JP2013203774A - Antifog and antifouling agent for organic substrate, and method for coating organic substrate with the antifog and antifouling agent - Google Patents

Antifog and antifouling agent for organic substrate, and method for coating organic substrate with the antifog and antifouling agent Download PDF

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JP2013203774A
JP2013203774A JP2012071234A JP2012071234A JP2013203774A JP 2013203774 A JP2013203774 A JP 2013203774A JP 2012071234 A JP2012071234 A JP 2012071234A JP 2012071234 A JP2012071234 A JP 2012071234A JP 2013203774 A JP2013203774 A JP 2013203774A
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antifouling agent
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JP5804996B2 (en
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Akihito Hirai
明仁 平井
Keiji Tanaka
敬二 田中
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CENTRAL AUTOMOTIVE PRODUCTS Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide an antifog and antifouling agent for organic substrate, capable of providing an inorganic cured coating having excellent antifouling and antifogging performances in addition to high hydrophilicity, hardness, adhesive strength to an organic substrate, and water resistance, and a method for coating an organic substrate with the antifog and antifouling agent.SOLUTION: An antifog and antifouling agent for organic substrate contains: 20-80 wt.% of methanol and/or ethanol; 20-80 wt.% of isopropyl alcohol, normal propyl alcohol or glycol ether; 1.0-70.0 wt.% of organosilica sol; 0.1-3.0 wt.% of tetrahydrofuran; and 0.02-0.4 wt.% of boric acid. The antifog and antifouling agent is brought into contact with a surface of an organic substrate followed by drying at ordinary temperature, whereby a coating is formed.

Description

本発明は、有機基材用防曇防汚剤及び当該防曇防汚剤で有機基材を被覆する方法に関する。特に、有機基材に親水性被覆を形成してセルフクリーニング効果を発揮する有機基材用防曇防汚剤及び当該防曇防汚剤で有機基材を被覆する方法に関する。   The present invention relates to an anti-fogging and antifouling agent for an organic substrate and a method for coating an organic substrate with the antifogging and antifouling agent. In particular, the present invention relates to an antifogging and antifouling agent for organic substrates that forms a hydrophilic coating on an organic substrate and exhibits a self-cleaning effect, and a method for coating an organic substrate with the antifogging and antifouling agent.

自動車車体、ガラス基板等に親水性を付与するコーティング方法はよく知られている（特許文献１〜４等）。たとえば、特許文献１には、オルガノシリカゾルを有機溶媒（イソプロパノールとジアセトンアルコール）で希釈してなるシリカ濃度0.2wt%の液状物を疎水処理された自動車車体に塗布することが記載されている。特許文献２には、イソプロパノール分散オルガノシリカゾルと、水と、イソプロパノールと、テトラエトキシシランと、エチレングリコールとを含むコーティング材が、親水性、防曇性、防汚性、耐候性、耐久性、透明性、塗膜強度向上に効果があることが記載されている。特許文献３には、イソプロパノール分散オルガノシリカゾルと、水と、イソプロパノールと、テトラエトキシシランと、メタノール95％以上と、を含む塗料組成物をガラス基板にスプレーコーティングすること、メタノールはスプレー缶に充填して使用するために必要であることが記載されている。特許文献４には、合成樹脂表面に、有機溶媒を分散媒とするコロイダルシリカとフルオロアルキル基を有する界面活性剤とからなる無機質粒子分散液を塗布し、乾燥して無機質粒子層を形成すること、合成樹脂成型物の流滴性、防曇性、防霧性を向上させることが記載されている。   Coating methods for imparting hydrophilicity to automobile bodies, glass substrates and the like are well known (Patent Documents 1 to 4, etc.). For example, Patent Document 1 describes that a liquid substance having a silica concentration of 0.2 wt% obtained by diluting an organosilica sol with an organic solvent (isopropanol and diacetone alcohol) is applied to a hydrophobically treated automobile body. In Patent Document 2, a coating material containing isopropanol-dispersed organosilica sol, water, isopropanol, tetraethoxysilane, and ethylene glycol is hydrophilic, antifogging, antifouling, weather resistant, durable, and transparent. It is described that it is effective in improving the properties and coating film strength. In Patent Document 3, a glass substrate is spray-coated with a coating composition containing isopropanol-dispersed organosilica sol, water, isopropanol, tetraethoxysilane, and 95% or more of methanol, and methanol is filled in a spray can. It is described that it is necessary for use. In Patent Document 4, an inorganic particle dispersion liquid composed of colloidal silica using an organic solvent as a dispersion medium and a surfactant having a fluoroalkyl group is applied to the surface of a synthetic resin and dried to form an inorganic particle layer. Further, it is described that the flowability, antifogging property and antifogging property of a synthetic resin molding are improved.

しかし、従来のコーティング剤は、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂などの耐有機溶媒性が低い有機基材へのコーティングには適していなかった。このため、有機基材にコーティング剤を塗布する前にプライマーを塗布してプライマー層を形成させ、その上にコーティング剤を塗布する方法が採用されている。しかし、コーティング剤は有機基材を直接被覆していないため、有機基材との密着強度が低く、耐久性に劣るという問題もあった。   However, conventional coating agents are not suitable for coating on organic substrates having low organic solvent resistance such as acrylic resin, polycarbonate resin, and polyester resin. For this reason, the method of apply | coating a primer before apply | coating a coating agent to an organic base material, forming a primer layer, and apply | coating a coating agent on it is employ | adopted. However, since the coating agent does not directly cover the organic substrate, there is a problem that the adhesion strength with the organic substrate is low and the durability is inferior.

特開平11-10077号公報Japanese Patent Laid-Open No. 11-10077 特開2002-161239号公報Japanese Patent Laid-Open No. 2002-161239 特開2001-123118号公報JP 2001-123118 A 特開平5-59203号公報Japanese Patent Laid-Open No. 5-59203

プライマーを用いることなく、親水性、硬度、有機基材に対する密着強度及び耐水性が高く防汚防曇性能に優れる無機硬化塗膜を付与する有機基材用防汚防曇剤及び当該防曇防汚剤で有機基材を被覆する方法を提供する。   Antifouling and antifogging agent for organic substrates and an antifogging agent for imparting an inorganic cured coating film having high hydrophilicity, hardness, adhesion strength to water and high water resistance and excellent antifouling and antifogging performance without using a primer A method of coating an organic substrate with a soiling agent is provided.

本発明によれば、メタノール及び／又はエタノール２０〜８０wt%と、イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテル２０〜８０wt%と、オルガノシリカゾル１．０〜７０．０wt％と、テトラヒドロフラン０．１〜３．０wt%と、ホウ酸０．０２〜０．４wt%と、を含有する、有機基材用防曇防汚剤が提供される。   According to the present invention, methanol and / or ethanol 20-80 wt%, isopropyl alcohol, normal propyl alcohol or glycol ether 20-80 wt%, organosilica sol 1.0-70.0 wt%, tetrahydrofuran 0.1-3 An anti-fogging and antifouling agent for an organic substrate containing 0.0 wt% and boric acid 0.02 to 0.4 wt% is provided.

本発明の有機基材用防曇防汚剤は、メタノール及び／又はエタノール３５〜５５wt%と、イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテル３５〜５５wt%と、オルガノシリカゾル１．５〜２０．０wt％と、テトラヒドロフラン０．５〜２．０wt%と、ホウ酸０．０５〜０．１５wt%を含有することがより好ましい。   The anti-fogging and antifouling agent for organic substrates of the present invention comprises methanol and / or ethanol of 35 to 55 wt%, isopropyl alcohol, normal propyl alcohol or glycol ether of 35 to 55 wt%, and organosilica sol of 1.5 to 20.0 wt%. It is more preferable to contain 0.5 to 2.0 wt% of tetrahydrofuran and 0.05 to 0.15 wt% of boric acid.

メタノール及び／又はエタノールと、イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテルとの含有比率は１：２〜２：１の範囲にあることが好ましい。   The content ratio of methanol and / or ethanol to isopropyl alcohol, normal propyl alcohol or glycol ether is preferably in the range of 1: 2 to 2: 1.

本発明の有機基材用防曇防汚剤に含まれるオルガノシリカゾルは、鎖状シリカゾルであるか、又は鎖状シリカゾルと球状シリカゾルとの併用であることが好ましい。
本発明の有機基材用防曇防汚剤は、さらに、ケイ酸ナトリウム、オルトケイ酸テトラエチル、アルカリ土類金属塩から選択される少なくとも1種の添加剤を含有していてもよい。 The organosilica sol contained in the antifogging and antifouling agent for organic substrates of the present invention is preferably a chain silica sol or a combination of a chain silica sol and a spherical silica sol.
The anti-fogging and antifouling agent for organic substrates of the present invention may further contain at least one additive selected from sodium silicate, tetraethyl orthosilicate, and alkaline earth metal salt.

本発明の有機基材用防曇防汚剤を適用できる有機基材は、アクリル樹脂、ポリカーボネート樹脂及びポリエステル樹脂から好ましく選択される。
また、本発明の有機基材用防曇防汚剤を有機基材に接触又は塗布して、有機基材の表面を膨潤させ、膨潤した有機基材中にオルガノシリカゾルを侵入させ、常温で乾燥させてアルコール系有機溶剤を除去し、シリカ被膜を形成することを含む、有機基材を防曇防汚剤で被覆する方法も提供される。 The organic substrate to which the anti-fogging and antifouling agent for organic substrates of the present invention can be applied is preferably selected from acrylic resins, polycarbonate resins and polyester resins.
In addition, the antifogging and antifouling agent for organic substrates of the present invention is brought into contact with or applied to the organic substrate to swell the surface of the organic substrate, infiltrate the organosilica sol into the swollen organic substrate, and dry at room temperature. There is also provided a method of coating an organic substrate with an anti-fogging and antifouling agent comprising removing the alcohol-based organic solvent to form a silica film.

本発明の有機基材用防汚防曇剤は、有機基材に親水性の無機硬化塗膜を形成させ、セルフクリーニングによる防汚効果を発揮する。
本発明の有機基材用防汚防曇剤により有機基材上に形成される無機硬化塗膜は、紫外線による劣化や黄変が少なく、長期にわたりセルフクリーニングによる防汚効果を維持できる。 The antifouling and antifogging agent for organic substrates of the present invention forms a hydrophilic inorganic cured coating film on an organic substrate and exhibits an antifouling effect by self-cleaning.
The inorganic cured coating film formed on the organic substrate by the antifouling antifogging agent for organic substrates of the present invention has little deterioration and yellowing due to ultraviolet rays, and can maintain the antifouling effect by self-cleaning over a long period of time.

本発明の有機基材用防汚防曇剤は、水接触角20度以下の親水性を示し、防曇効果を発揮する。
本発明の有機基材用防汚防曇剤は、有機基材に塗布した後は常温乾燥により有機基剤に浸透し密着するため、密着強度が高く、長期にわたり防汚防曇効果を維持できる。 The antifouling antifogging agent for organic substrates of the present invention exhibits hydrophilicity with a water contact angle of 20 degrees or less and exhibits an antifogging effect.
The antifouling and antifogging agent for organic substrates of the present invention penetrates into and adheres to the organic base by drying at room temperature after being applied to the organic substrate. .

本発明の有機基材用防汚防曇剤は、有機基材に塗布した後は常温乾燥するだけで有機基材に密着するため、熱処理を不要とし、耐熱性が低い樹脂表面への適用及び当該樹脂表面の改質が可能である。   The antifouling and antifogging agent for organic substrates of the present invention adheres to the organic substrate only by drying at room temperature after being applied to the organic substrate, so that heat treatment is unnecessary, and application to a resin surface with low heat resistance and The resin surface can be modified.

本発明の有機基材用防汚防曇剤は、アルコールベースの透明液体であり、常温乾燥後、無色透明な無機硬化塗膜を形成するため、鏡面への適用に適する。   The antifouling antifogging agent for organic substrates of the present invention is an alcohol-based transparent liquid, and after drying at room temperature, forms a colorless and transparent inorganic cured coating film, which is suitable for application to a mirror surface.

図1は、本発明の有機基材用防曇防汚剤を有機基材に塗布し蒸発乾燥させる際の塗膜形成機序を説明する概略図である。FIG. 1 is a schematic diagram for explaining a coating film forming mechanism when the antifogging and antifouling agent for organic substrates of the present invention is applied to an organic substrate and evaporated to dryness. 図２は、本発明の有機基材用防曇防汚剤をアクリル樹脂に塗布し、蒸発乾燥させて形成させたシリカ被膜及びアクリル樹脂の透過型電子顕微鏡（FE-TEM/EDS）による断面観察写真である。FIG. 2 is a cross-sectional observation of a silica film and an acrylic resin formed by applying the antifogging antifouling agent for an organic substrate of the present invention to an acrylic resin and evaporating it to dry, using a transmission electron microscope (FE-TEM / EDS). It is a photograph. 図３は、（１）アクリル樹脂及び（２）本発明の有機基材用防曇防汚剤をアクリル樹脂に塗布した際の表面の原子間力顕微鏡写真である。FIG. 3 is an atomic force micrograph of the surface when (1) acrylic resin and (2) the antifogging antifouling agent for organic substrates of the present invention are applied to an acrylic resin. 図４は、アクリル樹脂の水接触角度、及び本発明の有機基材用防曇防汚剤をアクリル樹脂に塗布した後の水接触角度を示す写真である。FIG. 4 is a photograph showing the water contact angle of the acrylic resin and the water contact angle after applying the antifogging and antifouling agent for organic substrates of the present invention to the acrylic resin. 図５は、本発明の有機基材用防曇防汚剤を塗布したアクリル樹脂を用いた屋外での自然暴露試験の状況及び結果を示す写真である。FIG. 5 is a photograph showing the situation and results of an outdoor natural exposure test using an acrylic resin coated with the antifogging and antifouling agent for organic substrates of the present invention. 図６は、本発明の有機基材用防曇防汚剤をガラス板に塗布した場合の水滴の付着の有無を示す写真である。FIG. 6 is a photograph showing the presence or absence of water droplets when the antifogging and antifouling agent for organic substrates of the present invention is applied to a glass plate.

好ましい実施形態の説明DESCRIPTION OF PREFERRED EMBODIMENTS

本発明の有機基材用防曇防汚剤は、メタノール及び／又はエタノール２０〜８０wt%、好ましくは３５〜５５wt%と、イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテル２０〜８０wt%、好ましくは３５〜５５wt%と、オルガノシリカゾル１．０〜７０．０wt％、好ましくは１．５〜２０．０wtと、テトラヒドロフラン０．１〜３．０wt%、好ましくは０．５〜２．０wt%と、を含有する。メタノール及び／又はエタノールと、イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテルとの含有比率は、１：２〜２：１、好ましくは１：１．５〜１．５：１の範囲にあることが望ましい。   The anti-fogging and antifouling agent for organic substrates of the present invention comprises methanol and / or ethanol 20 to 80 wt%, preferably 35 to 55 wt%, and isopropyl alcohol, normal propyl alcohol or glycol ether 20 to 80 wt%, preferably 35 to 55 wt%. 55 wt%, organosilica sol 1.0-70.0 wt%, preferably 1.5-20.0 wt, tetrahydrofuran 0.1-3.0 wt%, preferably 0.5-2.0 wt% To do. The content ratio of methanol and / or ethanol to isopropyl alcohol, normal propyl alcohol or glycol ether is desirably in the range of 1: 2 to 2: 1, preferably 1: 1.5 to 1.5: 1. .

メタノール及び／又はエタノールは、有機基材表面を膨潤若しくは一部溶解させて、有機基材用防汚防曇剤の有機基材への密着強度を高めると共に、オルガノシリカゾルの分散溶剤として作用する。含有量が上記範囲よりも少量である場合には有機基材への密着性が低下し、上記範囲よりも多量である場合には有機基材表面を著しく浸食するおそれがある。   Methanol and / or ethanol swells or partially dissolves the surface of the organic substrate to increase the adhesion strength of the antifouling and antifogging agent for organic substrates to the organic substrate, and also acts as a dispersion solvent for the organosilica sol. When the content is less than the above range, the adhesion to the organic substrate is lowered, and when it is more than the above range, the surface of the organic substrate may be significantly eroded.

イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテルは、有機基材表面を膨潤若しくは一部溶解させて、有機基材用防汚防曇剤の有機基材への密着強度を高めると共に、オルガノシリカゾルの分散溶剤として作用し、さらに有機基材への塗布後常温乾燥時の乾燥速度を調整する。含有量が上記範囲よりも少量である場合には乾燥速度が速すぎて塗膜が不均一になり、上記範囲よりも多量である場合には有機基材表面の膨潤不良となるおそれがある。   Isopropyl alcohol, normal propyl alcohol, or glycol ether swells or partially dissolves the surface of the organic substrate to increase the adhesion strength of the antifouling and antifogging agent for organic substrates to the organic substrate, and is a dispersion solvent for organosilica sol Furthermore, it adjusts the drying speed at the time of normal temperature drying after application to an organic substrate. When the content is less than the above range, the drying rate is too high and the coating film becomes non-uniform, and when the content is more than the above range, the organic substrate surface may be poorly swelled.

テトラヒドロフランは、有機基材表面を膨潤若しくは一部溶解させて、有機基材用防汚防曇剤の有機基材への密着強度を高める作用をする。特に、低級アルコールやグリコールのみでは膨潤しにくいポリカーボネート樹脂及びポリエステル樹脂の表面の膨潤を助長する作用をする。含有量が上記範囲よりも少量である場合には有機基材表面への密着性が低下し、上記範囲よりも多量である場合には有機基材表面を著しく浸食するおそれがある。   Tetrahydrofuran swells or partially dissolves the surface of the organic base material and acts to increase the adhesion strength of the antifouling and antifogging agent for organic base material to the organic base material. In particular, it acts to promote the swelling of the surfaces of polycarbonate resins and polyester resins that are difficult to swell with only lower alcohols or glycols. When the content is less than the above range, the adhesion to the organic substrate surface is lowered, and when the content is more than the above range, the organic substrate surface may be significantly eroded.

オルガノシリカゾルは、無機硬化塗膜に親水性を付与すると共に、膨潤した有機基材に侵入して有機基材と無機硬化塗膜との界面の密着性を向上させる作用をする。特に、鎖状オルガノシリカゾルを用いることにより、無機硬化塗膜の親水性を著しく高めることができる。また、鎖状オルガノシリカゾルと球状シリカゾルとの併用により、親水性と共に無機硬化塗膜の強度を向上させることができる。含有量が上記範囲よりも少量である場合には親水性が低くなり、上記範囲よりも多量である場合には無機硬化塗膜にクラックを生じさせたり、塗膜に着色がみられたりする。   The organosilica sol imparts hydrophilicity to the inorganic cured coating film and acts to improve the adhesion at the interface between the organic substrate and the inorganic cured coating film by penetrating into the swollen organic substrate. In particular, the hydrophilicity of the inorganic cured coating film can be remarkably increased by using a chain organosilica sol. Further, the combined use of the chain organosilica sol and the spherical silica sol can improve the strength of the inorganic cured coating film as well as the hydrophilicity. When the content is less than the above range, the hydrophilicity is lowered, and when the content is more than the above range, the inorganic cured coating film is cracked or the coating film is colored.

ホウ酸は、有機基材と無機硬化塗膜との密着性を強化する作用をする。含有量が上記範囲よりも少量である場合には有機基材への無機硬化塗膜の密着強度が低く、上記範囲よりも多量である場合には無機硬化塗膜の親水性が低下し、塗膜が白化するおそれがある。   Boric acid acts to strengthen the adhesion between the organic substrate and the inorganic cured coating film. When the content is less than the above range, the adhesion strength of the inorganic cured coating film to the organic substrate is low, and when the content is more than the above range, the hydrophilicity of the inorganic cured coating film decreases, The film may be whitened.

本発明の有機基材用防汚防曇剤は、追加の成分として、ケイ酸ナトリウム、オルトケイ酸テトラエチル、アルカリ土類金属塩から選択される少なくとも1種の添加剤を含有してもよい。アルカリ土類金属塩としては、水酸化マグネシウム、水酸化カルシウム、炭酸マグネシウム、炭酸カルシウム、塩化マグネシウム、塩化カルシウムなどの無機酸塩及び酢酸マグネシウム、酢酸カルシウム、クエン酸マグネシウム、クエン酸カルシウムなどの有機酸塩を好ましく用いることができる。水への溶解性が高いと、電離した際に生じる２価の金属イオン濃度が高くなるため、オルガノシリカゾルが凝集しゲル化しやすく、取り扱いが難しくなるため、水への溶解性が低い方が好ましく、水酸化物塩を特に好ましく用いることができる。ケイ酸ナトリウム及びオルトケイ酸テトラエチルは、無機硬化塗膜に親水性を付与し、膜強度を補強する作用をする。アルカリ土類金属塩は、無機硬化塗膜と有機基材との密着性を向上させる作用をする。ケイ酸ナトリウムの含有量は０．００１〜０．０２５wt%、好ましくは０．０５〜０．０２０wt%であり、オルトケイ酸テトラエチルの含有量は０．０１〜０．２０wt%、好ましくは０．０５〜０．１５wt％であり、アルカリ土類金属塩の含有量は０．００００１〜０．０１wt%、好ましくは０．００２〜０．００５wt%である。ケイ酸ナトリウム及びアルカリ土類金属塩の添加量が上記範囲よりも多量である場合には、有機基材用防汚防曇剤がゲル化してしまい、有機基材に塗布することが困難となり、塗膜が不均一になるおそれがある。ケイ酸ナトリウム及びオルトケイ酸テトラエチルの添加量が上記範囲よりも少量である場合には、無機硬化塗膜の強度が低下するおそれがある。オルトケイ酸テトラエチルの添加量が上記範囲よりも多量である場合には、無機硬化塗膜の親水性が低下するおそれがある。   The antifouling antifogging agent for organic substrates of the present invention may contain at least one additive selected from sodium silicate, tetraethyl orthosilicate, and alkaline earth metal salt as an additional component. Alkaline earth metal salts include inorganic acid salts such as magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, magnesium chloride and calcium chloride, and organic acids such as magnesium acetate, calcium acetate, magnesium citrate and calcium citrate. A salt can be preferably used. If the solubility in water is high, the concentration of divalent metal ions generated upon ionization increases, so the organosilica sol tends to aggregate and gel, making handling difficult. Therefore, it is preferable that the solubility in water is low. Hydroxide salts can be particularly preferably used. Sodium silicate and tetraethyl orthosilicate serve to impart hydrophilicity to the inorganic cured coating film and reinforce the film strength. The alkaline earth metal salt acts to improve the adhesion between the inorganic cured coating film and the organic substrate. The content of sodium silicate is 0.001 to 0.025 wt%, preferably 0.05 to 0.020 wt%, and the content of tetraethyl orthosilicate is 0.01 to 0.20 wt%, preferably 0.05. The content of the alkaline earth metal salt is 0.00001 to 0.01 wt%, preferably 0.002 to 0.005 wt%. When the addition amount of sodium silicate and alkaline earth metal salt is larger than the above range, the antifouling antifogging agent for organic base material gels, and it becomes difficult to apply to the organic base material, The coating film may become non-uniform. When the addition amount of sodium silicate and tetraethyl orthosilicate is less than the above range, the strength of the inorganic cured coating film may be lowered. When the amount of tetraethyl orthosilicate added is larger than the above range, the hydrophilicity of the inorganic cured coating film may be lowered.

本発明の有機基材用防曇防汚剤は、有機溶剤に耐性がなく、基材表面に塗布するために予めプライマーを設けることが必要であった有機基材に直接適用することができる。本発明の有機基材用防曇防汚剤を使用することができる有機基材としては、特に、アクリル樹脂、ポリカーボネート樹脂及びポリエステル樹脂を好適に挙げることができる。   The anti-fogging and antifouling agent for organic substrates of the present invention is not resistant to organic solvents, and can be directly applied to organic substrates that had to be provided with a primer in advance for application to the substrate surface. As an organic base material which can use the antifogging antifouling agent for organic base materials of this invention, an acrylic resin, a polycarbonate resin, and a polyester resin can be mentioned suitably especially.

本発明の有機基材用防曇防汚剤を有機基材に接触又は塗布して、有機基材の表面を膨潤させ、膨潤した有機基材中にオルガノシリカゾルを侵入させ、常温で乾燥させてアルコール系有機溶剤を除去し、シリカ被膜を形成する。本願において「有機基材用防曇防汚剤を有機基材に接触させる」とは、有機基材に直接接触する塗布具を使用せずに有機基材用防曇防汚剤を有機基材と接触させることを意味し、たとえばディップコート、スピンコート、スプレーコート法を用いることで行うことができる。「有機基材用防曇防汚剤を有機基材に塗布する」とは、有機基材に直接接触する塗布具を使用して有機基材用防曇防汚剤を有機基材に付着させることを意味し、たとえばバーコート、刷毛塗り、スポンジ塗りなどの方法で行うことができる。有機基材用防曇防汚剤と有機基材との接触又は塗布は10分以内が好ましい。接触時間が10〜60秒で基材最表面の膨潤が生じる。接触時間が10分を超えると、基材深部の溶解が進行し、乾燥後に干渉縞が生じるおそれがある。有機基材に付着した有機基材用防曇防汚剤は10分以内に揮発するため、塗布時間は10分以上であってもよい。   The anti-fogging and antifouling agent for an organic base material of the present invention is contacted or applied to the organic base material, the surface of the organic base material is swollen, the organosilica sol enters the swollen organic base material, and is dried at room temperature The alcohol-based organic solvent is removed to form a silica film. In the present application, “to make an organic base material an anti-fogging and antifouling agent in contact with an organic base material” means that the organic base material is antifogging and antifouling agent without using an applicator that is in direct contact with the organic base material. For example, using dip coating, spin coating, or spray coating. “Applying an organic substrate antifogging and antifouling agent to an organic substrate” means attaching an organic substrate antifogging and antifouling agent to an organic substrate using an applicator that is in direct contact with the organic substrate. It can be performed by methods such as bar coating, brush coating, and sponge coating. The contact or application of the antifogging and antifouling agent for organic base material with the organic base material is preferably within 10 minutes. When the contact time is 10 to 60 seconds, swelling of the outermost surface of the substrate occurs. If the contact time exceeds 10 minutes, dissolution of the deep part of the substrate proceeds, and interference fringes may occur after drying. Since the anti-fogging and antifouling agent for organic substrates attached to the organic substrate volatilizes within 10 minutes, the application time may be 10 minutes or more.

本発明の有機基材用防曇防汚剤を有機基材に接触又は塗布して塗膜を形成するまでの機序を図1に示す。有機基材に有機基材用防曇防汚剤を接触させ又は塗布すると、溶剤であるメタノール及び／又はエタノール、及びイソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテルが有機基材表面を膨潤又は表面の一部を溶解させ、膨潤又は一部溶解した有機基材の表面からオルガノシリカゾルが有機基材内部に侵入し、有機基材と強固に結びつく。次いで常温乾燥させることにより、溶剤が揮発し、有機基材の膨潤又は一部溶解が終了し、有機基材内部に潜り込んで強固に結びついたシリカを埋設して、親水性の無機硬化塗膜（シリカ被膜）が形成される。   FIG. 1 shows the mechanism until the coating film is formed by contacting or applying the anti-fogging and antifouling agent for organic substrates of the present invention to the organic substrate. When an organic substrate is brought into contact with or applied with an antifogging antifouling agent for organic substrates, the solvents methanol and / or ethanol, and isopropyl alcohol, normal propyl alcohol, or glycol ether swell or swell the surface of the organic substrate. The organosilica sol penetrates into the organic base material from the surface of the organic base material that has been dissolved and swollen or partially dissolved, and is firmly bonded to the organic base material. Next, by drying at room temperature, the solvent is volatilized, the swelling or partial dissolution of the organic base material is completed, the silica embedded inside the organic base material and firmly bonded is embedded, and a hydrophilic inorganic cured coating film ( (Silica coating) is formed.

以下、実施例及び比較例により本発明を更に具体的に説明するが、本発明はこれらに限定されるものではない。
［実施例１］
水4.893wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)42.000wt%、イソプロピルアルコール(和光純薬製)42.500wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)8.000wt%を順次添加し、スターラーで30分撹拌し、防汚防曇剤1を得た。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these.
[Example 1]
Boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.100 wt% was added to water 4.893 wt% and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, methanol (Wako Pure Chemical Industries, Ltd.) 42.000 wt%, isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) 42.500 wt%, and tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) 0.500 wt% were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 8.000 wt% was added sequentially, and the mixture was stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 1.

［実施例２］
水4.893wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)50.000wt%、イソプロピルアルコール(和光純薬製)42.500wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)0.400wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)1.600wt%を順次添加し、スターラーで30分撹拌し、防汚防曇剤2を得た。 [Example 2]
Boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.100 wt% was added to water 4.893 wt% and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, 50.000 wt% of methanol (manufactured by Wako Pure Chemical Industries), 42.500 wt% of isopropyl alcohol (manufactured by Wako Pure Chemical Industries), and 0.500 wt% of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 0.400wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 1.600 wt% was sequentially added, and the mixture was stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 2.

［実施例３］
水4.893wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)42.000wt%、イソプロピルアルコール(和光純薬製)42.500wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてMA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)10.000wt%を添加し、スターラーで30分撹拌し、防汚防曇剤3を得た。 [Example 3]
Boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.100 wt% was added to water 4.893 wt% and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, methanol (Wako Pure Chemical Industries, Ltd.) 42.000 wt%, isopropyl alcohol (Wako Pure Chemical Industries, Ltd.) 42.500 wt%, and tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) 0.500 wt% were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, MA-ST-UP (particle size 40-100 nm, solid content 15%: manufactured by Nissan Chemical Industries) 10.000 wt% is added as organosilica sol and stirred with a stirrer for 30 minutes to obtain antifouling and antifogging agent 3 It was.

［実施例４］
水8.050wt%にエタノール(和光純薬製)0.800wt%、2N塩酸0.010wt%及びオルトケイ酸テトラエチル(TEOS)(和光純薬製)0.100wt%を順次添加し、TEOS溶液を得た。別途、水5.393wt%にホウ酸(和光純薬製)0.090wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)37.800wt%、イソプロピルアルコール(和光純薬製)38.250wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)1.800wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)7.200wt%、TEOS溶液を順次添加し、スターラーで30分撹拌し、防汚防曇剤4を得た。 [Example 4]
Ethanol (manufactured by Wako Pure Chemical Industries) 0.800 wt%, 2N hydrochloric acid 0.010 wt% and orthosilicate tetraethyl (TEOS) (manufactured by Wako Pure Chemical Industries) 0.100 wt% were sequentially added to 8.050 wt% of water to obtain a TEOS solution. Separately, 0.090 wt% boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 5.393 wt% water and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, 37.800 wt% of methanol (manufactured by Wako Pure Chemical Industries), 38.250 wt% of isopropyl alcohol (manufactured by Wako Pure Chemical Industries), and 0.500 wt% of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 1.800wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 7.200 wt%, TEOS solution was sequentially added and stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 4.

［実施例５］
水4.893wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、エタノール(和光純薬製)42.000wt%、イソプロピルアルコール(和光純薬製)42.500wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてIPA-ST(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、IPA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)8.000wt%を順次添加し、スターラーで30分撹拌し、防汚防曇剤5を得た。 [Example 5]
Boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.100 wt% was added to water 4.893 wt% and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) 42.000 wt%, isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) 42.500 wt%, and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 0.500 wt% were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, IPA-ST (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, IPA-ST-UP (particle size 40-100nm, solid content 15%: Nissan Chemical Industry) as organosilica sol (Product made) 8.000 wt% was added sequentially, and the mixture was stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 5.

［実施例6］
水8.050wt%にエタノール(和光純薬製)0.750wt%、2N塩酸0.005wt%及びオルトケイ酸テトラエチル(TEOS)(和光純薬製)0.050wt%を順次添加し、TEOS溶液を得た。別途、水5.030wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.010wt%、水酸化マグネシウム0.005wt%を添加した。その後、メタノール(和光純薬製)10.800wt%、イソプロピルアルコール(和光純薬製)65.250wt%、及びテトラヒドロフラン(和光純薬製)0.450wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)7.500wt%、TEOS溶液を順次添加し、スターラーで30分撹拌し、防汚防曇剤6を得た。 [Example 6]
Ethanol (manufactured by Wako Pure Chemical Industries) 0.750 wt%, 2N hydrochloric acid 0.005 wt% and orthosilicate tetraethyl (TEOS) (manufactured by Wako Pure Chemical Industries) 0.050 wt% were sequentially added to 8.050 wt% of water to obtain a TEOS solution. Separately, 0.100 wt% boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 5.030 wt% water and stirred until it was completely dissolved. 0.010 wt% sodium silicate (Fuji Chemical) and 0.005 wt% magnesium hydroxide were added to the stirring boric acid aqueous solution. Thereafter, methanol (manufactured by Wako Pure Chemical Industries, Ltd.) 10.800 wt%, isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) 65.250 wt%, and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 0.450 wt% were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 7.500 wt%, TEOS solution was sequentially added, and stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 6.

［実施例7］
水8.050wt%にエタノール(和光純薬製)0.800wt%、2N塩酸0.010wt%及びオルトケイ酸テトラエチル(TEOS)(和光純薬製)0.100wt%を順次添加し、TEOS溶液を得た。別途、水2.393wt%にホウ酸(和光純薬製)0.090wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)65.250wt%、イソプロピルアルコール(和光純薬製)10.800wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)10.000wt%、TEOS溶液を順次添加し、スターラーで30分撹拌し、防汚防曇剤7を得た。 [Example 7]
Ethanol (manufactured by Wako Pure Chemical Industries) 0.800 wt%, 2N hydrochloric acid 0.010 wt% and orthosilicate tetraethyl (TEOS) (manufactured by Wako Pure Chemical Industries) 0.100 wt% were sequentially added to 8.050 wt% of water to obtain a TEOS solution. Separately, 0.090 wt% boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 2.393 wt% water and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, 65.250 wt% of methanol (manufactured by Wako Pure Chemical Industries), 10.800 wt% of isopropyl alcohol (manufactured by Wako Pure Chemical Industries), and 0.500 wt% of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 10.000 wt% TEOS solution was sequentially added and stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 7.

［実施例8］
水8.050wt%にエタノール(和光純薬製)0.800wt%、2N塩酸0.010wt%及びオルトケイ酸テトラエチル(TEOS)(和光純薬製)0.100wt%を順次添加し、TEOS溶液を得た。別途、水5.425wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.010wt%、水酸化マグネシウム0.005wt%を添加した。その後、メタノール(和光純薬製)16.800wt%、イソプロピルアルコール(和光純薬製)53.250wt%、及びテトラヒドロフラン(和光純薬製)0.450wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)7.500wt%、TEOS溶液を順次添加し、スターラーで30分撹拌し、防汚防曇剤8を得た。 [Example 8]
Ethanol (manufactured by Wako Pure Chemical Industries) 0.800 wt%, 2N hydrochloric acid 0.010 wt% and orthosilicate tetraethyl (TEOS) (manufactured by Wako Pure Chemical Industries) 0.100 wt% were sequentially added to 8.050 wt% of water to obtain a TEOS solution. Separately, 0.100 wt% boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 5.425 wt% water and stirred until it was completely dissolved. 0.010 wt% sodium silicate (Fuji Chemical) and 0.005 wt% magnesium hydroxide were added to the stirring boric acid aqueous solution. Thereafter, 16.800 wt% of methanol (manufactured by Wako Pure Chemical Industries), 53.250 wt% of isopropyl alcohol (manufactured by Wako Pure Chemical Industries), and 0.450 wt% of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 7.500 wt%, TEOS solution was sequentially added and stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 8.

［実施例9］
水8.050wt%にエタノール(和光純薬製)0.800wt%、2N塩酸0.010wt%及びオルトケイ酸テトラエチル(TEOS)(和光純薬製)0.100wt%を順次添加し、TEOS溶液を得た。別途、水5.393wt%にホウ酸(和光純薬製)0.090wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)56.250wt%、イソプロピルアルコール(和光純薬製)19.800wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)1.800wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)7.200wt%、TEOS溶液を順次添加し、スターラーで30分撹拌し、防汚防曇剤9を得た。
［比較例１］
水5.393wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)42.000wt%、イソプロピルアルコール(和光純薬製)42.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)8.000wt%を順次添加し、スターラーで30分撹拌し、防汚防曇剤10を得た。 [Example 9]
Ethanol (manufactured by Wako Pure Chemical Industries) 0.800 wt%, 2N hydrochloric acid 0.010 wt% and orthosilicate tetraethyl (TEOS) (manufactured by Wako Pure Chemical Industries) 0.100 wt% were sequentially added to 8.050 wt% of water to obtain a TEOS solution. Separately, 0.090 wt% boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added to 5.393 wt% water and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, 56.250 wt% of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), 19.800 wt% of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.500 wt% of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were dropped in small portions and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 1.800wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 7.200 wt%, TEOS solution was sequentially added and stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 9.
[Comparative Example 1]
Boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.100 wt% was added to 5.393 wt% of water and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, methanol (made by Wako Pure Chemical Industries) 42.000 wt% and isopropyl alcohol (made by Wako Pure Chemical Industries) 42.500 wt% were dropped in small portions and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 8.000 wt% was added sequentially, and the mixture was stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 10.

［比較例２］
水69.393wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)10.000wt%、イソプロピルアルコール(和光純薬製)10.000wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)8.000wt%を順次添加し、スターラーで30分撹拌し、防汚防曇剤11を得た。 [Comparative Example 2]
Boric acid (manufactured by Wako Pure Chemical Industries) 0.100 wt% was added to water 69.393 wt% and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, methanol (manufactured by Wako Pure Chemical Industries, Ltd.) 10.000 wt%, isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) 10.000 wt%, and tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 0.500 wt% were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 8.000 wt% was added sequentially, and the mixture was stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 11.

［比較例３］
水4.393wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)85.000wt%、イソプロピルアルコール(和光純薬製)5.000wt%、及びテトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)1.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)4.000wt%を順次添加し、スターラーで30分撹拌し、防汚防曇剤12を得た。 [Comparative Example 3]
Boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.100 wt% was added to 4.393 wt% of water and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, 85.000 wt% of methanol (manufactured by Wako Pure Chemical Industries), 5.000 wt% of isopropyl alcohol (manufactured by Wako Pure Chemical Industries), and 0.500 wt% of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) were added dropwise little by little and stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 1.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 4.000 wt% was sequentially added, and the mixture was stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 12.

［比較例４］
水9.393wt%にホウ酸(和光純薬製)0.100wt%を添加し、完全に溶解するまで撹拌した。撹拌しているホウ酸水溶液にケイ酸ナトリウム(富士化学製)0.005wt%、水酸化マグネシウム0.002wt%を添加した。その後、メタノール(和光純薬製)80.000wt%、テトラヒドロフラン(和光純薬製)0.500wt%を少量ずつ滴下し、スターラーで10分撹拌した。撹拌後、オルガノシリカゾルとしてメタノールシリカゾル(粒子径10〜20nm、固形分30%：日産化学工業製)2.000wt%、MA-ST-UP(粒子径40〜100nm、固形分15%：日産化学工業製)8.000wt%を順次添加し、スターラーで30分撹拌し、防汚防曇剤13を得た。 [Comparative Example 4]
Boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) 0.100 wt% was added to water 9.393 wt% and stirred until it was completely dissolved. To the stirring boric acid aqueous solution, 0.005 wt% sodium silicate (Fuji Chemical) and 0.002 wt% magnesium hydroxide were added. Thereafter, 80.000 wt% of methanol (manufactured by Wako Pure Chemical Industries) and 0.500 wt% of tetrahydrofuran (manufactured by Wako Pure Chemical Industries) were added dropwise little by little, and the mixture was stirred with a stirrer for 10 minutes. After stirring, methanol silica sol (particle size 10-20nm, solid content 30%: manufactured by Nissan Chemical Industries) 2.000wt%, MA-ST-UP (particle size 40-100nm, solid content 15%: manufactured by Nissan Chemical Industries) as organosilica sol ) 8.000 wt% was added sequentially, and the mixture was stirred with a stirrer for 30 minutes to obtain an antifouling and antifogging agent 13.

［実施例10］
防曇防汚剤1〜13をアクリル基材、ポリカーボネート基材及びポリエステル基材の３種類の有機基材にスピンコート法を用いて10秒〜60秒間接触させた後、室温、低湿度環境下で常温乾燥させて、有機基材に無機硬化塗膜を形成させ、試験片１〜13とした。 [Example 10]
After contacting antifogging antifouling agent 1-13 with three types of organic base materials, acrylic base, polycarbonate base and polyester base, for 10 seconds to 60 seconds using a spin coating method, at room temperature and in a low humidity environment And dried at room temperature to form an inorganic cured coating film on the organic base material to obtain test pieces 1 to 13.

［塗膜性能試験］
次に、得られた試験片１〜13の外観を観察した後、接触角、密着強度及び耐久性を測定した。試験方法は以下のとおりである。 [Film performance test]
Next, after observing the appearance of the obtained test pieces 1 to 13, the contact angle, adhesion strength, and durability were measured. The test method is as follows.

・外観確認
試験片上の塗膜状態を目視で確認した。
・接触角測定
ぬれ性評価装置(株式会社ニック製)を用いて、純水1μlを試験片に滴下し、液滴の拡がりが終了した点での接触角を測定した。 -Appearance confirmation The state of the coating film on the test piece was visually confirmed.
-Contact angle measurement Using a wettability evaluation apparatus (manufactured by Nick Co., Ltd.), 1 μl of pure water was dropped onto a test piece, and the contact angle at the point where the expansion of the liquid droplet was completed was measured.

・密着強度試験
JIS K5600-5-6(クロスカット法)に準拠した方法で付着性を確認したところ、目視での確認が難しく、クロスカット法では塗膜の剥離が不明瞭であった。そこで、以下に示す方法で耐テープ剥離性試験を行った。 ・ Adhesion strength test
When adhesion was confirmed by a method based on JIS K5600-5-6 (cross-cut method), visual confirmation was difficult, and peeling of the coating film was unclear with the cross-cut method. Therefore, a tape peel resistance test was performed by the following method.

試験片の塗膜1cm四方の範囲を覆う程度のセロハンテープを貼り、しっかり指でこすった。5分程度放置した後、60°に近い角度で、0.5〜1.0秒で確実に引き離した。評価基準は下記に拠った。   A cellophane tape covering a 1 cm square area of the test piece was applied and rubbed firmly with fingers. After leaving it for about 5 minutes, it was pulled apart at an angle close to 60 ° in 0.5 to 1.0 seconds. The evaluation criteria were as follows.

◎：塗膜の剥離は認められなかった(テープの粘着成分が試験片上全面に残っているものを含む)
○：8割程度塗膜が残存した(テープの粘着成分が試験片上に8割程度残っているものを含む)
△：5割程度塗膜が残存した(テープの粘着成分が試験片上に5割程度残っているものを含む)
×：完全に塗膜が剥離した
・耐久性試験
試験片を屋外に2ヶ月間放置し、曝露試験を行った。2ヶ月曝露後の表面状態を目視により確認した。評価基準は下記に依った。 A: No peeling of the coating film was observed (including the adhesive component of the tape remaining on the entire surface of the test piece)
○: About 80% of the coating film remained (including tape adhesive component remaining about 80% on the test piece)
Δ: About 50% of the coating film remained (including the adhesive component of the tape remaining about 50% on the test piece)
X: The coating film was completely peeled. Durability test The test piece was left outdoors for 2 months, and an exposure test was conducted. The surface condition after 2 months exposure was confirmed visually. Evaluation criteria were as follows.

○：汚れの付着がほとんど認められない
△：汚れの付着は認められるが、流水で洗い流すことができた
実施例１〜9及び比較例１〜４の組成及び試験片１〜13の塗膜性能試験結果を下記表１〜表３にまとめた。 ○: Adherence of dirt is hardly observed Δ: Adherence of dirt is recognized but can be washed away with running water Composition of Examples 1 to 9 and Comparative Examples 1 to 4 and coating film performance of test pieces 1 to 13 The test results are summarized in Tables 1 to 3 below.

表１〜３に示されているように、本発明の有機基材用防汚防曇剤は、異なる３種類の有機基材に塗布して常温乾燥させるだけで、優れた親水性（接触角が5度以下）、優れた密着強度（耐テープ剥離性試験において試験片1〜9はすべて8割以上のテープ残存が認められた）、優れた耐久性（2ヶ月防汚性を維持した）のすべてを満たした無色透明の無機硬化塗膜を有機基材上に形成できることが確認された。一方、テトラヒドロフランを含まない比較例１の塗膜は、ポリカーボネート樹脂及びポリエステル樹脂に対する密着強度及び耐久性が低いことが確認された。また、メタノール、エタノール及びイソプロピルアルコールの含有量が本発明の範囲外である比較例３及び４では、密着強度及び耐久性が低く、干渉縞のある塗膜が形成されることが確認された。有機溶剤の含有量を少量として水の含有量を約69wt％とした比較例２では、有機基材の表面に膨潤が生じず、塗膜の形成もできなかった。 As shown in Tables 1 to 3, the antifouling and antifogging agent for organic substrates of the present invention is excellent in hydrophilicity (contact angle) by simply applying it to three different organic substrates and drying at room temperature. 5 degrees or less), excellent adhesion strength (80 to 80% or more of all test pieces 1 to 9 were found in the tape peel resistance test), excellent durability (maintained antifouling property for 2 months) It was confirmed that a colorless and transparent inorganic cured coating film satisfying all of the above can be formed on an organic substrate. On the other hand, it was confirmed that the coating film of Comparative Example 1 containing no tetrahydrofuran had low adhesion strength and durability to the polycarbonate resin and the polyester resin. Further, in Comparative Examples 3 and 4 in which the contents of methanol, ethanol and isopropyl alcohol were outside the scope of the present invention, it was confirmed that a coating film having interference fringes was formed with low adhesion strength and durability. In Comparative Example 2 in which the content of the organic solvent was small and the water content was about 69 wt%, the surface of the organic base material did not swell and a coating film could not be formed.

［有機基材表面の観察］
実施例１で調製した防汚防曇剤1を有機基材であるアクリル樹脂に接触させ、常温乾燥させた後のアクリル樹脂表面の原子間力顕微鏡（AFM）による表面解析の結果、アクリル樹脂表面に20〜80nm程度の凹凸が形成され、親水効果が強化されていることが確認された（図３参照）。透過型電子顕微鏡（FE-TEM/EDS）による断面観察を行ったところ、界面より約90nmまで浸透していることが確認された（図２参照）。図２に示すFE-TEM/EDSの断面観察及び元素マッピングにおいて観察しやすくするために、表面にPtを蒸着した。図２中、黒く見える部分がPtであり、Ptと塗膜界面から約29nm付近で防汚防曇剤１の酸素（成分１）が22％程度、ケイ素（成分２）が12％程度存在していることがわかる。 [Observation of organic substrate surface]
Antifouling and antifogging agent 1 prepared in Example 1 was brought into contact with an acrylic resin as an organic substrate and dried at room temperature. As a result of surface analysis using an atomic force microscope (AFM) on the acrylic resin surface, the acrylic resin surface As a result, it was confirmed that irregularities of about 20 to 80 nm were formed and the hydrophilic effect was enhanced (see FIG. 3). When a cross-sectional observation was performed with a transmission electron microscope (FE-TEM / EDS), it was confirmed that the film penetrated to about 90 nm from the interface (see FIG. 2). In order to facilitate observation in cross-sectional observation and element mapping of FE-TEM / EDS shown in FIG. 2, Pt was vapor-deposited on the surface. In FIG. 2, the part that appears black is Pt, and the oxygen (component 1) of the antifouling and antifogging agent 1 is about 22% and silicon (component 2) is about 12% around 29 nm from the Pt-coating interface. You can see that

［親水性（水接触角）］
本発明の有機基材用防曇防汚剤を接触させて形成されたシリカ被膜は、アクリル樹脂に親水性を付与する。親水性が付与されるとアクリル樹脂に汚れが付着しにくくなり、また付着した汚れも水と共に流下されるので、有機基材表面の防汚性が強化される。本発明の有機基材用防曇防汚剤を塗布して表面に無機硬化塗膜（シリカ被膜）を形成したアクリル樹脂の親水性の指標である水接触角は20度以下となることが確認された（図４参照）。図４に示す例（実施例５で調製した防汚防曇剤5）では、塗布前のアクリル樹脂表面の水接触角が70度に対して、塗布後の水接触角は7度と著しく親水性が改善されたことがわかる。 [Hydrophilicity (water contact angle)]
The silica film formed by contacting the organic substrate antifogging and antifouling agent of the present invention imparts hydrophilicity to the acrylic resin. When hydrophilicity is imparted, it becomes difficult for dirt to adhere to the acrylic resin, and the attached dirt also flows down together with water, so that the antifouling property of the organic substrate surface is enhanced. It is confirmed that the water contact angle, which is an index of hydrophilicity of an acrylic resin having an inorganic cured coating film (silica coating) formed on the surface by applying the antifogging antifouling agent for organic substrates of the present invention, is 20 degrees or less (See FIG. 4). In the example shown in FIG. 4 (antifouling antifogging agent 5 prepared in Example 5), the water contact angle on the surface of the acrylic resin before application is 70 degrees, and the water contact angle after application is 7 degrees, which is extremely hydrophilic. It can be seen that the sex has improved.

［防汚性］
本発明の有機基材用防曇防汚剤をアクリル樹脂製ミラー及びポリエステル樹脂表面に塗布し、屋外での自然暴露試験を行ったところ、本発明の有機基材用防曇防汚剤を塗布した加工面では水滴も汚れも認められず、良好な視認性が維持されていることが確認できた（図５参照）。図５上の写真は、実施例３で調製した防汚防曇剤3をアクリル樹脂ミラーに接触、塗布して常温乾燥させたサンプルについて雨天時に撮影した水滴の残りの有無を示し、下の写真は実施例１で調製した防汚防曇剤1をポリエステル樹脂表面に接触、塗布して常温乾燥させたサンプルについて汚れの程度を示す。これらのサンプルでは約7ヶ月間の屋外暴露試験の結果、親水効果を維持していたことが確認されている。 [Anti-fouling]
The anti-fogging and antifouling agent for organic substrates of the present invention was applied to an acrylic resin mirror and the surface of a polyester resin and subjected to an outdoor natural exposure test. No water droplets or dirt were observed on the processed surface, and it was confirmed that good visibility was maintained (see FIG. 5). The upper photo in FIG. 5 shows the presence or absence of remaining water droplets taken in the rain on a sample obtained by contacting and applying the antifouling and antifogging agent 3 prepared in Example 3 to an acrylic resin mirror and drying at room temperature. Shows the degree of soiling of a sample obtained by bringing the antifouling and antifogging agent 1 prepared in Example 1 into contact with the polyester resin surface, applying it, and drying it at room temperature. In these samples, it was confirmed that the hydrophilic effect was maintained as a result of an outdoor exposure test for about 7 months.

［防曇性］
実施例１で調製した防汚防曇剤1をガラス板にスピンコートし、常温乾燥させた後、温水の入ったビーカーの上に置いて放置したところ、本発明の有機基材用防曇防汚剤で被覆した部分には水滴が付着しないことが確認できた（図６参照）。同様にアクリル板に適用した場合も図６と同様の効果を示すことを確認している。 [Anti-fogging property]
The antifouling and antifogging agent 1 prepared in Example 1 was spin-coated on a glass plate, dried at room temperature, and then left standing on a beaker containing warm water. It was confirmed that water droplets did not adhere to the portion covered with the soiling agent (see FIG. 6). Similarly, when applied to an acrylic plate, it has been confirmed that the same effect as in FIG. 6 is exhibited.

本発明の有機基材用防汚防曇剤は、セルフクリーニング効果による防汚効果を発揮するため、雨水や散水などを利用できる箇所、特に高所や狭所などの清掃しにくい箇所での使用に適切である。   The antifouling antifogging agent for organic substrates of the present invention exhibits an antifouling effect due to a self-cleaning effect, so it is used in places where rainwater or water spraying can be used, especially in places where it is difficult to clean such as high places and narrow places Is appropriate.

Claims (9)

メタノール及び／又はエタノール２０〜８０wt%と、
イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテル２０〜８０wt%と、
オルガノシリカゾル１．０〜７０．０wt％と、
テトラヒドロフラン０．１〜３．０wt%と、
ホウ酸０．０２〜０．４wt%と、
を含有する、有機基材用防曇防汚剤。 20-80 wt% methanol and / or ethanol,
Isopropyl alcohol, normal propyl alcohol or glycol ether 20-80 wt%,
Organosilica sol 1.0-70.0 wt%,
0.1 to 3.0 wt% of tetrahydrofuran,
0.02-0.4 wt% boric acid,
An anti-fogging and antifouling agent for organic base materials. メタノール及び／又はエタノール３５〜５５wt%と、
イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテル３５〜５５wt%と、
オルガノシリカゾル１．５〜２０．０wt％と、
テトラヒドロフラン０．５〜２．０wt%と、
ホウ酸０．０５〜０．１５wt%
を含有する、請求項１に記載の有機基材用防曇防汚剤。 Methanol and / or ethanol 35-55 wt%;
Isopropyl alcohol, normal propyl alcohol or glycol ether 35-55 wt%,
Organosilica sol 1.5-20.0 wt%,
0.5 to 2.0 wt% tetrahydrofuran,
Boric acid 0.05-0.15wt%
The anti-fogging antifouling agent for organic base materials of Claim 1 containing. メタノール及び／又はエタノールと、イソプロピルアルコール、ノルマルプロピルアルコール又はグリコールエーテルとの含有比率は１：２〜２：１の範囲にある、請求項１又は２に記載の有機基材用防曇防汚剤。   The antifogging antifouling agent for organic substrates according to claim 1 or 2, wherein the content ratio of methanol and / or ethanol to isopropyl alcohol, normal propyl alcohol or glycol ether is in the range of 1: 2 to 2: 1. . 前記オルガノシリカゾルは、鎖状シリカゾルである、請求項１〜３の何れかに記載の有機基材用防曇防汚剤。   The anti-fogging and antifouling agent for organic substrates according to any one of claims 1 to 3, wherein the organosilica sol is a chain silica sol. 前記オルガノシリカゾルは、鎖状シリカゾルと球状シリカゾルとの併用である、請求項１〜４のいずれかに記載の有機基材用防曇防汚剤。   The anti-fogging and antifouling agent for organic substrates according to any one of claims 1 to 4, wherein the organosilica sol is a combination of a chain silica sol and a spherical silica sol. さらに、ケイ酸ナトリウム、オルトケイ酸テトラエチル、アルカリ土類金属塩から選択される少なくとも1種の添加剤を含有する、請求項１〜５の何れかに記載の有機基材用防曇防汚剤。   Furthermore, the antifogging antifouling agent for organic base materials in any one of Claims 1-5 containing the at least 1 sort (s) of additive selected from sodium silicate, orthoethyl tetrasilicate, and alkaline-earth metal salt. 前記有機基材は、アクリル樹脂、ポリカーボネート樹脂及びポリエステル樹脂から選択される、請求項１〜６の何れかに記載の有機基材用防曇防汚剤。   The said organic base material is an anti-fogging antifouling agent for organic base materials in any one of Claims 1-6 selected from an acrylic resin, a polycarbonate resin, and a polyester resin. 請求項１〜７の何れかに記載の有機基材用防曇防汚剤を有機基材に接触又は塗布して、有機基材の表面を膨潤させ、膨潤した有機基材中にオルガノシリカゾルを侵入させ、常温で乾燥させてアルコール系有機溶剤を除去し、シリカ被膜を形成することを含む、有機基材を防曇防汚剤で被覆する方法。   The antifogging antifouling agent for organic substrates according to any one of claims 1 to 7 is contacted or applied to the organic substrate to swell the surface of the organic substrate, and the organosilica sol is added to the swollen organic substrate. A method of coating an organic base material with an antifogging and antifouling agent, which comprises infiltrating and drying at room temperature to remove an alcoholic organic solvent and forming a silica film. 前記有機基材は、アクリル樹脂、ポリカーボネート樹脂及びポリエステル樹脂から選択される、請求項８に記載の方法。   The method according to claim 8, wherein the organic substrate is selected from an acrylic resin, a polycarbonate resin, and a polyester resin.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015227533A (en) * 2014-05-30 2015-12-17 積水樹脂株式会社 Reflection mirror for road and manufacturing method of reflection mirror for road
JP2017182065A (en) * 2016-03-29 2017-10-05 リコーイメージング株式会社 Optical element and manufacturing method of the same
JP2018024903A (en) * 2016-08-09 2018-02-15 豊田合成株式会社 Antifouling plated article and manufacturing method therefor
KR101882762B1 (en) * 2017-05-10 2018-07-27 주식회사 크래프트맨 Method for producing adhesive sheet comprising a surface-coating film layer having antifouling property and scratch-resisting property and surface coating layer forming solution for forming surface-coating film layer
JPWO2017150393A1 (en) * 2016-02-29 2018-08-09 富士フイルム株式会社 Aqueous coating composition, antireflection film, laminate, method for producing laminate, and solar cell module
EP3663809A1 (en) 2018-12-07 2020-06-10 Canon Kabushiki Kaisha Transparent member and image pickup apparatus, and method of manufacturing transparent member
WO2020129424A1 (en) 2018-12-21 2020-06-25 コニカミノルタ株式会社 Dielectric film, method for producing same and optical member using same
WO2021060211A1 (en) 2019-09-27 2021-04-01 日東電工株式会社 Peelable coating film, coating-material set, and coating-material for forming hydrophilic coating film
EP3901671A1 (en) * 2018-12-21 2021-10-27 Konica Minolta, Inc. Dielectric multilayer film, method for producing same and optical member using same

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000318084A (en) * 1999-03-09 2000-11-21 Toto Ltd Hydrophilic member
JP2004099647A (en) * 2002-09-05 2004-04-02 Toto Ltd Coating composition for forming photocatalytic and hydrophilic film, photocatalytic and hydrophilic member and method for producing the same
JP2005113023A (en) * 2003-10-08 2005-04-28 Dainippon Shikizai Kogyo Kk Photocatalyst-containing silicon composition
WO2006049008A1 (en) * 2004-11-08 2006-05-11 Asahi Glass Company, Limited Inorganic coating composition, hydrophilic coating film and method for forming hydrophilic coating film

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000318084A (en) * 1999-03-09 2000-11-21 Toto Ltd Hydrophilic member
JP2004099647A (en) * 2002-09-05 2004-04-02 Toto Ltd Coating composition for forming photocatalytic and hydrophilic film, photocatalytic and hydrophilic member and method for producing the same
JP2005113023A (en) * 2003-10-08 2005-04-28 Dainippon Shikizai Kogyo Kk Photocatalyst-containing silicon composition
WO2006049008A1 (en) * 2004-11-08 2006-05-11 Asahi Glass Company, Limited Inorganic coating composition, hydrophilic coating film and method for forming hydrophilic coating film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JPWO2017150393A1 (en) * 2016-02-29 2018-08-09 富士フイルム株式会社 Aqueous coating composition, antireflection film, laminate, method for producing laminate, and solar cell module
JP2017182065A (en) * 2016-03-29 2017-10-05 リコーイメージング株式会社 Optical element and manufacturing method of the same
JP2018024903A (en) * 2016-08-09 2018-02-15 豊田合成株式会社 Antifouling plated article and manufacturing method therefor
KR101882762B1 (en) * 2017-05-10 2018-07-27 주식회사 크래프트맨 Method for producing adhesive sheet comprising a surface-coating film layer having antifouling property and scratch-resisting property and surface coating layer forming solution for forming surface-coating film layer
CN116041993A (en) * 2018-12-07 2023-05-02 佳能株式会社 Transparent member, image pickup apparatus, and method for manufacturing transparent member
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EP3663809A1 (en) 2018-12-07 2020-06-10 Canon Kabushiki Kaisha Transparent member and image pickup apparatus, and method of manufacturing transparent member
EP4328260A2 (en) 2018-12-07 2024-02-28 Canon Kabushiki Kaisha Application liquid, method of manufacturing a member, and member
EP4328260A3 (en) * 2018-12-07 2024-05-01 Canon Kabushiki Kaisha Application liquid, method of manufacturing a member, and member
US12096104B2 (en) 2018-12-07 2024-09-17 Canon Kabushiki Kaisha Transparent member and image pickup apparatus, and method of manufacturing transparent member
WO2020129424A1 (en) 2018-12-21 2020-06-25 コニカミノルタ株式会社 Dielectric film, method for producing same and optical member using same
EP3901671A1 (en) * 2018-12-21 2021-10-27 Konica Minolta, Inc. Dielectric multilayer film, method for producing same and optical member using same
EP3901671A4 (en) * 2018-12-21 2022-02-23 Konica Minolta, Inc. Dielectric multilayer film, method for producing same and optical member using same
US12024767B2 (en) 2018-12-21 2024-07-02 Konica Minolta, Inc. Dielectric film, method for producing same and optical member using same
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