた後、120℃で乾燥し、粉末とする。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。こ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微粒子の屈折率とする。   Examples 1, 2, 5, and 6 are shown below as examples. Examples 3 and 4 are shown as comparative examples. Hereinafter, the mass% is simply indicated by%. In addition, about the refractive index of a hollow silica particle, it carries out with the following method. That is, the dispersion medium is evaporated from the hollow silica fine particle-dispersed sol by an evaporator and then dried at 120 ° C. to obtain a powder. 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. This operation is performed with various standard refracting liquids, and the refractive index of the standard refracting liquid when the mixed liquid becomes transparent is used as the refractive index of the fine particles.

[例1]
容量200mlのガラス製反応容器に、中空状シリカ微粒子の分散ゾル(平均粒子径60nm、空孔径30nm、屈折率1.3、固形分含有量20%のイソプロパノールを溶媒とする分散液、なお、イソプロパノールは圧力0.1MPaでの沸点が82.3℃である。)を5g、イソプロパノール85g、N,N−ジメチルアセトアミド(圧力0.1MPaでの沸点166℃、水に対する溶解度:任意の割合で溶解する)10gを加え、混合した後、20℃で1時間撹拌して、固形分含有量1%の無機塗料組成物を得る。なお、N,N−ジメチルアセトアミドの含有量は10%であり、イソプロパノールの含有量は89%である。
[Example 1]
In a glass reaction vessel having a capacity of 200 ml, a dispersion sol of hollow silica fine particles (a dispersion in which isopropanol having an average particle size of 60 nm, a pore size of 30 nm, a refractive index of 1.3, and a solid content of 20% is used as a solvent, Has a boiling point of 82.3 ° C. at a pressure of 0.1 MPa), 85 g of isopropanol, N, N-dimethylacetamide (boiling point of 166 ° C. at a pressure of 0.1 MPa, solubility in water: soluble at an arbitrary ratio) ) After adding 10 g and mixing, the mixture is stirred at 20 ° C. for 1 hour to obtain an inorganic coating composition having a solid content of 1%. The content of N, N-dimethylacetamide is 10%, and the content of isopropanol is 89%.

[評価試験]
得られる無機塗料組成物を使用して、エタノール拭きしたポリカーボネート板(縦100mm×横100mm、厚さ3.5mm、屈折率:1.584)上に、塗布して、回転数150rpmで70秒間スピンコートした後、100℃で20秒間乾燥し、厚さ100nmの塗膜を形成する。
[Evaluation test]
Using the resulting inorganic coating composition, it was applied onto a polycarbonate plate (length 100 mm × width 100 mm, thickness 3.5 mm, refractive index: 1.584) wiped with ethanol and spun at 150 rpm for 70 seconds. After coating, it is dried at 100 ° C. for 20 seconds to form a coating film having a thickness of 100 nm.

以下、塗膜の形成されたサンプルについて、下記に示す方法で評価を行う。評価結果を表1に示す。なお、例2〜6においても、得られる無機塗料組成物を使用して例1と同様に操作を行い、評価を行う。評価結果を併せて表1に示す。   Hereinafter, the sample on which the coating film is formed is evaluated by the following method. The evaluation results are shown in Table 1. In Examples 2 to 6, the obtained inorganic coating composition is used for the same operation as in Example 1 for evaluation. The evaluation results are also shown in Table 1.

外観評価として、得られる塗膜の塗布ムラを目視により判断する。塗布ムラがなく外観上良好なものを〇、塗布ムラがあり実用的でないものを×として評価する。   As appearance evaluation, the coating unevenness of the coating film obtained is judged visually. The case where there is no coating unevenness and the appearance is good is evaluated as ◯, and the case where there is coating unevenness and impractical is evaluated as ×.

透明性評価として、ヘイズ値により評価を行う。ヘイズ測定はJIS K7150に則り、評価を行う。基板上の塗膜のヘイズ値をヘーズコンピューター(スガ試験機社製、型名:HGM−3DP)で測定する。ヘイズ値が1%以下のものは合格、1%を超えるものは不合格とする。   As the transparency evaluation, evaluation is performed based on the haze value. The haze measurement is evaluated according to JIS K7150. The haze value of the coating film on the substrate is measured with a haze computer (manufactured by Suga Test Instruments Co., Ltd., model name: HGM-3DP). Those having a haze value of 1% or less are accepted, and those exceeding 1% are rejected.

反射率評価として、得られる塗膜の反射率を分光光度計(日立製作所社製、型式:U−4100)を使用して測定する。波長550nmにおける反射率が1%未満のものを合格とする。   As reflectance evaluation, the reflectance of the coating film obtained is measured using a spectrophotometer (Hitachi Ltd. make, model: U-4100). A reflectance of less than 1% at a wavelength of 550 nm is regarded as acceptable.

屈折率評価として、得られる塗膜の屈折率をエリプソメーター(ULVAC社製、型式:ESM−1AT)を使用して測定する。屈折率が1.1〜1.4の範囲のものを合格とする。   As refractive index evaluation, the refractive index of the obtained coating film is measured using an ellipsometer (manufactured by ULVAC, model: ESM-1AT). Those having a refractive index in the range of 1.1 to 1.4 are considered acceptable.

密着性評価として、サンプルにおいて塗膜にセロハンテープを接着し、このセロハンテープを剥がした時の塗膜の剥離状況を肉眼で観察する。塗膜が全く剥がれない場合を○、一部が剥がれるものの半分以上の面積が残っている場合を△、半分以上が剥離する場合を×とする。   For adhesion evaluation, a cellophane tape is adhered to the coating film in the sample, and the peeling state of the coating film when the cellophane tape is peeled off is observed with the naked eye. The case where the coating film is not peeled off at all is indicated by ○, the case where a part of the coating film is peeled off is left as Δ, and the case where more than half is peeled off is indicated as ×.

耐磨耗性評価として、サンプルの塗膜表面を、綿布で100回往復磨耗した後、塗膜の剥離状況を肉眼で観察する。塗膜が全く剥がれない場合を○、一部が剥がるものの半分以上の面積が残っている場合を△、半分以上が剥離する場合を×とする。   As the abrasion resistance evaluation, the surface of the coating film of the sample is worn back and forth 100 times with a cotton cloth, and the peeling state of the coating film is observed with the naked eye. The case where the coating film is not peeled off at all is indicated by ○, the case where more than half of the part of the coating film is left is Δ, and the case where more than half is peeled is indicated by ×.

[例2]
例1において、イソプロパノール85gを、水85g及び含有量0.1%のノニオン性界面活性剤(日本ユニカー社製、商品名:L−77)エタノール溶液(なお、エタノールは圧力0.1MPaでの沸点が78.2℃である。)0.1gに変更する以外は同様にして操作を行い、固形分含有量1%の無機塗料組成物を得る。なお、N,N−ジメチルアセトアミドの含有量は10%であり、イソプロパノールと水とエタノールとの総量の含有量は89%である。
[Example 2]
In Example 1, 85 g of isopropanol was added to 85 g of water and a nonionic surfactant having a content of 0.1% (manufactured by Nihon Unicar Co., Ltd., trade name: L-77) in an ethanol solution (note that ethanol has a boiling point at a pressure of 0.1 MPa. Is 78.2 ° C.) The same operation is carried out except that the content is changed to 0.1 g to obtain an inorganic coating composition having a solid content of 1%. The content of N, N-dimethylacetamide is 10%, and the total content of isopropanol, water and ethanol is 89%.

[例3]
例1において、イソプロパノールを65g、N,N−ジメチルアセトアミドを30gとする以外は例1と同様にして操作を行い、固形分含有量1%の無機塗料組成物を得る。なお、N,N−ジメチルアセトアミドの含有量は30%であり、イソプロパノールの含有量は69%である。
[Example 3]
The same operation as in Example 1 was conducted except that 65 g of isopropanol and 30 g of N, N-dimethylacetamide were used in Example 1, to obtain an inorganic coating composition having a solid content of 1%. In addition, the content of N, N-dimethylacetamide is 30%, and the content of isopropanol is 69%.

[例4]
例1において、N,N−ジメチルアセトアミドを使用せずに、イソプロパノールを95gとする以外は例1と同様にして操作を行い、固形分含有量1%の無機塗料組成物を得る。なお、イソプロパノールの含有量は99%である。
[Example 4]
In Example 1, the same operation as in Example 1 was carried out except that N, N-dimethylacetamide was not used and 95 g of isopropanol was used to obtain an inorganic coating composition having a solid content of 1%. The content of isopropanol is 99%.

[例5]
例1において、イソプロパノールを93gとし、N,N−ジメチルアセトアミドの代わりに2−ピロリジノン(圧力0.1MPaでの沸点245℃、水に対する溶解度:任意の割合で溶解する)を2gとする以外は例1と同様にして操作を行い、固形分含有量1%の無機塗料組成物を得ることができる。なお、2−ピロリジノンの含有量は2%であり、イソプロパノールの含有量は97%である。
[Example 5]
Example 1 except that in Example 1, 93 g of isopropanol was used, and 2-pyrrolidinone (boiling point 245 ° C. at a pressure of 0.1 MPa, solubility in water: dissolved in an arbitrary ratio) was 2 g instead of N, N-dimethylacetamide. In the same manner as in No. 1, an inorganic coating composition having a solid content of 1% can be obtained. The 2-pyrrolidinone content is 2% and the isopropanol content is 97%.

[例6]
例1において、基材をポリメチルメタクリレート(屈折率:1.521)に変更する以外は、例1と同様にして操作を行い、塗膜を形成する。
[Example 6]
In Example 1, except that the base material is changed to polymethyl methacrylate (refractive index: 1.521), the same operation as in Example 1 is performed to form a coating film.

Figure 2006057119
Figure 2006057119

本発明の無機塗料組成物を使用することにより、ディスプレイパネルのカバー材料や、光学レンズ、光学フィルタ、偏光フィルム等の有機基材を有する様々な物品に低屈折率性塗膜を付与することができる。

なお、2004年11月26日に出願された日本特許出願2004−342184号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
By using the inorganic coating composition of the present invention, a low refractive index coating film can be applied to various articles having an organic substrate such as a display panel cover material, an optical lens, an optical filter, and a polarizing film. it can.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2004-342184 filed on November 26, 2004 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (8)

(a)平均粒子径5〜3000nmの中空状シリカ粒子を0.1〜20質量%;(b)有機基材を膨潤又は溶解することができ、かつ、気圧0.1MPaの状態で沸点130℃以上の、水に混和しうる有機溶剤Aを1〜20質量%;(c)有機基材を実質上膨潤又は溶解させることなく、かつ、気圧0.1MPaの状態で沸点50〜120℃の、水に混和しうる有機溶剤B及び/又は(d)水を60〜98.9質量%を含有し、有機基材上に低屈折率性塗膜を形成することのできる無機塗料組成物。   (A) 0.1 to 20% by mass of hollow silica particles having an average particle diameter of 5 to 3000 nm; (b) an organic base material can be swollen or dissolved and has a boiling point of 130 ° C. at a pressure of 0.1 MPa. 1-20 mass% of the above organic solvent A miscible with water; (c) without boiling or dissolving the organic base material, and having a boiling point of 50-120 ° C. at a pressure of 0.1 MPa, An inorganic coating composition which contains an organic solvent B miscible with water and / or (d) 60 to 98.9% by mass of water and can form a low refractive index coating film on an organic substrate. 前記有機基材がポリカーボネート又はアクリル樹脂からなる請求項1に記載の無機塗料組成物。   The inorganic coating composition according to claim 1, wherein the organic substrate is made of polycarbonate or acrylic resin. 前記有機溶剤Aが、ジグライム、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、アセト酢酸エチル、N−メチル−2−ピロリジノン、2−ピロリジノン、1,3−ジメチル−2−イミダゾリジノン及びジメチルスルホキシドからなる群より選ばれる少なくとも1種である請求項1又は2に記載の無機塗料組成物。   The organic solvent A is diglyme, N, N-dimethylformamide, N, N-dimethylacetamide, ethyl acetoacetate, N-methyl-2-pyrrolidinone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone and The inorganic coating composition according to claim 1 or 2, which is at least one selected from the group consisting of dimethyl sulfoxide. 前記有機基材を実質上膨潤又は溶解させることなく、かつ、気圧0.1MPaの状態で沸点50〜120℃の、水に混和しうる有機溶剤が、メタノール、エタノール、n−プロパノール、イソプロパノール、n−ブタノール、イソブタノール、sec−ブタノール及びt−ブタノールからなる群より選ばれる少なくとも1種である請求項1〜3のいずれかに記載の無機塗料組成物。   An organic solvent miscible with water having a boiling point of 50 to 120 ° C. in a state of atmospheric pressure of 0.1 MPa without substantially swelling or dissolving the organic base material is methanol, ethanol, n-propanol, isopropanol, n The inorganic coating composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of butanol, isobutanol, sec-butanol, and t-butanol. 請求項1〜4のいずれかに記載の無機塗料組成物を有機基材に塗布することにより得られる低屈折率性塗膜。   The low-refractive-index coating film obtained by apply | coating the inorganic coating composition in any one of Claims 1-4 to an organic base material. 前記低屈折率性塗膜のJIS K−7150の規格に則ったヘイズが1%以下である請求項5に記載の低屈折率性塗膜。   The low-refractive-index coating film according to claim 5, wherein the low-refractive-index coating film has a haze according to JIS K-7150 standards of 1% or less. 前記低屈折率性塗膜の屈折率が1.1〜1.4である請求項5又は6に記載の低屈折率性塗膜。   The low refractive index coating film according to claim 5 or 6, wherein the low refractive index coating film has a refractive index of 1.1 to 1.4. (a)平均粒子径5〜3000nmの中空状シリカ粒子を0.1〜20質量%;(b)有機基材を膨潤又は溶解することができ、かつ、気圧0.1MPaの状態で沸点130℃以上の、水に混和しうる有機溶剤Aを1〜20質量%;(c)有機基材を実質上膨潤又は溶解させることなく、かつ、気圧0.1MPaの状態で沸点50〜120℃の、水に混和しうる有機溶剤B及び/又は(d)水を60〜98.9質量%;を含有する無機塗料組成物を調製する工程、及び該無機塗料組成物を有機基材上に塗布、乾燥することにより低屈折率性塗膜を形成する工程、を経る低屈折率性塗膜の形成方法。   (A) 0.1 to 20% by mass of hollow silica particles having an average particle diameter of 5 to 3000 nm; (b) an organic base material can be swollen or dissolved and has a boiling point of 130 ° C. at a pressure of 0.1 MPa. 1-20 mass% of the above organic solvent A miscible with water; (c) without boiling or dissolving the organic base material, and having a boiling point of 50-120 ° C. at a pressure of 0.1 MPa, A step of preparing an inorganic coating composition containing an organic solvent B miscible with water and / or (d) 60 to 98.9% by mass of water; and applying the inorganic coating composition on an organic substrate; A method for forming a low refractive index coating film, which comprises a step of forming a low refractive index coating film by drying.
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