JP2009173787A - Water-repelling material, manufacturing method of optical member using the same, optical member, and spectacle plastic lens - Google Patents
Water-repelling material, manufacturing method of optical member using the same, optical member, and spectacle plastic lens Download PDFInfo
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- JP2009173787A JP2009173787A JP2008014713A JP2008014713A JP2009173787A JP 2009173787 A JP2009173787 A JP 2009173787A JP 2008014713 A JP2008014713 A JP 2008014713A JP 2008014713 A JP2008014713 A JP 2008014713A JP 2009173787 A JP2009173787 A JP 2009173787A
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Landscapes
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Abstract
Description
本発明は、撥水材料、それを用いた光学部材の製造方法、光学部材並びに眼鏡用プラスチックレンズに関し、詳しくは、耐摩擦性及び耐摩耗性を有し、傷がつきにくく、防汚性が高く、寿命が長い、撥水及び撥油性を有する撥水膜が形成できる、撥水材料、それを用いた光学部材の製造方法、光学部材並びに眼鏡用プラスチックレンズに関する。 The present invention relates to a water-repellent material, a method for producing an optical member using the same, an optical member, and a plastic lens for spectacles. Specifically, the material has friction resistance and wear resistance, is hardly scratched, and has antifouling properties. The present invention relates to a water repellent material capable of forming a water repellent film having a high water repellent property and a long life, a method for producing an optical member using the water repellent material, an optical member, and a plastic lens for spectacles.
レンズ等の光学部材上に施された反射防止膜は、一般にＺｒＯ2，ＳｉＯ2などの無機酸化物により形成されている。そのため、汗、指紋などによる汚れが付着しやすく、かつこれらの汚れを除去することが困難であった。こうした問題を解決するために、例えば、特許文献１には、ｍ−キシレンヘキサクロライド希釈溶液から真空蒸着法にて反射防止膜上に撥水性を有する薄膜を形成する方法が開示されている。また、この特許文献１には、銅などの熱伝導性の高い金属粉末を焼結してなる多孔性材料に、フッ素含有のシラザン系有機ケイ素化合物をキシリレンヘキサフロライド、トリクロロモノフルオロメタンなどのフッ素系溶媒で希釈して得た撥水処理液を含浸させ、真空下で加熱して光学部材上に蒸着し成膜する方法が開示されている。また、特許文献２〜５にはこれ以外のフッ素含有有機ケイ素化合物からなる撥水剤が開示されている。しかしながら、これらの撥水剤からなる撥水膜に対して更なる性能の向上が望まれていた。
特に、撥水膜は光学部材の最外層に形成されていることから、表面に付着した汚れの拭き取りや、外界の影響などにより、撥水性が時間とともに低下する。このため、撥水性が長期間維持できることが望まれている。また、指紋や皮脂などが付着した場合、拭き取るにはかなりの時間と繰り返しの作業が必要であり、さらに容易に拭き取れることが望まれていた。
この様な課題に対応するものとして、特許文献６〜１０には、基材の表面を処理して、撥水性に加えて、滑り性、防汚性などの性能も付与することが記載されている。
このように撥水膜を設けても、プラスチック最外層の膜ということで、外界の様々な要因（皮脂、汗、拭き取り時の摩擦、薬品等）を受けやすく、撥水膜の経時劣化を早めてしまう。このような問題に対応するものとして、特許文献７あるいは特許文献１２のように耐摩擦性を付与した膜を設けた基材もあるが、さらなる各性能の向上が要求されている。
また、プラスチック表面に指紋（皮脂）やその他外的要因による汚れが付着した際に、不織布やティッシュペーパー等で汚れを拭き取るが、それを繰り返すうちに、防止性の効果が薄れてしまうという問題があった。
特許文献１０には、眼鏡レンズ表面にフッ素シラン化合物を用いることで防汚性を付与するという製造技術が開示され、玉型加工の際に滑るのを防止し、加工精度を上げることが記載されている。しかしながら、玉型加工時に軸ずれを防止するために、表面はあえて滑りにくい性能になっているため、拭き取り等の手入れをしようとした時に必要以上の力がかかってしまい、結果的に表面コーティングの寿命が短くなってしまう。
また、特許文献１１には、フッ素シラン化合物を用いて汚染防止性を高め、汚染物の除去が容易とした防汚性レンズが開示されている。しかしながら、特許文献１１の発明では、レンズ表面層が、耐摩擦性、耐摩耗性、滑り性を付与していないため、長期使用時には耐久性が落ちてしまい、寿命が短くなってしまう。
An antireflection film applied on an optical member such as a lens is generally formed of an inorganic oxide such as ZrO 2 or SiO 2 . For this reason, dirt due to sweat, fingerprints and the like is likely to adhere, and it has been difficult to remove these dirt. In order to solve such a problem, for example, Patent Document 1 discloses a method of forming a thin film having water repellency on an antireflection film from a diluted m-xylene hexachloride solution by vacuum deposition. In Patent Document 1, a porous material formed by sintering a metal powder having high thermal conductivity such as copper, a fluorine-containing silazane-based organosilicon compound, xylylene hexafluoride, trichloromonofluoromethane, etc. A method of forming a film by impregnating with a water repellent treatment liquid obtained by diluting with a fluorine-based solvent, heating under vacuum and depositing on an optical member is disclosed. Patent Documents 2 to 5 disclose water repellents composed of other fluorine-containing organosilicon compounds. However, further improvement in performance has been desired for water-repellent films made of these water-repellent agents.
In particular, since the water repellent film is formed on the outermost layer of the optical member, the water repellency decreases with time due to wiping off dirt adhering to the surface, the influence of the outside world, and the like. For this reason, it is desired that water repellency can be maintained for a long time. In addition, when fingerprints or sebum adheres, it takes a considerable amount of time and repeated operations to wipe it off, and it has been desired to wipe it off more easily.
In order to deal with such a problem, Patent Documents 6 to 10 describe that the surface of a base material is treated to provide performance such as slipperiness and antifouling property in addition to water repellency. Yes.
Even if a water-repellent film is provided in this way, it is a plastic outermost layer film, which is susceptible to various external factors (sebum, sweat, friction during wiping, chemicals, etc.), and accelerates the deterioration of the water-repellent film over time. End up. As a countermeasure to such a problem, there is a base material provided with a film imparted with friction resistance as in Patent Document 7 or Patent Document 12, but further improvements in performance are required.
In addition, when fingerprints (sebum) or other dirt from the outside adheres to the plastic surface, the dirt is wiped off with a non-woven fabric or tissue paper. there were.
Patent Document 10 discloses a manufacturing technology that imparts antifouling properties by using a fluorine silane compound on the surface of a spectacle lens, and describes that it prevents slipping during processing of the target lens shape and increases processing accuracy. ing. However, in order to prevent axial misalignment when processing the target lens shape, the surface is deliberately difficult to slip, so excessive force is required when wiping or other cleaning is performed, resulting in surface coating. Life is shortened.
Patent Document 11 discloses an antifouling lens that uses a fluorine silane compound to enhance antifouling properties and facilitates removal of contaminants. However, in the invention of Patent Document 11, since the lens surface layer does not impart friction resistance, wear resistance, and slipperiness, the durability decreases during long-term use, and the life is shortened.
本発明は前記の課題を解決するためになされたもので、耐摩擦性及び耐摩耗性を有し、傷がつきにくく、防汚性が高く、寿命が長い撥水膜が形成できる、撥水材料、それを用いた光学部材の製造方法、光学部材並びに眼鏡用プラスチックレンズを提供することを目的とするものである。 The present invention has been made in order to solve the above-described problems, and has a friction and wear resistance, is not easily scratched, has a high antifouling property, and can form a water repellent film having a long life. An object of the present invention is to provide a material, a method for producing an optical member using the material, an optical member, and a plastic lens for spectacles.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、下記一般式[１]のパーフルオロポリエーテル−ポリシロキサン共重合体変性シランを用い、さらに、（ａ）下記一般式[２]で示されるフッ素置換アルキル基含有有機ケイ素化合物、（ｂ）下記一般式[３−１]、[３−２] 及び[３−３]の中から選ばれた少なくとも一種のシラン化合物、（ｃ）両末端に加水分解基を有するアミノ変性ポリシロキサン、及び（ｄ）アミノ基と反応するエポキシ基含有シラン又はポリシロキサンから選ばれる少なくとも一種を含むことで動摩擦係数が０．０５以下であり、更に耐摩耗性＋８．０以下の撥水膜が得られ、上記課題を解決し得ることを見出した。本発明はかかる知見に基づいて完成したものである。 As a result of intensive studies to achieve the above object, the present inventors have used a perfluoropolyether-polysiloxane copolymer-modified silane represented by the following general formula [1], and (a) the following general formula A fluorine-substituted alkyl group-containing organosilicon compound represented by [2], (b) at least one silane compound selected from the following general formulas [3-1], [3-2] and [3-3]; The dynamic friction coefficient is 0.05 or less by including at least one selected from (c) an amino-modified polysiloxane having hydrolyzable groups at both ends, and (d) an epoxy group-containing silane or polysiloxane that reacts with an amino group. Furthermore, it has been found that a water-repellent film having abrasion resistance of +8.0 or less can be obtained and the above-mentioned problems can be solved. The present invention has been completed based on such findings.
すなわち、本発明は、少なくとも下記一般式[１]で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランと、（ａ）下記一般式[２]で示されるフッ素置換アルキル基含有有機ケイ素化合物、（ｂ）下記一般式[３−１]、[３−２] 及び[３−３]の中から選ばれた少なくとも一種のシラン化合物、（ｃ）両末端に加水分解基を有するアミノ変性ポリシロキサン、及び（ｄ）アミノ基と反応するエポキシ基含有シラン又はポリシロキサンから選ばれる少なくとも一種とを含む撥水材料であり、この撥水材料を用いて光学部材上に撥水膜を形成する光学部材の製造方法、この撥水材料を用いて光学部材上に撥水膜が形成されてなる光学部材並びに眼鏡用プラスチックレンズを提供するものである。
一般式[１]
（ａ）成分
一般式[２]
（ｂ）成分
一般式[３−１] Ｒ'−Ｓｉ(ＯＲ’’)3
一般式[３−２] Ｓｉ(ＯＲ’’)4
一般式[３−３] ＳｉＯ（ＯＲ’’）3Ｓｉ（ＯＲ’’）3
（式中、Ｒ'は有機基であり、Ｒ’’はアルキル基である。）
That is, the present invention provides at least a perfluoropolyether-polysiloxane copolymer-modified silane represented by the following general formula [1] and (a) a fluorine-substituted alkyl group-containing organosilicon compound represented by the following general formula [2] (B) at least one silane compound selected from the following general formulas [3-1], [3-2] and [3-3], and (c) an amino-modified poly having hydrolyzable groups at both ends. An optical material comprising a water repellent material containing siloxane and (d) at least one selected from epoxy group-containing silane or polysiloxane that reacts with amino groups, and using this water repellent material, a water repellent film is formed on an optical member. A member manufacturing method, an optical member in which a water-repellent film is formed on an optical member using the water-repellent material, and a plastic lens for spectacles are provided.
General formula [1]
(A) Component general formula [2]
(B) Component General Formula [3-1] R′—Si (OR ″) 3
General formula [3-2] Si (OR ″) 4
Formula [3-3] SiO (OR ″) 3 Si (OR ″) 3
(In the formula, R ′ is an organic group, and R ″ is an alkyl group.)
本発明の撥水材料を用いると、耐摩擦性及び耐摩耗性を有し、傷がつきにくく、防汚性が高く、寿命が長い、撥水及び撥油性を有する撥水膜が形成できる。 When the water-repellent material of the present invention is used, it is possible to form a water-repellent film having water and oil repellency that has friction resistance and wear resistance, is hardly scratched, has high antifouling properties, and has a long life.
本発明の撥水材料は、少なくとも下記一般式[１]で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランと、ａ）下記一般式[２]で示されるフッ素置換アルキル基含有有機ケイ素化合物、（ｂ）下記一般式[３−１]、[３−２] 及び[３−３]の中から選ばれた少なくとも一種のシラン化合物、（ｃ）両末端に加水分解基を有するアミノ変性ポリシロキサン、及び（ｄ）アミノ基と反応するエポキシ基含有シラン又はポリシロキサンから選ばれる少なくとも一種を含む。
以下、一般式[１]について説明する。
一般式[１]
The water repellent material of the present invention comprises at least a perfluoropolyether-polysiloxane copolymer-modified silane represented by the following general formula [1], and a) a fluorine-substituted alkyl group-containing organosilicon represented by the following general formula [2] Compound, (b) at least one silane compound selected from the following general formulas [3-1], [3-2] and [3-3], (c) amino-modified having hydrolyzable groups at both ends It contains at least one selected from polysiloxane and (d) an epoxy group-containing silane that reacts with an amino group or polysiloxane.
Hereinafter, the general formula [1] will be described.
General formula [1]
一般式[１]において、Ｒｇ基は、式：−（ＣjＦ2jＯ）−（ｊは１〜５の整数であり、好ましくは（１〜３）の整数であり、該一般式中の（ＣjＦ2jＯ）の配列はランダムである。）で表わされる繰り返し単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する二価の基であり、繰り返し単位数が３０〜６０（好ましくは３０〜５０）であり、異なるｊの繰り返し単位を同時に含んでいても良い。 In the general formula [1], the Rg group is represented by the formula:-(C j F 2j O)-(j is an integer of 1 to 5, preferably an integer of (1 to 3). (C j F 2j O) is a divalent group having a linear perfluoropolyalkylene ether structure having no branch, including a repeating unit represented by (C j F 2j O). 30 to 60 (preferably 30 to 50), and may contain j repeating units at the same time.
ここで、Ｒｇは、二価の直鎖型パーフルオロポリエーテル基であり、各種鎖長のパーフルオロポリエーテル基が含まれるが、好ましくは炭素数１〜５程度のパーフルオロポリエーテル基を繰返し単位とする二価の直鎖型パーフルオロポリエーテルである。この二価の直鎖型パーフルオロポリエーテルとしては、例えば、以下に示すようなものが挙げられる。
−ＣＦ2ＣＦ2Ｏ（ＣＦ2ＣＦ2ＣＦ2Ｏ）kＣＦ2ＣＦ2−
−ＣＦ2（ＯＣ2Ｆ4）p−（ＯＣＦ2）q−
上記化学構造式中のｋ、ｐ及びｑはそれぞれ１以上の整数を示す。ｋ及びｐ+ｑは３０〜６０の範囲が好ましい。なお、パーフルオロポリエーテルの分子構造は、これら例示したものに限定されるものではない。
Here, Rg is a divalent linear perfluoropolyether group, including perfluoropolyether groups of various chain lengths, preferably repeating a perfluoropolyether group having about 1 to 5 carbon atoms. It is a divalent linear perfluoropolyether as a unit. Examples of the divalent linear perfluoropolyether include those shown below.
-CF 2 CF 2 O (CF 2 CF 2 CF 2 O) k CF 2 CF 2 -
-CF 2 (OC 2 F 4) p - (OCF 2) q -
K, p, and q in the above chemical structural formula each represent an integer of 1 or more. k and p + q are preferably in the range of 30-60. The molecular structure of perfluoropolyether is not limited to those exemplified.
一般式[１]において、Ｒ1は同一又は異なっていてもよい炭素数１〜４のアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基）又はフェニル基である。
一般式[１]において、ｗは３０〜１００であり、３０〜６０であると好ましい。ａ，ｂ及びｃは、それぞれ独立に１〜５の整数であり、１〜３であると好ましい。
一般式[１]において、Ｒ2は炭素数１〜４のアルキル基（例えば、メチル基、エチル基、プロピル基、ブチル基）又はフェニル基である。
In the general formula [1], R 1 is an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group) or phenyl group which may be the same or different.
In General formula [1], w is 30-100, and it is preferable in it being 30-60. a, b and c are each independently an integer of 1 to 5, preferably 1 to 3.
In the general formula [1], R 2 is an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group) or a phenyl group.
一般式[１]において、Ｘ1は加水分解性基であり、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシ基；メトキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基等のアルコキシアルコキシ基；アリロキシ基、イソプロペノキシ等のアルケニルオキシ基；アセトキシ基、プロピオニルオキシ基、ブチルカルボニルオキシ基、ベンゾイルオキシ基等のアシロキシ基；ジメチルケトオキシム基、メチルエチルケトオキシム基、ジエチルケトオキシム基、シクロペンタノキシム基、シクロヘキサノキシム基等のケトオキシム基；Ｎ−メチルアミノ基、Ｎ−エチルアミノ基、Ｎ−プロピルアミノ基、Ｎ−ブチルアミノ基、Ｎ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、Ｎ−シクロヘキシルアミノ基等のアミノ基；Ｎ−メチルアセトアミド基、Ｎ−エチルアセトアミド基、Ｎ−メチルベンズアミド基等のアミド基；Ｎ，Ｎ−ジメチルアミノオキシ基、Ｎ，Ｎ−ジエチルアミノオキシ基等のアミノオキシ基等を挙げることができる。
これらの中で、メトキシ基、エトキシ基が好適である。
一般式[１]において、ｄは２又は３で、加水分解および縮合反応性、および被膜の密着性の観点から考えると３であることが好ましく、ｙは１〜５の整数であり、１〜３であると好ましい。
一般式[１]の化合物は、１種単独でも２種以上を組合せても使用することができる。
本発明の撥水材料においては、一般式[１]で表される化合物を５０質量％以上含有すると好ましい。
In the general formula [1], X 1 is a hydrolyzable group, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group; an alkoxyalkoxy such as a methoxymethoxy group, a methoxyethoxy group, or an ethoxyethoxy group Groups; alkenyloxy groups such as allyloxy groups and isopropenoxy; acyloxy groups such as acetoxy groups, propionyloxy groups, butylcarbonyloxy groups, and benzoyloxy groups; dimethyl ketoxime groups, methyl ethyl ketoxime groups, diethyl ketoxime groups, cyclopentanoximes Group, ketoxime group such as cyclohexanoxime group; N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, Ami such as N-cyclohexylamino group Group; amide groups such as N-methylacetamide group, N-ethylacetamide group and N-methylbenzamide group; aminooxy groups such as N, N-dimethylaminooxy group and N, N-diethylaminooxy group Can do.
Among these, a methoxy group and an ethoxy group are preferable.
In the general formula [1], d is 2 or 3, and is preferably 3 from the viewpoint of hydrolysis and condensation reactivity and film adhesion, and y is an integer of 1 to 5, 3 is preferable.
The compound of general formula [1] can be used singly or in combination of two or more.
In the water repellent material of the present invention, the compound represented by the general formula [1] is preferably contained in an amount of 50% by mass or more.
以下、（ａ）〜（ｄ）成分について説明する。
（ａ）成分：一般式[２] で示されるフッ素置換アルキル基含有有機ケイ素化合物
一般式[２]のフッ素置換アルキル基含有有機ケイ素化合物
Component (a): Fluorine-substituted alkyl group-containing organosilicon compound represented by formula [2] Fluorine-substituted alkyl group-containing organosilicon compound represented by formula [2]
一般式[２]において、Ｒｆ基は、式：−（ＣkＦ2kＯ）−（式中、ｋは１〜６、好ましくは１〜４の整数であり、該一般式中の（ＣkＦ2kＯ）の配列はランダムである。）で表わされる単位を含み、分岐を有しない直鎖状のパーフルオロポリアルキレンエーテル構造を有する二価の基である。なお、前記一般式[２]中のｎ及びｎ’がいずれも０である場合、前記一般式[２]中の酸素原子（Ｏ）に結合する前記Ｒｆ基の末端は、酸素原子ではない。 In the general formula [2], the Rf group is represented by the formula: — (C k F 2k O) — (wherein k is an integer of 1 to 6, preferably 1 to 4, and (C k The sequence of F 2k O) is random. It is a divalent group having a linear perfluoropolyalkylene ether structure that includes a unit represented by When n and n ′ in the general formula [2] are both 0, the terminal of the Rf group bonded to the oxygen atom (O) in the general formula [2] is not an oxygen atom.
ここで、Ｒｆは、二価の直鎖型パーフルオロポリエーテル基であり、各種鎖長のパーフルオロポリエーテル基が含まれるが、好ましくは炭素数１〜６程度のパーフルオロポリエーテル基を繰返し単位とする二価の直鎖型パーフルオロポリエーテルである。この二価の直鎖型パーフルオロポリエーテルとしては、例えば、以下に示すようなものが挙げられる。
−ＣＦ2ＣＦ2Ｏ（ＣＦ2ＣＦ2ＣＦ2Ｏ）rＣＦ2ＣＦ2−
−ＣＦ2（ＯＣ2Ｆ4）s−（ＯＣＦ2）t−
上記化学構造式中のｒ、ｓ及びｔはそれぞれ１以上の整数を示す。具体的には１〜５０、より好ましくは１０〜４０の範囲が好ましい。なお、パーフルオロポリエーテルの分子構造は、これら例示したものに限定されるものではない。
Here, Rf is a divalent linear perfluoropolyether group, which includes perfluoropolyether groups of various chain lengths, preferably repeating a perfluoropolyether group having about 1 to 6 carbon atoms. It is a divalent linear perfluoropolyether as a unit. Examples of the divalent linear perfluoropolyether include those shown below.
-CF 2 CF 2 O (CF 2 CF 2 CF 2 O) r CF 2 CF 2 -
-CF 2 (OC 2 F 4) s - (OCF 2) t -
R, s, and t in the above chemical structural formula each represents an integer of 1 or more. Specifically, a range of 1 to 50, more preferably 10 to 40 is preferable. The molecular structure of perfluoropolyether is not limited to those exemplified.
一般式[２]において、Ｘは加水分解性基又はハロゲン原子である。上記Ｘが加水分解性基である場合としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシ基；メトキシメトキシ基、メトキシエトキシ基、エトキシエトキシ基等のアルコキシアルコキシ基；アリロキシ基、イソプロペノキシ等のアルケニルオキシ基；アセトキシ基、プロピオニルオキシ基、ブチルカルボニルオキシ基、ベンゾイルオキシ基等のアシロキシ基；ジメチルケトオキシム基、メチルエチルケトオキシム基、ジエチルケトオキシム基、シクロペンタノキシム基、シクロヘキサノキシム基等のケトオキシム基；Ｎ−メチルアミノ基、Ｎ−エチルアミノ基、Ｎ−プロピルアミノ基、Ｎ−ブチルアミノ基、Ｎ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、Ｎ−シクロヘキシルアミノ基等のアミノ基；Ｎ−メチルアセトアミド基、Ｎ−エチルアセトアミド基、Ｎ−メチルベンズアミド基等のアミド基；Ｎ，Ｎ−ジメチルアミノオキシ基、Ｎ，Ｎ−ジエチルアミノオキシ基等のアミノオキシ基等を挙げることができる。
また、上記Ｘがハロゲン原子である場合としては、例えば、塩素原子、臭素原子、ヨウ素原子等が挙げられる。
これらの中で、メトキシ基、エトキシ基及び塩素原子が好適である。
In the general formula [2], X is a hydrolyzable group or a halogen atom. Examples of the case where X is a hydrolyzable group include, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; an alkoxyalkoxy group such as a methoxymethoxy group, a methoxyethoxy group, and an ethoxyethoxy group; Alkenyloxy groups such as isopropenoxy; acyloxy groups such as acetoxy group, propionyloxy group, butylcarbonyloxy group, benzoyloxy group; dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, cyclopentanoxime group, cyclohexano group Ketoxime groups such as oxime groups; N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, N-cyclohexylamino group Amino groups such as groups N- methylacetamide group, N- ethyl acetamide group, an amido group such as N- methylbenzamide group; N, N- dimethylamino group, N, can be mentioned an amino group, such as N- diethylamino group.
Moreover, as a case where said X is a halogen atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.
Among these, a methoxy group, an ethoxy group, and a chlorine atom are preferable.
一般式[２]において、Ｒは炭素原子数１〜８の一価炭化水素基であり、Ｒが複数存在する場合には、Ｒは互いに同一でも異なってもよい。Ｒの具体例としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、キシリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基等のアルケニル基等が挙げられる。これらの中でも炭素原子数１〜３の一価炭化水素基が好ましく、特にメチル基が好適である。 In the general formula [2], R is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and when a plurality of Rs are present, the Rs may be the same or different. Specific examples of R include, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; Aryl groups such as benzyl group and phenethyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group. Among these, a monovalent hydrocarbon group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable.
一般式[２]において、ｎ及びｎ’はそれぞれ０〜２の整数であり、好ましくは１である。ｎとｎ’は互いに同一であっても異なっていてもよい。また、ｍ及びｍ’はそれぞれ１〜５の整数であり、３であることが好ましい。ｍとｍ’は互いに同一であっても異なっていてもよい。
次に、ａ及びｂは各々２又は３であり、加水分解及び縮合反応性、及び被膜の密着性の観点から、３であることが好ましい。
一般式[２]で表されるフッ素置換アルキル基含有有機ケイ素化合物の分子量は、特に制限されないが、安定性、取扱い易さ等の点から、数平均分子量で５００〜２０，０００、好ましくは１０００〜１０，０００のものが適当である。
In the general formula [2], n and n ′ are each an integer of 0 to 2, preferably 1. n and n ′ may be the same or different from each other. M and m ′ are each an integer of 1 to 5, and is preferably 3. m and m ′ may be the same as or different from each other.
Next, a and b are each 2 or 3, and preferably 3 from the viewpoints of hydrolysis and condensation reactivity and coating adhesion.
The molecular weight of the fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula [2] is not particularly limited, but from the viewpoint of stability, ease of handling, etc., the number average molecular weight is 500 to 20,000, preferably 1000. A value of ˜10,000 is suitable.
一般式[２]で表されるフッ素置換アルキル基含有有機ケイ素化合物の具体例としては、例えば、下記構造式で示されるものが挙げられる。但し、下記例示に限定されるものではない。
（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＦ2ＣＦ2Ｏ（ＣＦ2ＣＦ2ＣＦ2Ｏ）lＣＦ2ＣＦ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3
（ＣＨ3Ｏ）2ＣＨ3ＳｉＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＦ2ＣＦ2Ｏ（ＣＦ2ＣＦ2ＣＦ2Ｏ）lＣＦ2ＣＦ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2ＳｉＣＨ3（ＯＣＨ3）2
（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＦ2（ＯＣ2Ｆ4）p（ＯＣＦ2）qＯＣＦ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3
（ＣＨ3Ｏ）2ＣＨ3ＳｉＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＦ2（ＯＣ2Ｆ4）p（ＯＣＦ2）qＯＣＦ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2ＳｉＣＨ3（ＯＣＨ3）2
（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＣＦ2（ＯＣ2Ｆ4）p（ＯＣＦ2）qＯＣＦ2ＣＨ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3
（Ｃ2Ｈ5Ｏ）3ＳｉＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＦ2（ＯＣ2Ｆ4）p（ＯＣＦ2）qＯＣＦ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＯＣ2Ｈ5）3
一般式[２]の化合物は、１種単独でも２種以上を組合せても使用することができる。また、場合により、上記フッ素置換アルキル基含有有機ケイ素化合物とその部分加水分解縮合物とを組み合わせて使用することができる。
Specific examples of the fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula [2] include, for example, those represented by the following structural formula. However, it is not limited to the following illustration.
(CH 3 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 1 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 3
(CH 3 O) 2 CH 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 1 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 SiCH 3 (OCH 3 ) 2
(CH 3 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 3
(CH 3 O) 2 CH 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 CH 2 OCH 2 CH 2 CH 2 SiCH 3 (OCH 3 ) 2
(CH 3 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CH 2 CF 2 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 CH 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 3
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F 4) p (OCF 2) q OCF 2 CH 2 OCH 2 CH 2 CH 2 Si (OC 2 H 5) 3
The compound of general formula [2] can be used singly or in combination of two or more. Moreover, depending on the case, the said fluorine-substituted alkyl group containing organosilicon compound and its partial hydrolysis-condensation product can be used in combination.
一般式[２]で表されるフッ素置換アルキル基含有有機ケイ素化合物は、溶媒で希釈されたものを用いるとよい。使用できる溶媒としては、例えば、フッ素変性脂肪族炭化水素系溶剤（パーフルオロヘプタン、パーフルオロオクタン等）、フッ素変性芳香族炭化水素系溶剤（１，３−ジ（トリフルオロメチル）ベンゼン、トリフルオロメチルベンゼン等）、のフッ素変性エーテル系溶剤（メチルパーフルオロブチルエーテル、パーフルオロ（２−ブチルテトラヒドロフラン）等）、フッ素変性アルキルアミン系溶剤（パーフルオロトリブチルアミン、パーフルオロトリペンチルアミン等）、炭化水素系溶剤（石油ベンジン、ミネラルスピリッツ、トルエン、キシレン等）、ケトン系溶剤（アセトン、メチルエチルケトン、メチルイソブチルケトン等）、アルコール溶剤（メタノール、エタノール、イソプロパノール、ｎ−プロパノール等）等が挙げられる。これらは１種単独でも２種以上を組み合わせてもよい。これらのなかでも、変性シランの溶解性、濡れ性等の点で、フッ素変性された溶剤が好ましく、特に、１，３−ジ（トリフルオロメチル）ベンゼン、パーフルオロ（２−ブチルテトラヒドロフラン）、及びパーフルオロトリブチルアミンが好ましい。
（ａ）成分を撥水材料に添加することにより、耐摩耗性、洗浄剥離防止、撥水性向上という効果を撥水膜に付与することができる。
The fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula [2] may be diluted with a solvent. Examples of the solvent that can be used include fluorine-modified aliphatic hydrocarbon solvents (perfluoroheptane, perfluorooctane, etc.), fluorine-modified aromatic hydrocarbon solvents (1,3-di (trifluoromethyl) benzene, trifluoro Fluorine-modified ether solvents (methyl perfluorobutyl ether, perfluoro (2-butyltetrahydrofuran), etc.), fluorine-modified alkylamine solvents (perfluorotributylamine, perfluorotripentylamine, etc.), hydrocarbons Solvents (petroleum benzine, mineral spirits, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, isopropanol, n-propanol, etc.), etc. These may be used alone or in combination of two or more. Among these, a fluorine-modified solvent is preferable in terms of solubility, wettability, etc. of the modified silane, and in particular, 1,3-di (trifluoromethyl) benzene, perfluoro (2-butyltetrahydrofuran), and Perfluorotributylamine is preferred.
By adding the component (a) to the water-repellent material, it is possible to impart the effects of abrasion resistance, washing peeling prevention and water repellency to the water-repellent film.
（ｂ）成分：下記一般式[３−１]、[３−２] 及び[３−３]の中から選ばれた少なくとも一種のシラン化合物
一般式[３−１] Ｒ'−Ｓｉ(ＯＲ’’)3
一般式[３−２] Ｓｉ(ＯＲ’’)4
一般式[３−３] ＳｉＯ（ＯＲ’’）3Ｓｉ（ＯＲ’’）3
前記Ｒ'は有機基であり、炭素数１〜５０（好ましくは１〜１０）のアルキル基（メチル基、エチル基、プロピル基等）、エポキシエチル基、グリシジル基、アミノ基等が挙げられ、これらは置換されていても良い。
前記Ｒ’’は炭素数１〜４８のアルキル基（メチル基、エチル基、プロピル基等）であり、メチル基又はエチル基が好ましい。
一般式[３−１]〜[３−３]で表されるシラン化合物の具体例としては、例えば、構造式、（Ｃ2Ｈ5Ｏ）3ＳｉＣ3Ｈ6ＮＨ2、（ＣＨ3Ｏ）3ＳｉＣ3Ｈ6ＮＨ2、（Ｃ2Ｈ5Ｏ）4Ｓｉ、（Ｃ2Ｈ5Ｏ）3Ｓｉ-Ｏ-Ｓｉ（ＯＣ2Ｈ5）3等が挙げられる。但し、上記例示に限定されるものではない。
一般式[３−１]〜[３−３] の化合物は、１種単独でも２種以上を組合せても使用することができる。
（ｂ）成分のシラン化合物は、一般式[３−１]の化合物を単独あるいは他の成分より多く用いることがより好ましい。
（ｂ）成分を撥水材料に添加することにより、耐摩耗性、耐擦傷性という効果を撥水膜に付与することができる。
(B) Component: At least one silane compound selected from the following general formulas [3-1], [3-2] and [3-3] General formula [3-1] R′—Si (OR ′) ') 3
General formula [3-2] Si (OR ″) 4
Formula [3-3] SiO (OR ″) 3 Si (OR ″) 3
R ′ is an organic group, and examples thereof include an alkyl group having 1 to 50 (preferably 1 to 10) carbon atoms (methyl group, ethyl group, propyl group, etc.), epoxyethyl group, glycidyl group, amino group, and the like. These may be substituted.
R ″ is an alkyl group having 1 to 48 carbon atoms (methyl group, ethyl group, propyl group, etc.), preferably a methyl group or an ethyl group.
Specific examples of the silane compounds represented by the general formulas [3-1] to [3-3] include, for example, a structural formula, (C 2 H 5 O) 3 SiC 3 H 6 NH 2 , (CH 3 O). 3 SiC 3 H 6 NH 2 , (C 2 H 5 O) 4 Si, (C 2 H 5 O) 3 Si—O—Si (OC 2 H 5 ) 3 and the like. However, it is not limited to the above example.
The compounds of the general formulas [3-1] to [3-3] can be used singly or in combination of two or more.
As the silane compound (b), it is more preferable to use the compound of the general formula [3-1] alone or more than other components.
By adding the component (b) to the water repellent material, the effects of abrasion resistance and scratch resistance can be imparted to the water repellent film.
（ｃ）成分：両末端に加水分解基を有するアミノ変性ポリシロキサン
（ｃ）成分としては、例えば、下記式で表されるものが挙げられる。
商品例としては、例えば、ＫＦ８５７（信越化学工業（株）製：粘度６５ｍｍ2／ｓ（２５℃），比重０．９８，屈折率１．４１１，官能基当量７９０）等が挙げられる。
（ｃ）成分は、１種単独でも２種以上を組合せても使用することができる。
（ｃ）成分を撥水材料に添加することにより、形成される撥水膜に硬さを付与することができる。
Component (c): Amino-modified polysiloxane having hydrolyzable groups at both ends. Examples of the component (c) include those represented by the following formula.
As an example of goods, KF857 (Shin-Etsu Chemical Co., Ltd. product: viscosity 65mm < 2 > / s (25 degreeC), specific gravity 0.98, refractive index 1.411, functional group equivalent 790) etc. are mentioned, for example.
Component (c) can be used alone or in combination of two or more.
By adding the component (c) to the water repellent material, it is possible to impart hardness to the formed water repellent film.
（ｄ）成分：アミノ基と反応するエポキシ基含有シラン又はポリシロキサン
（ｄ）成分としては、例えば、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、２−（３,４エポキシシクロヘキシル）エチルトリメトキシシラン、２−（３,４エポキシシクロヘキシル）エチルトリエトキシシラン等が挙げられ、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピルメチルジエトキシシランが好ましい。
商品例としては、例えば、ＫＢＥ４０３（信越化学工業（株）製：３−グリシドキシプロピルトリエトキシシラン，分子量２７８．４）、ＳＩＬＱＵＥＳＴ ＷＥＴＬＩＮＫ ７８ ＳＩＬＡＮ（モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製：３−グリシドキシプロピルメチルジエトキシシラン、分子量２４８．４）等が挙げられる。
（ｄ）成分は、１種単独でも２種以上を組合せても使用することができる。
（ｄ）成分を撥水材料に添加することにより、形成される撥水膜に耐摩耗性、耐摩擦性を向上することができる。
本発明の撥水材料においては、（ａ）〜（ｄ）成分を、それぞれ独立に、０〜５０質量％含有すると好ましい。
Component (d): Epoxy group-containing silane or polysiloxane that reacts with amino groups Examples of component (d) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycid And xylpropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc. -Glycidoxypropyltriethoxysilane and 3-glycidoxypropylmethyldiethoxysilane are preferred.
Examples of products include, for example, KBE403 (manufactured by Shin-Etsu Chemical Co., Ltd .: 3-glycidoxypropyltriethoxysilane, molecular weight 278.4), SILQUEST WELINK 78 SILAN (manufactured by Momentive Performance Materials Japan GK: 3-glycidoxypropylmethyldiethoxysilane, molecular weight 248.4) and the like.
Component (d) can be used alone or in combination of two or more.
By adding the component (d) to the water repellent material, it is possible to improve the wear resistance and friction resistance of the water repellent film to be formed.
In the water-repellent material of the present invention, it is preferable that the components (a) to (d) are independently contained in an amount of 0 to 50% by mass.
上記一般式[１]の化合物及び（ａ）〜（ｄ）成分は、溶媒で希釈して用いても良く、一般式[２]で説明した溶媒に加え、下記一般式(IV)のハイドロフルオロエーテルが好ましく挙げられる。
一般式(IV)
ＣＦ3−(ＣＦ2)d−ＯＲ’’’
一般式(IV)式中、ｄは１〜５０の整数であり、Ｒ’’’はメチル基又はエチル基である。ｄは好ましくは１〜２０、より好ましくは１〜１０である。
一般式(IV) で表されるハイドロフルオロエーテルの具体例としては、例えば、下記化学式Ｃ4Ｆ9ＯＣＨ3、Ｃ4Ｆ9ＯＣ2Ｈ5、Ｃ6Ｆ13ＯＣＨ3、Ｃ6Ｆ13ＯＣ2Ｈ5等が挙げられる。但し、これらの例示に限定されるものではない。
一般式(IV)の化合物は、１種単独でも２種以上を組合せても使用することができる。
特に、一般式(IV)のハイドロフルオロエーテルは、他の成分とは反応せず、揮発性も高いので加熱することにより蒸発して、撥水材料に含まれる成分が固まることから好ましい。
また、前記撥水材料には、一般式(IV)のハイドロフルオロエーテル以外に、他の溶媒やケイ素非含有のパーフルオロポリエ−テル、そしてジテトラエトキシシラン（Ｓｉ2Ｏ（ＯＣ2Ｈ5）6、例えば、商品名ＫＢＥ３０２６（信越化学工業（株）社製））に代表されるジテトラアルコキシシラン、ポリテトラエトキシシラン（ＳｉnＯn-1（ＯＣ2Ｈ5）2n+2，ｎは２〜１０、例えば、商品名Ｓ４０（コルコート（株）社製））に代表されるポリテトラアルコキシシランを添加しても良い。
The compound of the above general formula [1] and the components (a) to (d) may be diluted with a solvent. In addition to the solvent described in the general formula [2], the hydrofluoro of the following general formula (IV) Ether is preferred.
Formula (IV)
CF 3- (CF 2 ) d -OR '''
In the general formula (IV), d is an integer of 1 to 50, and R ′ ″ is a methyl group or an ethyl group. d is preferably 1 to 20, more preferably 1 to 10.
Specific examples of the hydrofluoroether represented by the general formula (IV) include, for example, the following chemical formulas C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , C 6 F 13 OCH 3 , C 6 F 13 OC 2 H 5 and the like. However, it is not limited to these examples.
The compounds of the general formula (IV) can be used singly or in combination of two or more.
In particular, the hydrofluoroether of the general formula (IV) is preferable because it does not react with other components and has high volatility, so that it evaporates by heating and the components contained in the water repellent material solidify.
In addition to the hydrofluoroether of general formula (IV), the water-repellent material includes other solvents, silicon-free perfluoropolyether, and ditetraethoxysilane (Si 2 O (OC 2 H 5 )). 6 , for example, ditetraalkoxysilane represented by trade name KBE3026 (manufactured by Shin-Etsu Chemical Co., Ltd.), polytetraethoxysilane (Si n O n-1 (OC 2 H 5 ) 2n + 2 , n is You may add polytetraalkoxysilane represented by 2-10, for example, brand name S40 (made by Colcoat Co., Ltd.).
本発明の光学部材の製造方法は、前記撥水材料を用いて光学部材上に撥水膜を形成するものであって、形成する手段は特に限定されず、例えば、蒸着、浸漬等によればよい。 The method for producing an optical member of the present invention is to form a water repellent film on the optical member using the water repellent material, and the means for forming is not particularly limited. For example, according to vapor deposition, immersion, etc. Good.
本発明の撥水材料を蒸着法で撥水膜を形成する場合は、溶液状態で又は必要に応じて添加されるフッ素系溶媒、例えば一般式(IV)のハイドロフルオロエーテル、他の溶媒やケイ素非含有のパーフルオロポリエ−テルを混合した溶液の形態で用いられ、基材上に蒸着されると好ましい。これらの溶液はそのまま容器に入れて加熱しても良いが、均一した蒸着膜を多く得られるとの観点から、多孔性材料に含浸させることがより好ましく、多孔性材料としては、銅やステンレスなどの熱伝導性の高い金属粉末を焼結した焼結フィルターを用いることが好ましい。又、多孔性材料は、適度な蒸着速度を得るという観点からそのメッシュを４０〜２００ミクロン、好ましくは、８０〜１２０ミクロンとすることが適当である。
なお、溶液を容器に入れる場合や多孔性材料に含浸させる場合のいずれであっても、好ましくはフッ素系溶媒を加えた後に加熱して固めた形態で用いることが好ましい。固める際の温度は、撥水材料が分解しない温度内に設定し、好ましくは、５０〜１００℃、より好ましくは７０〜９０℃である。加熱時間は６０分以上が好ましく、より好ましくは６０〜１８０分である。加熱手段は、ドライオーブンなどが利用できる。
When forming the water repellent film by the vapor deposition method of the water repellent material of the present invention, a fluorine-based solvent added in a solution state or as necessary, for example, a hydrofluoroether of the general formula (IV), other solvents or silicon It is preferably used in the form of a mixed solution of non-containing perfluoropolyether and deposited on a substrate. These solutions may be put in a container and heated as they are, but it is more preferable to impregnate a porous material from the viewpoint that many uniform vapor-deposited films can be obtained. Examples of porous materials include copper and stainless steel. It is preferable to use a sintered filter obtained by sintering a metal powder having high thermal conductivity. The porous material has a mesh of 40 to 200 microns, preferably 80 to 120 microns, from the viewpoint of obtaining an appropriate deposition rate.
In addition, it is preferable to use it in the form which heated and solidified, after adding a fluorine-type solvent, even if it is any of the case where a solution is put into a container or a porous material is impregnated. The temperature at the time of solidification is set within a temperature at which the water-repellent material does not decompose, and is preferably 50 to 100 ° C, more preferably 70 to 90 ° C. The heating time is preferably 60 minutes or more, more preferably 60 to 180 minutes. As the heating means, a dry oven or the like can be used.
本発明の光学部材の製造方法を蒸着する場合には、前記撥水材料を、減圧下、加熱蒸着、（ハロゲンヒーター、抵抗過熱、電子銃等を使用）によって光学部材上に蒸着され、電子銃を用いて加熱して蒸着すると、精度の良い薄膜を成製することができる。その場合の真空蒸着装置内の真空度としては、特に限定はないが、均質の撥水膜を得るとの観点から、好ましくは、１．３３×１０-1Ｐａ〜１．３３×１０-6Ｐａ（１０-3〜１０-8Ｔｏｒｒ）、特に好ましくは、６．６６×１０-1Ｐａ〜８．００×１０-4Ｐａ（５．０×１０-3〜６．０×１０-6Ｔｏｒｒ）である。 When the method for producing an optical member of the present invention is vapor-deposited, the water repellent material is vapor-deposited on the optical member by heating vapor deposition (using a halogen heater, resistance overheating, an electron gun, etc.) under reduced pressure, and an electron gun When heated and vapor-deposited using, a highly accurate thin film can be formed. In this case, the degree of vacuum in the vacuum vapor deposition apparatus is not particularly limited, but preferably from 1.33 × 10 −1 Pa to 1.33 × 10 −6 from the viewpoint of obtaining a homogeneous water-repellent film. Pa (10 −3 to 10 −8 Torr), particularly preferably 6.66 × 10 −1 Pa to 8.00 × 10 −4 Pa (5.0 × 10 −3 to 6.0 × 10 −6 Torr) ).
撥水材料を加熱する際の具体的温度は、その種類、複数の材料の混合比、蒸着する真空条件により異なるが、所望の真空度における撥水材料の蒸着開始温度以上から分解温度を超えない範囲で行うことが好ましい。蒸着開始温度は２００℃〜５５０℃、分解温度は２５０℃〜６００℃の範囲内にくるのが通常であるがこの限りではない。ここで蒸着開始温度とは前記撥水材料を含む溶液の蒸気圧が真空度と等しくなったときの温度をいい、また、前記撥水材料の分解温度とは１分間に前記撥水材料の５０質量％が分解する温度（窒素雰囲気下、該化合物と反応性のある物質が存在しない条件で）をいう。 The specific temperature when heating the water-repellent material varies depending on the type, the mixing ratio of a plurality of materials, and the vacuum conditions for vapor deposition, but does not exceed the decomposition temperature from the temperature above the deposition start temperature of the water-repellent material at the desired degree of vacuum. It is preferable to carry out within a range. Usually, the deposition start temperature is 200 ° C. to 550 ° C., and the decomposition temperature is 250 ° C. to 600 ° C. Here, the deposition start temperature refers to the temperature at which the vapor pressure of the solution containing the water repellent material becomes equal to the degree of vacuum, and the decomposition temperature of the water repellent material refers to 50% of the water repellent material per minute. The temperature at which mass% decomposes (under a condition in which no substance reactive with the compound exists in a nitrogen atmosphere).
蒸着速度は、加熱方法により異なるが、電子銃使用の場合、上記温度範囲に保つことを条件に、前記撥水材料加熱開始から蒸着を完結させるまでの時間を１２０秒以内とすることが好ましく、さらには５０秒以内、４０秒以内、３０秒以内とすることが好ましい。上記加熱温度範囲で、且つ短時間で蒸着を完結させること、即ち、前記撥水材料に短時間で高エネルギ−を与えることにより、耐久性に優れた撥水膜を有する光学部材を提供することができる。また、蒸着開始温度が多少異なる複数成分の撥水材料を用いても、蒸発開始温度の高い原料の蒸発開始温度から分解温度の低い原料の分解温度の範囲で蒸着温度を選択することにより、ほぼ同時に蒸着でき、均一な膜を得ることができる。 Although the deposition rate varies depending on the heating method, in the case of using an electron gun, it is preferable that the time from the start of heating the water-repellent material to the completion of deposition is within 120 seconds, provided that the temperature range is maintained. Furthermore, it is preferable to set it within 50 seconds, within 40 seconds, and within 30 seconds. Providing an optical member having a water-repellent film excellent in durability by completing vapor deposition within the heating temperature range in a short time, that is, by giving high energy to the water-repellent material in a short time. Can do. In addition, even when using a water repellent material having a plurality of components with slightly different deposition start temperatures, by selecting the deposition temperature within the range from the evaporation start temperature of the raw material with a high evaporation start temperature to the decomposition temperature of the raw material with a low decomposition temperature, Vapor deposition can be performed simultaneously and a uniform film can be obtained.
前記蒸着速度を達成する方法としては、前記有機ケイ素化合物に電子ビ−ムを照射する方法が好ましく用いられ、電子ビ−ムを発生する方法は、従来、蒸着装置で用いられている電子銃を用いることができる。電子銃を用いれば、前記撥水材料全体に、均一のエネルギ−を照射することができ均一な撥水膜を施しやすくなる。電子銃のパワーについては、使用物質、蒸着装置、真空度、照射面積によって異なるが、好ましい条件は、加速電圧が６ｋＶ前後で、印加電流５〜４０ｍＡ程度である。 As a method for achieving the vapor deposition rate, a method of irradiating the organosilicon compound with an electron beam is preferably used, and a method of generating an electron beam uses an electron gun conventionally used in a vapor deposition apparatus. Can be used. If an electron gun is used, the entire water repellent material can be irradiated with uniform energy, and a uniform water repellent film can be easily applied. The power of the electron gun varies depending on the substance used, the vapor deposition apparatus, the degree of vacuum, and the irradiation area, but preferable conditions are an acceleration voltage of about 6 kV and an applied current of about 5 to 40 mA.
また、本発明の撥水材料を浸漬法で撥水膜を形成する場合にも、蒸着法同様に溶液の形態で用いられ、基材上に浸漬されると好ましい。
その際、光学部材を、溶液とした前記撥水材料に、引き上げ速度５０〜１０００ｍｍ／分（好ましくは、１００〜５００ｍｍ／分）で、５〜６０秒間浸漬すると好ましく、その後、加熱（例えば４５〜６０℃で２時間）すると好ましい。
Further, when the water repellent material of the present invention is formed by a dipping method, it is preferably used in the form of a solution as in the vapor deposition method and dipped on a substrate.
At that time, the optical member is preferably immersed in the water-repellent material as a solution at a lifting speed of 50 to 1000 mm / min (preferably 100 to 500 mm / min) for 5 to 60 seconds, and then heated (for example, 45 to 45 mm / min). 2 hours at 60 ° C.).
本発明の撥水材料によって形成される撥水膜の厚さは、特に限定されないが１〜２０ｎｍであると好ましい。また、屈折率も特に限定されないが、１．４２０ 〜１．４８０であると好ましい。
本発明における光学部材としては、例えば、眼鏡レンズ、カメラレンズ、ワードプロセッサーのディスプレー等に付設する光学フィルター、自動車の窓ガラス等が挙げられ、特にプラスチックレンズ、中でも眼鏡用プラスチックレンズに適している。
本発明に用いる光学部材の材質としては、メチルメタクリレート単独重合体、メチルメタクリレートと１種以上の他のモノマーとをモノマー成分とする共重合体、ジエチレングリコールビスアリルカーボネート単独重合体、ジエチレングリコールビスアリルカーボネートと１種以上の他のモノマーとをモノマー成分とする共重合体、イオウ含有共重合体、ハロゲン含有共重合体、ポリカーボネート、ポリスチレン、ポリ塩化ビニル、不飽和ポリエステル、ポリエチレンテレフタレート、ポリウレタンなどのプラスチック製光学基板、あるいは無機ガラス製光学基板などが挙げられる。尚、上記基板は基板上にハードコート層を有するものであってもよい。ハードコート層としては、有機ケイ素化合物、アクリル化合物等を含んだ硬化膜を例示できる。
The thickness of the water repellent film formed by the water repellent material of the present invention is not particularly limited, but is preferably 1 to 20 nm. The refractive index is not particularly limited, but is preferably 1.420 to 1.480.
Examples of the optical member in the present invention include an eyeglass lens, a camera lens, an optical filter attached to a display of a word processor, an automobile window glass, and the like, and are particularly suitable for a plastic lens, particularly a plastic lens for eyeglasses.
As the material of the optical member used in the present invention, methyl methacrylate homopolymer, copolymer having methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bisallyl carbonate, Plastic optics such as copolymers containing one or more other monomers as monomer components, sulfur-containing copolymers, halogen-containing copolymers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, etc. Examples of the substrate include an optical substrate made of inorganic glass. The substrate may have a hard coat layer on the substrate. Examples of the hard coat layer include a cured film containing an organosilicon compound, an acrylic compound, and the like.
また、反射防止膜（蒸着膜）とは、例えばレンズ等の光学基板表面の反射を減少させるために設けられた ＺｒＯ2、ＳｉＯ2、ＴｉＯ2、Ｔａ2Ｏ5、Ｙ2Ｏ3、ＭｇＦ2、Ａｌ2Ｏ3などから形成される単層または多層膜（但し、最外層にＳｉＯ2膜を有することが好ましい）またはＣｒＯ2などの着色膜（但し、最外層にＳｉＯ2膜を有することが好ましい）を言う。本発明においては、反射防止膜の最外層に二酸化ケイ素を主成分とする層が用いられることが好ましい。ここで二酸化ケイ素を主成分とするとは、実質的に二酸化ケイ素からなる層、あるいは二酸化ケイ素、酸化アルミニウム及び有機化合物からなるハイブリッド層をいう。なお、反射防止膜は真空蒸着法によって作成されることが好ましい。 The antireflection film (deposited film) is, for example, ZrO 2 , SiO 2 , TiO 2 , Ta 2 O 5 , Y 2 O 3 , MgF 2 provided to reduce reflection on the surface of an optical substrate such as a lens. A single layer or a multilayer film formed of Al 2 O 3 or the like (however, it is preferable to have a SiO 2 film as the outermost layer) or a colored film such as CrO 2 (however, it may have a SiO 2 film as the outermost layer) Say). In the present invention, it is preferable to use a layer mainly composed of silicon dioxide as the outermost layer of the antireflection film. Here, silicon dioxide as a main component means a layer substantially composed of silicon dioxide or a hybrid layer composed of silicon dioxide, aluminum oxide and an organic compound. The antireflection film is preferably formed by a vacuum deposition method.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
１．反射防止膜付プラスチックレンズの作成
プラスチックレンズとして、ジエチレングリコールビスアリルカーボネート重合体系レンズ（ＨＯＹＡ（株）製Ｈｉ−Ｌｕｘ（商品名）、屈折率１．４９９、度数０．００）を用い、かかるプラスチックレンズ基材上に、特開昭６３−１０６４０号公報に開示されている硬化膜を施した。具体的には、ＳｉＯ2濃度４０％のコロイダルシリカ（スノーテッ
クス−４０、水分散シリカ、日産化学（株）製）２４０質量部に、０．５Ｎ塩酸２．０質量部、酢酸２０質量部を加えた溶液を、３５℃にして攪拌しながら、γ−グリシドキシプロピルトリメトキシシラン（３官能有機ケイ素化合物）９５質量部を滴下し、室温にて８時間攪拌し、室温にて１６時間放置した。この加水分解溶液に、メチルセロソルブ８０質量部、イソプロピルアルコール１２０質量部、ブチルアルコール４０質量部、アルミニウムアセチルアセトン１６質量部、シリコーン系界面活性剤（ＦＺ−７００６（商品名）、東レ・ダウコーニング（株）製）０．２質量部を加えて、８時間攪拌後、室温にて２４時間熟成させコーティング組成物を得た。該組成物を、引き上げ速度１５ｃｍ／ｍｉｎで浸漬法により塗布、室温にて１５分放置後、１２０℃で２時間加熱硬化して硬化膜を施した。
次に、前記硬化膜上に真空蒸着法（真空度２．６７×１０‐3Ｐａ（２×１０-5Ｔｏｒ
ｒ））により、二酸化ケイ素からなる下地層〔屈折率１．４６、膜厚０．５λ（λは５５０ｎｍである）〕を形成し、該下地層の上に、プラスチックレンズに酸素イオンビームを照射するイオンビームアシスト法で得られる二酸化チタンからなる層（膜厚０．０６λ）、真空蒸着法で得られる二酸化ケイ素からなる層（膜厚０．１２λ）、さらにイオンビームアシスト法で得られる二酸化チタンからなる層（膜厚０．０６λ）よりなる３層等価膜である第１層〔屈折率１．７０、膜厚０．２４λ〕を形成した。この第１層の上に、イオンビームアシスト法により二酸化チタンからなる第２層（屈折率２．４０、膜厚０．５λ）を形成し、該第２層の上に、真空蒸着法（真空度２．６７×１０‐3Ｐａ（２×１０-5
Ｔｏｒｒ））により二酸化ケイ素からなる第３層〔屈折率１．４６、膜厚０．２５λ〕を形成して、反射防止膜付きプラスチックレンズを得た。このレンズの視感反射率は０．４％であった。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
1. Preparation of plastic lens with antireflection film As a plastic lens, a diethylene glycol bisallyl carbonate polymer lens (Hi-Lux (trade name) manufactured by HOYA, refractive index 1.499, power 0.00) is used. A cured film disclosed in JP-A-63-1640 was applied on the substrate. Specifically, 240 parts by mass of colloidal silica having a SiO 2 concentration of 40% (Snowtex-40, water-dispersed silica, manufactured by Nissan Chemical Co., Ltd.) is added with 2.0 parts by mass of 0.5N hydrochloric acid and 20 parts by mass of acetic acid. While stirring the added solution at 35 ° C., 95 parts by mass of γ-glycidoxypropyltrimethoxysilane (trifunctional organosilicon compound) was added dropwise, stirred at room temperature for 8 hours, and allowed to stand at room temperature for 16 hours. did. In this hydrolyzed solution, 80 parts by mass of methyl cellosolve, 120 parts by mass of isopropyl alcohol, 40 parts by mass of butyl alcohol, 16 parts by mass of aluminum acetylacetone, silicone surfactant (FZ-7006 (trade name), Toray Dow Corning Co., Ltd. ) Product) 0.2 parts by mass was added, stirred for 8 hours, and then aged at room temperature for 24 hours to obtain a coating composition. The composition was applied by a dipping method at a lifting speed of 15 cm / min, allowed to stand at room temperature for 15 minutes, and then cured by heating at 120 ° C. for 2 hours to give a cured film.
Next, a vacuum deposition method (vacuum degree: 2.67 × 10 −3 Pa (2 × 10 −5 Tor) is applied on the cured film.
r)), a base layer made of silicon dioxide (refractive index 1.46, film thickness 0.5λ (λ is 550 nm)) is formed, and a plastic lens is irradiated with an oxygen ion beam on the base layer. A layer made of titanium dioxide (film thickness 0.06λ) obtained by an ion beam assist method, a layer made of silicon dioxide (film thickness 0.12λ) obtained by a vacuum deposition method, and a titanium dioxide obtained by an ion beam assist method A first layer (refractive index: 1.70, film thickness: 0.24λ), which is a three-layer equivalent film made of a layer made of (film thickness: 0.06λ), was formed. A second layer made of titanium dioxide (refractive index 2.40, film thickness 0.5λ) is formed on the first layer by an ion beam assist method, and a vacuum deposition method (vacuum) is formed on the second layer. Degree 2.67 × 10 −3 Pa (2 × 10 −5
A third layer made of silicon dioxide (refractive index 1.46, film thickness 0.25λ) was formed by Torr)) to obtain a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%.
２．物性評価
本実施例及び比較例で得られたプラスチックレンズは以下に示す評価方法により諸物性を評価した。
（１）水に対する静止接触角
接触角計（協和界面科学（株）製品、ＣＡ−Ｄ型）を使用し、２５℃において直径２ｍｍの水滴を針先に作り、これをレンズの凸面の最上部に触れさせて、液滴を作った。この時に生ずる液滴と面との角度を測定し静止接触角とした。静止接触角θは水滴の半径（水滴がレンズ表面に接触している部分の半径）をｒとし、水滴の高さをｈとしたときに、以下の式で求められる。
θ＝２×ｔａｎ‐1（ｈ／ｒ）
なお、静止接触角の測定は水の蒸発による測定誤差を最小限にするために水滴をレンズに触れさせた後１０秒以内に行った。
（２）外観
目視にて干渉色の色ムラ及び干渉色変化があるかどうかを調べ、眼鏡レンズとして使用できる外観かどうか評価した。
（３）耐久性
レンズクリーニング布(商品名:HOYA Clearcloth)で５００ｇの荷重をかけて撥水膜を有するプラスチックレンズ表面を３６００回、前後に擦り（２５℃、相対湿度５０〜６０％）、その後（１）に記載した方法で水に対する静止接触角を測定した。
（４）耐摩耗性
新東科学（株）製往復摩擦磨耗試験機にて、撥水膜を有するプラスチックレ ンズ表面に、荷重４kg、砂消しゴム５０往復摩耗テストを実施し、村上色彩製 ヘーズメーターＭＨ−１５０にてヘーズ値を測定、ヘーズ値の変化を測定した 。
（使用砂消しゴム、ライオン ギャザ半砂）
（５）動摩擦係数
新東科学（株）製の連続加重式表面性測定機ＴＹＰＥ：２２Ｈを使用し、移動距離２０ｍｍの平均動摩擦係数を各々３回測定し、平均値を出した。
2. Evaluation of physical properties The plastic lenses obtained in the examples and comparative examples were evaluated for various physical properties by the following evaluation methods.
(1) Static contact angle for water Using a contact angle meter (product of Kyowa Interface Science Co., Ltd., CA-D type), a water drop with a diameter of 2 mm is made on the needle tip at 25 ° C., and this is the top of the convex surface of the lens. To make a droplet. The angle between the droplet and the surface generated at this time was measured to obtain a static contact angle. The static contact angle θ can be obtained by the following equation, where r is the radius of the water droplet (the radius of the portion where the water droplet is in contact with the lens surface) and h is the height of the water droplet.
θ = 2 × tan− 1 (h / r)
The measurement of the static contact angle was performed within 10 seconds after the water droplet touched the lens in order to minimize the measurement error due to water evaporation.
(2) Appearance Visual inspection was conducted to determine whether there was any interference color unevenness and interference color change, and to evaluate whether the appearance could be used as a spectacle lens.
(3) Durability With a lens cleaning cloth (trade name: HOYA Clearcloth), rub the plastic lens surface with a water repellent film 3600 times back and forth with a load of 500 g (25 ° C., relative humidity 50-60%), then The static contact angle with respect to water was measured by the method described in (1).
(4) Abrasion resistance Using a reciprocating friction and abrasion tester manufactured by Shinto Kagaku Co., Ltd., a plastic lens surface with a water-repellent film was subjected to a reciprocating abrasion test with a load of 4 kg and sand eraser 50. The haze value was measured with MH-150, and the change in haze value was measured.
(Used sand eraser, Lion Gaza half sand)
(5) Coefficient of dynamic friction Using a continuous load type surface property measuring machine TYPE: 22H manufactured by Shinto Kagaku Co., Ltd., the average coefficient of dynamic friction at a moving distance of 20 mm was measured three times, and an average value was obtained.
製造例１：混合撥水剤−１の調製
前記（ｃ）成分としてＫＦ８５７（商品名：信越化学工業（株）製）４gと(ｄ)成分としてＫＢＥ４０３（商品名：信越化学工業（株）製）１gを、混合し２４時間攪拌し、混合物−１を５g得た。
前記混合物−１全量に、前記（ｂ）成分としてＫＢＥ９０３（商品名：信越化学工業（株）製）５ｇを混合し、２４時間攪拌して、混合物−２を１０g得た。
一般式[１]で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランとして下記化合物（１）５ｇに、前記混合物−２を１ｇ混合し、さらに、希釈剤としてＨＦＥ７２００（住友３Ｍ（株）製）を３ｇ混合、１時間攪拌を行い、混合撥水剤−１を得た。
Production Example 1: Preparation of Mixed Water Repellent Agent-1 As the component (c), 4 g of KF857 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) and KBE403 (product name: manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (d) ) 1 g was mixed and stirred for 24 hours to obtain 5 g of mixture-1.
5 g of KBE903 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (b) was mixed with the total amount of the mixture-1 and stirred for 24 hours to obtain 10 g of the mixture-2.
As a perfluoropolyether-polysiloxane copolymer-modified silane represented by the general formula [1], 1 g of the mixture-2 is mixed with 5 g of the following compound (1), and further, HFE7200 (Sumitomo 3M Co., Ltd.) is used as a diluent. 3 g) was mixed and stirred for 1 hour to obtain a mixed water repellent-1.
化合物（１）
Ａ−Ｏ−ＣＨ2ＣＨ2ＣＨ2−Ｒｇ−ＣＨ2−Ｏ−ＣＨ2ＣＨ2ＣＨ2−Ｓｉ（ＣＨ3）2−Ｏ−（Ｓｉ（ＣＨ3）2−Ｏ）50−Ｓｉ（ＣＨ3）2−ＣＨ2ＣＨ2ＣＨ2−Ｏ−ＣＨ2−Ｒｇ−ＣＨ2ＣＨ2ＣＨ2−Ｏ−Ａ
Ｒｇ： −ＣＦ2（ＯＣ2Ｆ4）p（ＯＣＦ2）qＯＣＦ2−
Ａ ： −ＣＨ2ＣＨ2ＣＨ2−Ｓｉ（ＣＨ3）2−Ｏ−Ｓｉ（ＣＨ3）2−ＣＨ2ＣＨ2ＣＨ2−Ｓｉ−ＣＨ3（ＯＣＨ3）2
（式中、ｐ＝１５、ｑ＝１５、繰り返し単位（ＯＣ2Ｆ4）及び（ＯＣＦ2）の配列はランダムである。）
Compound (1)
A-O-CH 2 CH 2 CH 2 -Rg-CH 2 -O-CH 2 CH 2 CH 2 -Si (CH 3) 2 -O- (Si (CH 3) 2 -O) 50 -Si (CH 3 ) 2 —CH 2 CH 2 CH 2 —O—CH 2 —Rg—CH 2 CH 2 CH 2 —OA
Rg: —CF 2 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 —
A: -CH 2 CH 2 CH 2 -Si (CH 3) 2 -O-Si (CH 3) 2 -CH 2 CH 2 CH 2 -Si-CH 3 (OCH 3) 2
(In the formula, p = 15, q = 15, and the arrangement of the repeating units (OC 2 F 4 ) and (OCF 2 ) is random.)
製造例２：混合撥水剤−２の調製
前記（ｃ）成分としてＫＦ８００１（商品名：信越化学工業（株）製）４gと(ｄ)成分としてＫＢＥ４０２（商品名：信越化学工業（株）製）１gを、混合し２４時間攪拌し、混合物−３を５g得た。
前記混合物−３全量に、前記（ｂ）成分としてＫＢＥ９０３（商品名：信越化学工業（株）製）５ｇを混合し、２４時間攪拌して、混合物−４を１０g得た。
一般式[１]で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランとして下記化合物（１）５ｇに、前記混合物−４を１ｇ混合し、さらに、希釈剤としてＨＦＥ７２００（住友３Ｍ（株）製）を３ｇ混合、１時間攪拌を行い、混合撥水剤−２を得た。
Production Example 2: Preparation of mixed water repellent-2 KF8001 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) 4 g as component (c) and KBE402 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) as component (d) ) 1 g was mixed and stirred for 24 hours to obtain 5 g of mixture-3.
5 g of KBE903 (trade name: manufactured by Shin-Etsu Chemical Co., Ltd.) as the component (b) was mixed with the total amount of the mixture-3 and stirred for 24 hours to obtain 10 g of the mixture-4.
As a perfluoropolyether-polysiloxane copolymer modified silane represented by the general formula [1], 1 g of the mixture-4 is mixed with 5 g of the following compound (1), and further, HFE7200 (Sumitomo 3M Co., Ltd.) is used as a diluent. 3 g) was mixed and stirred for 1 hour to obtain a mixed water repellent-2.
比較製造例１：混合撥水剤−３の調製
製造例１において、化合物（１）の代わりに、一般式[２]で示されるフッ素置換アルキル基含有有機ケイ素化合物として、以下の構造を有する化合物（２）を用いた以外は同様にして、混合撥水剤−３を得た。
化合物（２）
（ＣＨ3Ｏ）3ＳｉＣＨ2ＣＨ2ＣＨ2ＯＣＨ2ＣＦ2（ＯＣ2Ｆ4）p（ＯＣＦ2）qＯＣＦ2ＣＨ2ＯＣＨ2ＣＨ2ＣＨ2Ｓｉ（ＯＣＨ3）3
（式中、ｐ＝２２、ｑ＝２２、繰り返し単位（ＯＣ2Ｆ4）及び（ＯＣＦ2）の配列はランダムである。）
Comparative Production Example 1: Preparation of Mixed Water Repellent-3 In Production Example 1, a compound having the following structure as a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula [2] instead of compound (1) A mixed water repellent-3 was obtained in the same manner except that (2) was used.
Compound (2)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 OCH 2 CF 2 (OC 2 F 4 ) p (OCF 2 ) q OCF 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 3
(In the formula, p = 22, q = 22, and the arrangement of the repeating units (OC 2 F 4 ) and (OCF 2 ) is random.)
実施例１
前記混合撥水剤−１を０．３ｍｌしみ込ませたステンレス製焼結フィルター（細孔径８０〜１００μｍ、直径１８ｍｍφ、厚さ３ｍｍ）を８０℃で２時間ドライオーブン加熱し、その後、真空蒸着装置内にセットした。以下の条件で電子銃（ＥＢ）を用いて焼結フィルター全体を加熱して、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
(1)真空度：３．１×１０-4〜８．０×１０-4Ｐａ（２．３×１０-6〜６．０×１０-6Ｔｏｒｒ）
(2)電子銃の条件
加速電圧：６ｋＶ、印加電流：１１ｍＡ、照射面積：３．５×３．５ｃｍ2、蒸着時間：１２０秒
Example 1
A stainless sintered filter (pore diameter 80-100 μm, diameter 18 mmφ, thickness 3 mm) impregnated with 0.3 ml of the mixed water repellent agent-1 was heated in a dry oven at 80 ° C. for 2 hours, and then in a vacuum deposition apparatus Set. 1. Heat the entire sintered filter using an electron gun (EB) under the following conditions: A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
(1) Degree of vacuum: 3.1 × 10 −4 to 8.0 × 10 −4 Pa (2.3 × 10 −6 to 6.0 × 10 −6 Torr)
(2) Electron gun conditions Acceleration voltage: 6 kV, applied current: 11 mA, irradiation area: 3.5 × 3.5 cm 2 , deposition time: 120 seconds
実施例２
前記混合撥水剤−１を０．３ｍｌしみ込ませたステンレス製焼結フィルター（細孔径８０〜１００μｍ、直径１８ｍｍφ、厚さ３ｍｍ）を８０℃で２時間ドライオーブン加熱し、その後、真空蒸着装置内にセットした。ハロゲンヒーターにて７００℃まで４分で上昇させ、さらに７００℃から８５０℃まで４分で上昇させ、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
Example 2
A stainless sintered filter (pore diameter 80-100 μm, diameter 18 mmφ, thickness 3 mm) impregnated with 0.3 ml of the mixed water repellent agent-1 was heated in a dry oven at 80 ° C. for 2 hours, and then in a vacuum deposition apparatus Set. Increase with a halogen heater to 700 ° C. in 4 minutes, and further increase from 700 ° C. to 850 ° C. in 4 minutes. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
実施例３
実施例１において、前記混合撥水剤−１の代わりに前記混合撥水剤−２を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
実施例４
実施例２において、前記混合撥水剤−１の代わりに前記混合撥水剤−２を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
Example 3
In Example 1, the same procedure was performed except that the mixed water repellent agent-2 was used instead of the mixed water repellent agent-1. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
Example 4
In Example 2, the same procedure was performed except that the mixed water repellent-2 was used instead of the mixed water repellent-1. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
比較例１
実施例１において、前記混合撥水剤−１の代わりに、一般式[１]で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランとして上記化合物（１）を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
比較例２
実施例２において、前記混合撥水剤−１の代わりに、一般式[１]で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランとして上記化合物（１）を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
Comparative Example 1
In Example 1, it replaced with the said mixed water repellent--1, and except having used the said compound (1) as a perfluoropolyether-polysiloxane copolymer modified silane shown by General formula [1], it is the same. 1. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
Comparative Example 2
In Example 2, in place of the mixed water repellent-1, the above compound (1) was used in the same manner as the perfluoropolyether-polysiloxane copolymer-modified silane represented by the general formula [1]. 1. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
比較例３
実施例１において、前記混合撥水剤−１の代わりに、一般式[２]で示されるフッ素置換アルキル基含有有機ケイ素化合物である化合物（２）を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
比較例４
実施例２において、前記混合撥水剤−１の代わりに、一般式[２]で示されるフッ素置換アルキル基含有有機ケイ素化合物である化合物（２）を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
比較例５
実施例１において、前記混合撥水剤−１の代わりに、前記混合撥水剤−２を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
比較例６
実施例２において、前記混合撥水剤−１の代わりに、前記混合撥水剤−２を用いた以外は同様にして、１．の反射防止膜付プラスチックレンズに撥水膜を形成した。このレンズの視感反射率は０．４％であった。上記（１）〜（５）の評価結果を表１に示す。
Comparative Example 3
In Example 1, in place of the mixed water repellent-1, compound (2) which is a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula [2] was used in the same manner. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
Comparative Example 4
In Example 2, instead of the mixed water repellent-1, compound (2) which is a fluorine-substituted alkyl group-containing organosilicon compound represented by the general formula [2] was used. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
Comparative Example 5
In Example 1, the same procedure was performed except that the mixed water repellent agent-2 was used instead of the mixed water repellent agent-1. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
Comparative Example 6
In Example 2, the same procedure was performed except that the mixed water repellent-2 was used instead of the mixed water repellent-1. A water repellent film was formed on a plastic lens with an antireflection film. The luminous reflectance of this lens was 0.4%. The evaluation results of the above (1) to (5) are shown in Table 1.
表１に示したように、一般式[１]で示されるパーフルオロポリエーテル−ポリシロキサン共重合体変性シランを含む混合撥水処理剤は、動摩擦係数を損なわず、耐摩耗性の向上が可能である。 As shown in Table 1, the mixed water repellent containing the perfluoropolyether-polysiloxane copolymer-modified silane represented by the general formula [1] can improve the wear resistance without impairing the dynamic friction coefficient. It is.
本発明の撥水材料を用いると、耐摩擦性及び耐摩耗性を有し、傷がつきにくく、防汚性が高く、寿命が長い、撥水及び撥油性を有する撥水膜が形成でき、眼鏡レンズ、カメラレンズ、パーソナルコンピュータのディスプレー等に付設する光学フィルター、自動車の窓ガラス等の光学部材に適用することができ、特に眼鏡用プラスチックレンズに適している。 Using the water-repellent material of the present invention, it is possible to form a water-repellent film having water and oil repellency, which has friction resistance and wear resistance, is hardly scratched, has high antifouling properties, has a long life, The present invention can be applied to optical members such as eyeglass lenses, camera lenses, optical filters attached to displays of personal computers, and window glass of automobiles, and is particularly suitable for plastic lenses for eyeglasses.
Claims (7)
（ａ）下記一般式[２]で示されるフッ素置換アルキル基含有有機ケイ素化合物、（ｂ）下記一般式[３−１]、[３−２] 及び[３−３]の中から選ばれた少なくとも一種のシラン化合物、（ｃ）両末端に加水分解基を有するアミノ変性ポリシロキサン、及び（ｄ）アミノ基と反応するエポキシ基含有シラン又はポリシロキサンから選ばれる少なくとも一種とを含む撥水材料。
一般式[１]
（ａ）成分
一般式[２]
（ｂ）成分
一般式[３−１] Ｒ'−Ｓｉ(ＯＲ’’)3
一般式[３−２] Ｓｉ(ＯＲ’’)4
一般式[３−３] ＳｉＯ（ＯＲ’’）3Ｓｉ（ＯＲ’’）3
（式中、Ｒ'は有機基であり、Ｒ’’はアルキル基である。） A perfluoropolyether-polysiloxane copolymer-modified silane represented by the following general formula [1]:
(A) a fluorine-substituted alkyl group-containing organosilicon compound represented by the following general formula [2], (b) selected from the following general formulas [3-1], [3-2] and [3-3] A water repellent material comprising at least one silane compound, (c) an amino-modified polysiloxane having hydrolyzable groups at both ends, and (d) at least one selected from an epoxy group-containing silane or polysiloxane that reacts with an amino group.
General formula [1]
(A) Component general formula [2]
(B) Component General Formula [3-1] R′—Si (OR ″) 3
General formula [3-2] Si (OR ″) 4
Formula [3-3] SiO (OR ″) 3 Si (OR ″) 3
(In the formula, R ′ is an organic group, and R ″ is an alkyl group.)
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| WO2019088116A1 (en) * | 2017-10-31 | 2019-05-09 | ダイキン工業株式会社 | Surface treatment composition |
| JPWO2019088116A1 (en) * | 2017-10-31 | 2020-05-28 | ダイキン工業株式会社 | Surface treatment composition |
| JP2021165409A (en) * | 2017-10-31 | 2021-10-14 | ダイキン工業株式会社 | Surface treatment composition |
| KR102426281B1 (en) * | 2017-10-31 | 2022-07-29 | 다이킨 고교 가부시키가이샤 | surface treatment composition |
| US11681079B2 (en) | 2017-10-31 | 2023-06-20 | Daikin Industries, Ltd. | Surface treatment composition |
| JP7339555B2 (en) | 2017-10-31 | 2023-09-06 | ダイキン工業株式会社 | surface treatment composition |
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