JP4593949B2 - Manufacturing method of optical member - Google Patents

Description

  The present invention relates to a method for producing an optical member having an antireflection film, and in particular, it has not only an excellent antireflection film having low reflectance and high transmittance, but also heat resistance and resistance on a plastic substrate. The present invention relates to a method for manufacturing an optical member having an antireflection film that is excellent in wear and productivity.

  2. Description of the Related Art Conventionally, there has been known an optical member in which an antireflection film formed by depositing an inorganic substance on a plastic substrate is provided. In addition, as an optical member having an antireflection film having good impact resistance, heat resistance, and wear resistance, Patent Document 1 discloses a plastic substrate and an optical member having an antireflection film formed by vacuum deposition. A technique using a hybrid layer in which at least one layer in an antireflection film is made of an inorganic substance and an organic substance is disclosed. In the technique disclosed in Patent Document 1, it is desirable to precisely control the film thickness of the hybrid film, in particular, the amount of the organic compound, but there has been a demand for a method for more easily manufacturing. In addition, there has been a demand for a proposal of an optical member with further improved wear resistance.

Japanese Patent Laid-Open No. 2003-202407

  An object of the present invention is to provide an optical member manufacturing method for manufacturing an optical member having an antireflection film excellent in wear resistance with high productivity under the above-described circumstances.

一般式（ｂ）：シラザン化合物

一般式（ｃ）：シクロシロキサン化合物

一般式（ｄ）：シクロシラザン化合物

[一般式（ａ）〜（ｄ）において、式中のｍ、ｎは、それぞれ独立に０以上の整数を表す。また、X₁〜X₈はそれぞれ独立に、水素、炭素数1〜6の炭化水素基（飽和・不飽和双方を含む）、−OR¹基、−CH₂OR²基、−COOR³基、−OCOR⁴基、−SR⁵基、−CH₂SR⁶基、−NR⁷ ₂基、または、−CH₂NR⁸ ₂基(R¹〜R⁸は水素または炭素数1〜6の炭化水素基（炭素原子間の結合において飽和・不飽和双方を含む）)を表す。｝
また、前記ケイ素非含有有機化合物が、以下の一般式（e）〜（g）で表されるいずれかの構造を有している。
一般式（e）：片末端にエポキシ基を有する炭素及び水素を必須成分とするケイ素非含有有機化合物

一般式（f）：両末端にエポキシ基を有する炭素及び水素を必須成分とするケイ素非含有有機化合物

一般式（g）：不飽和結合を含む、炭素及び水素を必須成分とするケイ素非含有有機化合物
ＣＸ₉Ｘ₁₀＝ＣＸ₁₁Ｘ₁₂ ・・・（ｇ）
（一般式（e）、（f）において、Ｒ⁹は水素、または酸素を含んでいてもよい炭素数1〜10の炭化水素基、Ｒ¹⁰ は、酸素を含んでいてもよい炭素数1〜7の二価の炭化水素基を表す。一般式（g）において、Ｘ₉〜Ｘ₁₂、はそれぞれ独立に水素、炭素数1〜10の炭化水素基、または炭素数1〜10の炭素、水素を必須成分とし、さらに酸素及び窒素の少なくとも一方を必須成分とする有機基を表す。）]
[前記反射防止膜の第１層〜第７層の膜厚におけるλは光の波長を示す。]
撥水膜は、前記反射防止膜の第７層上にフッ素置換アルキル基含有有機ケイ素化合物を原料として形成される光学部材の製造方法である。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a method for producing an optical member having the following configuration solves the problems described above, and has completed the present invention.
That is, the manufacturing method of the present invention is a manufacturing method of an optical member in which a multilayer antireflection film is formed on a plastic substrate by vacuum deposition, and a water repellent film is formed on the antireflection film, the antireflection film comprising: In order from the base material side to the outside air side, it is a 7-layer configuration described below,
First layer: a film thickness formed by depositing an organosilicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic substance containing silicon dioxide. Is a hybrid layer having a refractive index of 1.41 to 1.50 . Second layer: Tantalum oxide contains at least 50% by weight based on the second layer. The film thickness is 0.005λ to 0.10λ. Layer having a refractive index of 2.00 to 2.35 Third layer: containing an organosilicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and silicon dioxide Hybrid layer having an inorganic material as a deposition material and a film thickness of 0.005λ to 1.25λ and a refractive index of 1.41 to 1.50 Fourth layer: Tantalum oxide is at least 50% by weight based on the fourth layer The contained film thickness is 0.05λ ~ 0.45λ A layer having a refractive index of 2.00 to 2.35 Fifth layer: an organic silicon compound that is liquid at normal temperature and normal pressure and / or an inorganic compound containing silicon dioxide and a silicon-free organic compound that is liquid at normal temperature and normal pressure Is a hybrid layer having a film thickness of 0.005λ to 0.15λ and a refractive index of 1.41 to 1.50 . Sixth layer: tantalum oxide contains at least 50% by weight based on the sixth layer. Layer having a thickness of 0.05λ to 0.45λ and a refractive index of 2.00 to 2.35 Seventh layer: Organic silicon compound that is liquid at normal temperature and normal pressure and / or silicon non-liquid that is liquid at normal temperature and normal pressure A hybrid layer having a film thickness of 0.2λ to 0.29λ and a refractive index of 1.41 to 1.50, formed using an organic compound containing and an inorganic substance containing silicon dioxide as an evaporation source
[The organosilicon compound has any structure represented by the following general formulas (a) to (d).
Formula (a): Silane or siloxane compound

General formula (b): Silazane compound

General formula (c): cyclosiloxane compound

General formula (d): cyclosilazane compound

[In the general formulas (a) to (d), m and n in the formula each independently represent an integer of 0 or more. X _{1 to} X ₈ are each independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms (including both saturated and unsaturated), —OR ¹ group, —CH ₂ OR ² group, —COOR ³ group, -OCOR ⁴ group, -SR ⁵ group, -CH ₂ SR ⁶ group, -NR ⁷ ₂ group, or, -CH ₂ NR ⁸ ₂ group (R ¹ to R ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms (Including both saturated and unsaturated bonds in the bond between carbon atoms)). }
The silicon-free organic compound has any structure represented by the following general formulas (e) to (g).
General formula (e): Silicon-free organic compound containing carbon and hydrogen having an epoxy group at one end as essential components

Formula (f): Silicon-free organic compound containing carbon and hydrogen having epoxy groups at both ends as essential components

General formula (g): silicon-free organic compound containing unsaturated bonds and containing carbon and hydrogen as essential components
CX ₉ X ₁₀ = CX ₁₁ X ₁₂ (g)
(In the general formulas (e) and (f), R ⁹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms which may contain oxygen, and R ¹⁰ is a carbon number 1 to 1 which may contain oxygen. 7 represents a divalent hydrocarbon group of 7. In the general formula (g), X _{9 to} X ₁₂ are each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or a carbon or hydrogen having 1 to 10 carbon atoms. Is an essential component, and further represents an organic group having at least one of oxygen and nitrogen as an essential component.)]
[Λ in the film thicknesses of the first to seventh layers of the antireflection film represents the wavelength of light. ]
The water repellent film is a method for producing an optical member, which is formed using a fluorine-substituted alkyl group-containing organosilicon compound as a raw material on the seventh layer of the antireflection film.

  According to the production method of the present invention, not only has an excellent antireflection film with low reflectance and high transmittance, but also an optical member excellent in heat resistance and abrasion resistance on a plastic substrate is produced. It can be manufactured with good performance.

The manufacturing method of the antireflection film of the present invention is formed by vacuum deposition. Moreover, in order to obtain favorable film | membrane intensity | strength and adhesiveness, it is preferable to form by the ion assist method. The film constituent layers other than the hybrid layer of the antireflection film are tantalum oxide (Ta ₂ O ₅ ) layers as a high refractive index layer in order to obtain good antireflection effects and physical properties such as scratch resistance. The tantalum oxide layer contains at least 50% by weight of tantalum oxide in each layer, and more preferably 80% by weight or more.
In the present invention, the inorganic substance used in the hybrid layer needs to contain silicon dioxide, and at least one selected from aluminum oxide, titanium oxide, zirconium oxide, tantalum oxide, yttrium oxide, and niobium oxide. It may contain seeds. When a plurality of inorganic substances are used, they may be physically mixed or may be a composite oxide, specifically, SiO ₂ —Al ₂ O ₃ or the like. Of these, at least one inorganic oxide selected from silicon dioxide (SiO ₂ ) alone, silicon dioxide (SiO ₂ ) and aluminum oxide (Al ₂ O ₃ ) is preferable.

In the present invention, the organic substance used in the hybrid layer is an organic silicon compound in a liquid state at room temperature and normal pressure and / or liquid at room temperature and normal pressure from the viewpoint of film thickness control and deposition rate control. A silicon-free organic compound is used.
The organosilicon compound preferably has any structure represented by the following general formulas (a) to (d), for example.

Formula (a): Silane-siloxane compound

General formula (b): Silazane compound

General formula (c): cyclosiloxane compound

General formula (d): cyclosilazane compound

In the general formulas (a) to (d), m and n in the formula each independently represent an integer of 0 or more. X _{1 to} X ₈ are each independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms (including both saturated and unsaturated), —OR ¹ group, —CH ₂ OR ² group, —COOR ³ group, — OCOR ⁴ group, -SR ⁵ group, -CH ₂ SR ⁶ group, -NR ⁷ ₂ group, or, -CH ₂ NR ⁸ ₂ group (R ¹ to R ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms ( X _{1 to} X ₈ may be any functional group as described above, and all may be the same functional group or may be different from each other.
Specific examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ^{1 to} R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a pentyl group, and a hexyl group. Group, vinyl group, allyl group, ethynyl group, phenyl group, cyclohexyl group, propynyl group, isopropenyl group and the like.

Specific compounds represented by the general formula (a) include trimethylsilanol, tetramethylsilane, diethylsilane, dimethylethoxysilane, hydroxymethyltrimethylsilane, methoxytrimethylsilane, dimethoxydimethylsilane, methyltrimethoxysilane, mercaptomethyltrimethoxy. Silane, tetramethoxysilane, mercaptomethyltrimethylsilane, aminomethyltrimethylsilane, dimethyldimethylaminosilane, ethynyltrimethylsilane, diacetoxymethylsilane, allyldimethylsilane, trimethylvinylsilane, methoxydimethylvinylsilane, acetoxytrimethylsilane, trimethoxyvinylsilane, diethylmethyl Silane, ethyltrimethylsilane, ethoxytrimethylsilane, diethoxymethylsilane Ethyltrimethoxysilane, dimethylaminotrimethylsilane, bis (dimethylamino) methylsilane, phenylsilane, dimethyldivinylsilane, 2-propynyloxytrimethylsilane, dimethylethoxyethynylsilane, diacetoxydimethylsilane, allyltrimethylsilane, allyloxytrimethylsilane , Ethoxydimethylvinylsilane, isopropenoxytrimethylsilane, allylaminotrimethylsilane, trimethylpropylsilane, trimethylisopropylsilane, triethylsilane, diethyldimethylsilane, butyldimethylsilane, trimethylpropoxysilane, trimethylisopropoxysilane, triethylsilanol, diethoxydimethyl Silane, propyltrimethoxysilane, diethylaminodimethylsilane, bis ( Ethylamino) dimethylsilane, bis (dimethylamino) dimethylsilane, tri (dimethylamino) silane, methylphenylsilane, methyltrivinylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, allyloxydimethylvinylsilane, diethylmethylvinylsilane, diethoxy Methylvinylsilane, bis (dimethylamino) methylvinylsilane, butyldimethylhydroxymethylsilane, 1-methylpropoxytrimethylsilane, isobutoxytrimethylsilane, butoxytrimethylsilane, butyltrimethoxysilane, methyltriethoxysilane, isopropylaminomethyltrimethylsilane, diethylamino Trimethylsilane, methyltri (dimethylamino) silane, dimethylphenylsilane, tetravinylsilane , Triacetoxyvinylsilane, tetraacetoxysilane, ethyltriacetoxysilane, diallyldimethylsilane, 1,1-dimethylpropynyloxytrimethylsilane, diethoxydivinylsilane, butyldimethylvinylsilane, dimethylisobutoxyvinylsilane, acetoxytriethylsilane, triethoxy Vinylsilane, tetraethylsilane, dimethyldipropylsilane, diethoxydiethylsilane, dimethyldipropoxysilane, ethyltriethoxysilane, tetraethoxysilane, methylphenylvinylsilane, phenyltrimethylsilane, dimethylhydroxymethylphenylsilane, phenoxytrimethylsilane, dimethoxymethylphenyl Silane, phenyltrimethoxysilane, anilinotrimethylsilane, 1-cyclohexenilo Xytrimethylsilane, cyclohexyloxytrimethylsilane, dimethylisopentyloxyvinylsilane, allyltriethoxysilane, tripropylsilane, butyldimethyl-3-hydroxypropylsilane, hexyloxytrimethylsilane, propyltriethoxysilane, hexyltrimethoxysilane, dimethylphenyl Vinylsilane, trimethylsilylbenzoate, dimethylethoxyphenylsilane, methyltriisopropenoxysilane, methoxytripropylsilane, dibutoxydimethylsilane, methyltripropoxysilane, bis (butylamino) dimethylsilane, divinylmethylphenylsilane, diacetoxymethylphenyl Silane, diethylmethylphenylsilane, diethoxymethylphenylsilane, triisopropoxyvinylsilane , 2-ethylhexyloxytrimethylsilane, pentyltriethoxysilane, diphenylsilane, diphenylsilanediol phenyltrivinylsilane, triethylphenylsilane, phenyltriethoxysilane, tetraallyloxysilane, phenyltri (dimethylamino) silane, tetrapropoxysilane , Tetraisopropoxysilane, diphenylmethylsilane, diallylmethylphenylsilane, dimethyldiphenylsilane, dimethoxydiphenylsilane, dianilinodimethylsilane, diphenylethoxymethylsilane, tripentyloxysilane, diphenyldivinylsilane, diacetoxydiphenylsilane, diethyldiphenylsilane , Diethoxydiphenylsilane, bis (dimethylamino) diphenylsilane, tetrabutylsilane, Tetrabutoxysilane, triphenylsilane, diallyldiphenylsilane, trihexylsilane, triphenoxyvinylsilane, 1,1,3,3-tetramethyldisiloxane, pentamethyldisiloxane, hexamethyldisiloxane, 1,3-dimethoxytetramethyl Disiloxane, 1,3-diethynyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diethoxytetramethyldi Examples include siloxane, hexaethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane, and the like.
Specific compounds represented by the general formula (b) include 1,1,3,3-tetramethyldisilazane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyl. And compounds such as disilazane.
Specific compounds represented by the general formula (c) include compounds such as hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and octamethylcyclotetrasiloxane. Is mentioned.
Specific compounds represented by the general formula (d) include 1,1,3,3,5,5-hexamethylcyclotrisilazane, 1,1,3,3,5,5,7,7- Examples thereof include compounds such as octamethylcyclotetrasilazane.
The number average molecular weight of these organosilicon compounds is preferably 48 to 600, particularly preferably 140 to 500, from the viewpoint of controlling the organic components in the hybrid film and the strength of the film itself.

Furthermore, the silicon-free organic compound constituting the hybrid layer preferably has carbon and hydrogen containing reactive groups at its side chain or terminal as essential components, and more specifically, those represented by the general formulas (e) to (e) The compound represented by (g) is preferably used.
General formula (e): Silicon-free organic compound containing carbon and hydrogen having an epoxy group at one end as essential components

一般式（g）：二重結合を含む、炭素及び水素を必須成分とするケイ素非含有有機化合物
ＣＸ₉Ｘ₁₀＝ＣＸ₁₁Ｘ₁₂ ・・・（ｇ）
一般式（e）、（f）において、Ｒ⁹は水素、または酸素を含んでいてもよい炭素数1〜10の炭化水素基、Ｒ¹⁰は、酸素を含んでいてもよい炭素数1〜7の二価の炭化水素基を表す。一般式（g）において、Ｘ₉〜Ｘ₁₂はそれぞれ独立に水素、炭素数1〜10の炭化水素基、または炭素数1〜10の炭素、水素を必須成分とし、さらに酸素及び窒素の少なくとも一方を必須成分とする有機基を表す。 Formula (f): Silicon-free organic compound containing carbon and hydrogen having epoxy groups at both ends as essential components

General formula (g): a silicon-free organic compound containing carbon and hydrogen as essential components, including a double bond
CX ₉ X ₁₀ = CX ₁₁ X ₁₂ (g)
In the general formulas (e) and (f), R ⁹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms which may contain oxygen, and R ¹⁰ has 1 to 7 carbon atoms which may contain oxygen. Represents a divalent hydrocarbon group. In the general formula (g), X _{9 to} X ₁₂ are each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or carbon having 1 to 10 carbon atoms and hydrogen as essential components, and at least one of oxygen and nitrogen Represents an organic group having as an essential component.

Specific examples of the compound of the general formula (e) include methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-sec-butylphenyl glycidyl. Examples include ether, p-tert-butylphenyl glycidyl ether, 2-methyloctyl glycidyl ether, glycidol, and trimethylolpropane polyglycidyl ether.
Specific examples of the compound of the general formula (f) include neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and the like.

Specific examples of the general formula (g) include ethylene, propylene, vinyl chloride, vinyl fluoride, acrylamide, vinyl pyrrolidone, vinyl carbazole, methyl methacrylate, ethyl methacrylate, benzyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dimethylaminoethyl methacrylate. Methacrylic acid, glycidyl methacrylate, vinyl acetate, styrene and the like.
In addition, the number average molecular weight of the compounds represented by the general formulas (e) to (g) is preferably 28 to 400, particularly preferably, considering the control of organic components in the hybrid film and the film strength of the hybrid. Is 140-360.

As a method for forming a film of an organosilicon compound that is liquid at room temperature and pressure and / or a silicon-free organic compound that is liquid at room temperature and pressure (hereinafter sometimes referred to as “organic substance”) in the present invention, FIG. As shown in FIG. 5, when forming the hybrid layer, it is preferable to form a film by simultaneously depositing an inorganic substance and an organic substance in separate vapor deposition sources. Specifically, the inorganic substance is vaporized by heating using an electron gun or the like, the organic substance is stored in an external tank, the organic substance is vaporized in the tank, and the inorganic substance and the organic substance are vapor-deposited simultaneously. The method is preferred.
From the viewpoint of controlling the deposition rate, it is preferable to heat / depressurize the external tank for storing the organic material, supply the organic material into the chamber, and perform ion-assisted film formation using oxygen gas and / or argon gas. . Further, in the present invention, the organic substance is a liquid at normal temperature and normal pressure, and it is not necessary to use a solvent, and it can be directly heated and deposited. In addition, as shown in FIG. 1, it is effective to improve the impact resistance and wear resistance of the organic substance inlet, as shown in FIG. It is preferable to supply a silicon-free organic compound containing carbon and hydrogen containing reactive groups as essential components.
The heating temperature of the external tank varies depending on the evaporation temperature of the organic substance, but is preferably 30 to 200 ° C., preferably 50 to 150 ° C. from the viewpoint of obtaining an appropriate deposition rate.
A preferable in-film content of the organic material of the hybrid layer in the present invention is 0.02 to 25% by weight in consideration of a particularly good physical property modification effect.

The preferred film thickness and refractive index ranges in the present invention are as follows. Here, λ represents the wavelength of light.
1st layer 0.005λ ~ 1.25λ 1.41 ~ 1.50
Second layer 0.005λ to 0.10λ 2.00 to 2.35
3rd layer 0.005λ ~ 1.25λ 1.41 ~ 1.50
4th layer 0.05λ to 0.45λ 2.00 to 2.35
5th layer 0.005λ to 0.15λ 1.41 to 1.50
6th layer 0.05λ to 0.45λ 2.00 to 2.35
7th layer 0.2λ ~ 0.29λ 1.41 ~ 1.50
By adopting such a film configuration, desired physical properties can be easily obtained.

  In the ion assist method, a preferable range for the output is an acceleration voltage of 50 to 700 V and an acceleration current of 30 to 250 mA, particularly from the viewpoint of obtaining a good reaction. It is preferable to use argon (Ar) or a mixed gas of argon and oxygen as the ionization gas used when performing the ion assist method from the viewpoint of reactivity during film formation and oxidation prevention.

  The water repellent film is formed on the seventh layer of the antireflection film using a fluorine-substituted alkyl group-containing organosilicon compound as a raw material. The raw material and the forming method are preferably those described in European Patent Publication No. 1351071. As the method, the fluorine-substituted alkyl group-containing organosilicon compound diluted with a solvent is subjected to the deposition from the start of heating within a range of not less than the deposition start temperature of the organosilicon compound and not exceeding the decomposition temperature of the organosilicon compound under reduced pressure. It is preferable to complete within 2 seconds, preferably within 10 seconds. As a method for achieving such a deposition time, a method of irradiating the organosilicon compound with an electron beam is preferably used.

（式中、Rfは炭素数１〜１６の直鎖状のパーフルオロアルキル基、Ｘは水素または炭素数１〜５の低級アルキル基、Ｒ¹¹は加水分解可能な基、ｋは１〜５０の整数、ｒは０〜２の整数、ｐは１〜１０の整数）
Ｃ_qＦ_2q+1ＣＨ₂ＣＨ₂Ｓｉ（ＮＨ₂）₃ ・・・（ｉ）
（ただし、ｑは１以上の整数である）
ここで、上記Ｒ¹¹で示される加水分解可能な基としてはアミノ基、アルコキシ基、特にアルキル部が炭素数１〜２であるアルコキシ基、塩素原子等が挙げられる。
また、上記式（ｉ）で表される化合物の具体例としては、ｎ−CF₃CH₂CH₂Si(NH₂)₃；ｎ−トリフロロ（１，１，２，２−テトラヒドロ）プロピルシラザン、ｎ−C₃F₇CH₂CH₂Si(NH₂)₃；ｎ−ヘプタフロロ（１，１，２，２−テトラヒドロ）ペンチルシラザン、ｎ−C₄F₉CH₂CH₂Si(NH₂)₃；ｎ−ノナフロロ（１，１，２，２−テトラヒドロ）ヘキシルシラザン、ｎ−C₆F₁₃CH₂CH₂Si(NH₂)₃；ｎ−トリデオフロロ（１，１，２，２−テトラヒドロ）オクチルシラザン、ｎ−C₈F₁₇CH₂CH₂Si(NH₂)₃；ｎ−ヘプタデカフロロ（１，１，２，２−テトラヒドロ）デシルシラザン等を例示することができる As the fluorine-substituted alkyl group-containing organosilicon compound, those represented by the following general formula (h) or those represented by the following unit formula (i) are preferable.

Wherein Rf is a linear perfluoroalkyl group having 1 to 16 carbon atoms, X is hydrogen or a lower alkyl group having 1 to 5 carbon atoms, R ¹¹ is a hydrolyzable group, k is 1 to 50 An integer, r is an integer of 0-2, p is an integer of 1-10)
C _q F _{2q + 1} CH ₂ CH ₂ Si (NH ₂ ) ₃ (i)
(However, q is an integer of 1 or more)
Here, examples of the hydrolyzable group represented by R ¹¹ include an amino group, an alkoxy group, particularly an alkoxy group having an alkyl portion of 1 to 2 carbon atoms, a chlorine atom, and the like.
Specific examples of the compound represented by the formula (i) include n-CF ₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ; n-trifluoro (1,1,2,2-tetrahydro) propylsilazane, _{n-C 3 F 7 CH 2} CH 2 Si (NH 2) 3; n- Heputafuroro (1,1,2,2-tetrahydro) _{Penchirushirazan, n-C 4 F 9 CH} 2 CH 2 Si (NH 2) 3 N-nonafluoro (1,1,2,2-tetrahydro) hexylsilazane, nC ₆ F ₁₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ; n-tridefluoro (1,1,2,2-tetrahydro) octyl Examples include silazane, n-C ₈ F ₁₇ CH ₂ CH ₂ Si (NH ₂ ) ₃ ; n-heptadecafluoro (1,1,2,2-tetrahydro) decylsilazane, and the like.

  In addition, as a raw material for the water-repellent layer, a raw material mainly composed of two components of a fluorine-substituted alkyl group-containing organosilicon compound and a silicon-free perfluoropolyether can be used. A water repellent layer is formed by forming a second layer using a raw material mainly composed of silicon-free perfluoropolyether in contact with the first layer. It is also suitable to form.

The silicon-free perfluoropolyether has the following structural formula (j) which does not contain silicon:
^{- (R 12 O) - ···} (j)
(In the formula, R ¹² is a C 1-3 perfluoroalkylene group)
Are preferably used, and those having an average molecular weight of 1000 to 10000, particularly 2000 to 10000 are preferred. R is a perfluoroalkylene group having 1 to 3 carbon atoms, and specific examples thereof include CF ₂ , CF ₂ -CF ₂ , CF ₂ CF ₂ CF ₂ , and CF (CF ₃ ) CF ₂ . These perfluoropolyethers are liquid at room temperature and are called so-called fluorine oils.

  In addition, the optical member of the present invention has a catalytic action when forming a hybrid layer, which will be described later, such as nickel (Ni), silver, etc. A layer made of at least one selected from (Ag), platinum (Pt), niobium (Nb), and titanium (Ti) can be applied. A particularly preferable undercoat layer is a metal layer made of niobium in order to give better impact resistance. When a metal layer is used as the underlayer, the reaction of the hybrid layer provided on the underlayer is facilitated, a substance having an intramolecular stitch structure is obtained, and impact resistance is improved.

  The material of the plastic substrate used in the present invention is not particularly limited. For example, methyl methacrylate homopolymer, copolymer of methyl methacrylate and one or more other monomers, diethylene glycol Rubisallyl carbonate homopolymer, copolymer of diethylene glycol bisallyl carbonate and one or more other monomers, sulfur-containing copolymer, halogen copolymer, polycarbonate, polystyrene, Examples include polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, polythiourethane, and polymers made from compounds having an epithio group.

  Examples of compounds having an epithio group include bis (β-epithiopropylthio) methane, 1,2-bis (β-epithiopropylthio) ethane, and 1,3-bis (β-epithiopropylthio) propane. 1,2-bis (β-epithiopropylthio) propane, 1- (β-epithiopropylthio) -2- (β-epithiopropylthiomethyl) propane, 1,4-bis (β-epithio) Propylthio) butane, 1,3-bis (β-epithiopropylthio) butane, 1- (β-epithiopropylthio) -3- (β-epithiopropylthiomethyl) butane, 1,5-bis ( β-epithiopropylthio) pentane, 1- (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) pentane, 1,6-bis (β-epithiopropylthio) hexane, 1- (Β- (Pithiopropylthio) -5- (β-epithiopropylthiomethyl) hexane, 1- (β-epithiopropylthio) -2-[(2-β-epithiopropylthioethyl) thio] ethane, 1- Examples thereof include chain organic compounds such as (β-epithiopropylthio) -2-[[2- (2-β-epithiopropylthioethyl) thioethyl] thio] ethane. Tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β-epithiopropylthiomethyl) propane, 1,5-bis (β-epithiopropylthio) -2- (β -Epithiopropylthiomethyl) -3-thiapentane, 1,5-bis (β-epithiopropylthio) -2,4-bis (β-epithiopropylthiomethyl) -3-thiapentane, 1- (β- Epithiopropylthio) -2,2-bis (β-epithiopropylthiomethyl) -4-thiahexane, 1,5,6-tris (β-epithiopropylthio) -4- (β-epithiopropylthio) Methyl) -3-thiahexane, 1,8-bis (β-epithiopropylthio) -4- (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropyl) E) -4,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -4,4-bis (β-epithiopropylthiomethyl) ) -3,6-dithiaoctane, 1,8-bis (β-epithiopropylthio) -2,4,5-tris (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,8-bis (Β-epithiopropylthio) -2,5-bis (β-epithiopropylthiomethyl) -3,6-dithiaoctane, 1,9-bis (β-epithiopropylthio) -5- (β-epi Thiopropylthiomethyl) -5-[(2-β-epithiopropylthioethyl) thiomethyl] -3,7-dithianonane, 1,10-bis (β-epithiopropylthio) -5,6-bis [( 2-β-epithiopropylthio Ethyl) thio] -3,6,9-trithiadecane, 1,11-bis (β-epithiopropylthio) -4,8-bis (β-epithiopropylthiomethyl) -3,6,9-trithia Undecane, 1,11-bis (β-epithiopropylthio) -5,7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, 1,11-bis (β-epi Thiopropylthio) -5,7-[(2-β-epithiopropylthioethyl) thiomethyl] -3,6,9-trithiaundecane, 1,11-bis (β-epithiopropylthio) -4, Branched organic compounds such as 7-bis (β-epithiopropylthiomethyl) -3,6,9-trithiaundecane, compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group, etc. Is mentioned The Furthermore, 1,3 and 1,4-bis (β-epithiopropylthio) cyclohexane, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (β-epithio Propylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2,5-bis (β -Cycloaliphatic organic compounds such as epithiopropylthiomethyl) -1,4-dithiane and 2,5-bis (β-epithiopropylthioethylthiomethyl) -1,4-dithiane and episulfide groups of these compounds A compound in which at least one of hydrogens in the above is substituted with a methyl group, and 1,3 and 1,4-bis (β-epithiopropylthio) benzene, 1,3 and 1,4-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2,2-bis [4- (β-epithiopropyl) Thio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfone, 4,4′-bis (β-epithiopropyl) Aromatic organic compounds such as thio) biphenyl and compounds in which at least one hydrogen of the episulfide group of these compounds is substituted with a methyl group.

The optical member of the present invention may have a cured layer between the plastic substrate and the base layer.
For the formation of the hardened layer, the metal oxide colloidal particles and the following general formula (k)
(R ¹³ ) _a (R ¹⁴ ) _b Si (OR ¹⁵ ) _{4- (a + b)} (k)
Wherein R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, or an acyl group having 1 to 8 carbon atoms. , A halogen group, a glycidoxy group, an epoxy group, an amino group, a phenyl group, a mercapto group, a methacryloxy group, and a cyano group, R ¹³ represents an alkyl group having 1 to 8 carbon atoms and 1 to 1 carbon atoms. An organic group selected from an acyl group having 8 and a phenyl group having 6 to 8 carbon atoms, wherein a and b are each independently an integer of 0 or 1) Things are used.

Examples of the metal oxide colloidal particles include tungsten oxide (WO ₃ ), zinc oxide (ZnO), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), zirconium oxide ( ZrO ₂ ), tin oxide (SnO ₂ ), beryllium oxide (BeO), or antimony oxide (Sb ₂ O ₅ ), and the like can be used alone or in combination of two or more.

  The coating liquid for forming the cured layer can be prepared by a conventionally known method. If desired, various organic solvents and surfactants can be contained for the purpose of improving the curing catalyst, wettability during coating, and improving the smoothness of the cured layer. Furthermore, ultraviolet absorbers, antioxidants, light stabilizers and anti-aging agents can be added as long as they do not affect the physical properties of the coating composition and the cured film.

Curing of the coating composition is performed by hot air drying or active energy ray irradiation, and the curing conditions are preferably 70-200 ° C. in hot air, particularly preferably 90-150 ° C. Active energy rays include far infrared rays and the like, and damage due to heat can be kept low.
Moreover, the method of apply | coating the coating composition mentioned above to a base material as a method of forming the hardened layer which consists of a coating composition on a base material is mentioned. As a coating means, a commonly performed method such as a dipping method, a spin coating method, or a spray method can be applied, but a dipping method or a spin coating method is particularly preferable in terms of surface accuracy.

  Further, in order to ensure adhesion between the plastic substrate and the base layer or to make the initial film formation state of the vapor deposition substance uniform, an ionized gas treatment may be performed on the surface of the cured layer. As the ionization gas in the ion gun pretreatment, oxygen, argon (Ar), or the like can be used, and a preferable range of output is an acceleration voltage of 50 to 700 V and an acceleration current of 50 to 700 from the viewpoint of obtaining particularly good adhesion and wear resistance. 250mA.

In the present invention, it is not denied that a primer layer made of an organic compound is applied between the plastic substrate and the antireflection film, as described in JP-A-63-141001, etc. In order to further improve impact resistance, a primer layer made of an organic compound as a raw material may be provided between the plastic substrate and the antireflection film or between the plastic substrate and the cured layer.
Examples of the primer layer include those that form a urethane film using polyisocyanate and polyol as raw materials. Examples of polyisocyanates include hexamethylene diisocyanate, 4,4'-cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, an adduct obtained by bonding various molecules, isocyanurate, allophanate, burette, carbodiimide with acetoacetic acid, Examples of the polyol include those blocked with malonic acid, methyl ethyl ketoxime, and the like. On the other hand, examples of the polyol include polyester, polyether, polycaprolactone, polycarbonate, and polyacrylate having a plurality of hydroxyl groups in one molecule. Further, in order to improve the refractive index of the primer film, metal oxide fine particles such as titanium oxide fine particles can be contained in the primer layer.
In particular, by applying a primer layer to a plastic substrate made of a compound having an epithio group having a refractive index of about 1.68 to 1.76 as a raw material, and further applying the antireflection film of the present invention, the center thickness of the substrate is reduced. In addition, an optical member excellent in impact resistance, adhesion, and scratch resistance can be obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
In addition, the physical property evaluation of the optical member obtained in the Example and the comparative example was performed as follows.
(1) Luminous transmittance luminous transmittance Y ₁ of the plastic lens, a plastic lens having an antireflection film on both surfaces as a sample was measured using a Hitachi spectrophotometer U-3410.
The luminous reflectance Y ₂ (2) luminous reflectance plastic lens, a plastic lens having an antireflection film on both surfaces as a sample was measured using a Hitachi spectrophotometer U-3410.
(3) Impact resistance A lens with a lens center thickness (hereinafter referred to as “CT”) of 1.0 mm or 2.0 mm and a lens power of 0.00D (diopter) is manufactured to produce FDA (Food and A drop ball test defined in Drug Administration) was performed, and a pass was evaluated as “good” and a failure as “poor”. Here, the weight of the ball was 14 g. Further, the drop ball test was continued until the lens was damaged, and the strength was confirmed as the maximum load.
(4) Adhesiveness Create 100 squares of 1 mm x 1 mm with a razor on the surface of a plastic lens, apply cellophane tape (manufactured and sold by Nichiban Co., Ltd.) on the squares, peel off the tape at once, and evaluate by the number of squares remaining did. In the table, it is indicated by the number of remaining squares / 100.
(5) Abrasion resistance The surface of the plastic lens was subjected to a 98 kPa (1 kgf / cm ² ) load with steel wool (standard # 0000, manufactured by Nippon Steel Wool Co., Ltd.), rubbed for 10 strokes, and depending on the surface condition, Evaluated by criteria.
UA: almost no scratches A: several thin wounds B: many thin wounds, several thick wounds C: many thin wounds, many thick wounds D: almost film baldness

(6) Heat resistance The plastic lens was heated from 60 ° C. to 5 ° C. in a dry oven and heated for 1 hour, and the crack generation temperature was measured.
(7) Alkali resistance The plastic lens was immersed in a 10% NaOH aqueous solution at 20 ° C. for 1 hour and evaluated according to the following criteria according to the surface condition.
UA: Almost no change A: There are several point-shaped film baldness B: There are dot-shaped film baldness on the entire surface C: There are dot-shaped baldness on the entire surface, several sheet-shaped baldness D: Almost entire film baldness (8 ) Bayer Value Measurement Using a wear tester BTE ^™ Abrasion Tester (manufactured by COLTS, USA) and a haze value measuring device (Murakami Color Research Laboratory), the Bayer value was measured by the difference in haze value change from the reference lens.
(Number of samples, measuring method)
(A) Three reference lenses (CR39 base material) and three sample lenses were prepared.
(B) The haze value before the wear test was measured.
(C) Abrasion test was performed with BTE ^™ Abrasion Tester.
(Surface wear due to sand 600 round trips)
(D) The haze value was measured after the wear test.
(E) The Bayer value was calculated (the average value for three sheets). Here, the Bayer value is expressed by the change in transmittance of the reference lens / change in transmittance of the sample lens.
(9) Mechanical strength test (JIS static pressure test)
The test was conducted in accordance with JIS T 7331: 2000.

Plastic lens substrate to be used (a) Substrate A: Diethylene glycol bisallyl carbonate, refractive index 1.50, center thickness 2.0 mm, lens power 0.00
(B) Base material B: EYRY base material (trade name, manufactured by HOYA Co., Ltd.) Refractive index 1.70, central pressure 1.0 mm, lens power 0.00

Preparation of Coating Composition A In a glass container, 90 parts by weight of colloidal silica (Snotex-40, Nissan Chemical), 81.6 parts by weight of an organosilicon compound, methyltrimethoxysilane, γ-glycidoxypropyltri A solution obtained by adding 176 parts by weight of methoxysilane, 2.0 parts by weight of 0.5N hydrochloric acid, 20 parts by weight of acetic acid and 90 parts by weight of water was stirred for 8 hours at room temperature, and then allowed to stand for 16 hours at room temperature. Obtained. To this solution, 120 parts by weight of isopropyl alcohol, 120 parts by weight of n-butyl alcohol, 16 parts by weight of aluminum acetylacetone, 0.2 part by weight of a silicone-based surfactant and 0.1 part by weight of an ultraviolet absorber are added. The mixture was stirred at room temperature for 8 hours and then aged at room temperature for 24 hours to obtain a coating solution. Hereinafter, the cured layer obtained with this coating composition may be referred to as “hard coat layer A”.

Preparation of Coating Composition B In a glass container, 1045 parts by weight of γ-glycidoxypropyl (trimethoxy) silane and 200 parts by weight of γ-glycidoxypropylmethyl (diethoxy) silane were added while stirring. 299 parts by weight of mol / liter hydrochloric acid was added, and stirring was continued all day and night in a clean room at 10 ° C. to obtain a silane hydrolyzate.
In another container, composite fine particle sol mainly composed of titanium oxide, zirconium oxide and silicon oxide (methanol dispersion, total solid content 30 wt%, average particle size 5 to 8 mm) and 3998 parts by weight of methyl cellosolve 4018 parts by weight 830 parts by weight of isopropanol was added and mixed with stirring. Further, 4 parts by weight of a silicone surfactant (“L-7001” manufactured by Nihon Unicar Co., Ltd.) and 100 parts by weight of aluminum acetylacetonate were added. Stirring was continued overnight in a clean room at 0 ° C., and then the above hydrolyzate was combined and further stirred overnight. Thereafter, the mixture was filtered with a 3 μm filter to obtain a hard coat solution B. Hereinafter, the cured layer obtained with this coating composition may be referred to as “hard coat layer B”.

Formation of cured layer A plastic lens substrate A or B pretreated with an alkaline aqueous solution is immersed in the coating solution. After the immersion, the plastic lens pulled up at a lifting speed of 20 cm / min is heated at 120 ° C. for 2 hours. A cured layer (hard coat A layer, hard coat B layer) was formed.
On the ion gun-treated cured layer, ion irradiation was performed with an ion gun under the conditions of ion acceleration voltage, irradiation time, and gas atmosphere described in the table.

Formation of an antireflection film having a hybrid film An antireflection film comprising the first to seventh layers is formed on the hard coat A layer or B layer irradiated with ions under the conditions shown in Table 1, and a plastic lens is formed. Obtained.
Note that conditions were set so that the hybrid layer was deposited almost simultaneously as binary deposition of inorganic material and organic material using the apparatus shown in FIG. During the vapor deposition of the organic substance, the vaporized organic substance was introduced into the vapor deposition apparatus using a gas valve and a mass flow controller. When forming the hybrid layer, an ion assist method was used in an atmosphere of a mixed gas of argon gas and oxygen gas. Moreover, what is described as "-" in a table | surface formed the layer by the normal vacuum evaporation method, without using the ion assist method. In the table, M1 represents an inorganic substance, CM1 represents an organosilicon compound, and CM2 represents a silicon-free organic compound.

Details of the organic compounds described in the table are as follows.
(a) Epolite 70P (Propylene glycol diglycidyl ether, average molecular weight of about 188, manufactured by Kyoeisha Chemical Co., Ltd.)
(b) LS: 1371 (diethoxydimethylsilane, molecular weight 148.3, manufactured by Shin-Etsu Chemical Co., Ltd.)
(c) Epiol P200 (polypropylene glycol glycidyl ether, average molecular weight of about 304, manufactured by NOF Corporation)
(d) Denacol EX920 (polypropylene glycol diglycidyl ether, average molecular weight 354, manufactured by Nagase Chemtex Co., Ltd.)
KY-130 is a "fluorine-substituted alkyl group-containing organosilicon compound" (manufactured by Shin-Etsu Chemical Co., Ltd.) for antifouling film formation. Silicon compound "(manufactured by Shin-Etsu Chemical Co., Ltd.).

Formation of water-repellent film Sintered stainless steel filter (mesh 80-100 microns, 18φ × 3mm) impregnated with 0.3 ml of KY-130 ( manufactured by Shin - Etsu Chemical Co., Ltd.) containing a fluorine-substituted alkyl group-containing organosilicon compound ) Was set in a vacuum deposition apparatus, and the entire sintered filter was heated using an electron gun under the following conditions to form a water repellent film.
(A) Degree of vacuum: 2.3 × 10 ^{−6 to} 6.0 × 10 ⁻⁶ Torr
(B) Electron gun conditions Acceleration voltage: 6 KV, applied current: 40 mA, irradiation area: 3.5 × 3.5 cm square, vapor deposition time: 5 seconds In Example 5 and later, a primer is provided between the substrate and the cured layer. -Layered. The method for forming the primer layer is as follows.

Formation of primer layer Polyester type polyol (trade name of Sumitomo Bayer Urethane Co., Ltd., using Desmophen A-670) 6.65 parts by weight, block type polyisocyanate (trade name of Sumitomo Bayer Urethane Co., Ltd., BL -3175 use) 6.08 parts by weight, 0.17 parts by weight of dibutyltin dilaurate as a curing catalyst, 0.17 parts by weight of a fluorine-based leveling agent (trade name of Sumitomo 3M Co., Ltd., Fluorard FC-430) as a leveling agent And a mixture of 95.71 parts by weight of diacetone alcohol as a solvent was sufficiently stirred until uniform. The liquid primer thus obtained was applied on an alkali-treated base lens as a pretreatment by a dipping method (pickup speed: 24 cm / min), cured by heating at 100 ° C. for 40 minutes, and a thickness of 2 A primer layer of ˜3 μm was formed.

Examples 1-16 and Comparative Examples 1-4
With the configuration as shown in Table 1, an antireflection film was provided on the substrate, and physical properties were evaluated. The results are shown in Table 2. Note that λ indicates the wavelength of light.

  According to the production method of the present invention, an optical member having an excellent performance of low reflectance and high transmittance and having an antireflection film excellent in heat resistance and wear resistance is produced with high productivity. The optical member manufactured by this method is particularly excellent as a spectacle lens.

It is the schematic which shows the film-forming apparatus in this invention.

Explanation of sign

1: Optical film thickness monitor 2: Substrate 3: Dome for holding substrate 4: Organic substance introduction port A
5: Organic substance introduction port B
6: Evaporation source 7: RF ion gun 8: Ionized gas inlet 9: Connection to exhaust system 10: Connection to external monomer heating (vaporization) device

Claims (11)

A method of manufacturing an optical member in which a multilayer antireflection film is formed on a plastic substrate by vacuum deposition, and a water-repellent film is formed on the antireflection film, wherein the antireflection film is directed from the substrate side to the outside air side. In order, the seven-layer configuration described below,
First layer: a film thickness formed by depositing an organosilicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and an inorganic substance containing silicon dioxide. Is a hybrid layer having a refractive index of 1.41 to 1.50 . Second layer: Tantalum oxide contains at least 50% by weight based on the second layer. The film thickness is 0.005λ to 0.10λ. Layer having a refractive index of 2.00 to 2.35 Third layer: containing an organosilicon compound that is liquid at normal temperature and normal pressure and / or a silicon-free organic compound that is liquid at normal temperature and normal pressure, and silicon dioxide Hybrid layer having an inorganic material as a deposition material and a film thickness of 0.005λ to 1.25λ and a refractive index of 1.41 to 1.50 Fourth layer: Tantalum oxide is at least 50% by weight based on the fourth layer The contained film thickness is 0.05λ ~ 0.45λ A layer having a refractive index of 2.00 to 2.35 Fifth layer: an organic silicon compound that is liquid at normal temperature and normal pressure and / or an inorganic compound containing silicon dioxide and a silicon-free organic compound that is liquid at normal temperature and normal pressure Is a hybrid layer having a film thickness of 0.005λ to 0.15λ and a refractive index of 1.41 to 1.50 . Sixth layer: tantalum oxide contains at least 50% by weight based on the sixth layer. Layer having a thickness of 0.05λ to 0.45λ and a refractive index of 2.00 to 2.35 Seventh layer: Organic silicon compound that is liquid at normal temperature and normal pressure and / or silicon non-liquid that is liquid at normal temperature and normal pressure A hybrid layer having a film thickness of 0.2λ to 0.29λ and a refractive index of 1.41 to 1.50, formed using an organic compound containing and an inorganic substance containing silicon dioxide as an evaporation source
[The organosilicon compound has any structure represented by the following general formulas (a) to (d).
Formula (a): Silane or siloxane compound

General formula (b): Silazane compound

General formula (c): cyclosiloxane compound

General formula (d): cyclosilazane compound

[In the general formulas (a) to (d), m and n in the formula each independently represent an integer of 0 or more. X _{1 to} X ₈ are each independently hydrogen, a hydrocarbon group having 1 to 6 carbon atoms (including both saturated and unsaturated), —OR ¹ group, —CH ₂ OR ² group, —COOR ³ group, -OCOR ⁴ group, -SR ⁵ group, -CH ₂ SR ⁶ group, -NR ⁷ ₂ group, or, -CH ₂ NR ⁸ ₂ group (R ¹ to R ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms (Including both saturated and unsaturated bonds in the bond between carbon atoms)). }
The silicon-free organic compound has any structure represented by the following general formulas (e) to (g).
General formula (e): Silicon-free organic compound containing carbon and hydrogen having an epoxy group at one end as essential components

Formula (f): Silicon-free organic compound containing carbon and hydrogen having epoxy groups at both ends as essential components

General formula (g): silicon-free organic compound containing unsaturated bonds and containing carbon and hydrogen as essential components
CX ₉ X ₁₀ = CX ₁₁ X ₁₂ (g)
(In the general formulas (e) and (f), R ⁹ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms which may contain oxygen, and R ¹⁰ is a carbon number 1 to 1 which may contain oxygen. 7 represents a divalent hydrocarbon group of 7. In the general formula (g), X _{9 to} X ₁₂ are each independently hydrogen, a hydrocarbon group having 1 to 10 carbon atoms, or a carbon or hydrogen having 1 to 10 carbon atoms. Is an essential component, and further represents an organic group having at least one of oxygen and nitrogen as an essential component.)]
[Λ in the film thicknesses of the first to seventh layers of the antireflection film represents the wavelength of light. ]
The method for producing an optical member, wherein the water repellent film is formed using a fluorine-substituted alkyl group-containing organosilicon compound as a raw material on the seventh layer of the antireflection film.   The hybrid layer vaporizes the inorganic substance by heating using an electron gun, stores the organosilicon compound and / or silicon-free organic compound in a tank, and stores the organosilicon compound and the organic compound in the tank. The method for producing an optical member according to claim 1, wherein the organic compound is formed by heating and / or vaporizing a silicon-free organic compound, and vapor-depositing the inorganic substance and the organic silicon compound and / or silicon-free organic compound simultaneously.   The method for manufacturing an optical member according to claim 1, wherein the hybrid layer is formed by an ion assist method.   The method for producing an optical member according to any one of claims 1 to 3, wherein the organosilicon compound and / or the silicon-free organic compound is deposited by heating without adding a solvent. Number average molecular weight of the organic silicon compound, the optical member manufacturing method according to any one of claims 1 to 4, wherein a 48 to 600. Number average molecular weight of the silicon-free organic compound, the optical member manufacturing method according to any one of claims 1-5, wherein a 28 to 400.   The method for producing an optical member according to claim 1, wherein an in-film content of the organic silicon compound and / or silicon-free organic compound in the hybrid layer is 0.02 to 25% by weight. Between the plastic substrate and the antireflection film, a film thickness of 1 to 5 nm made of at least one selected from nickel (Ni), silver (Ag), platinum (Pt), niobium (Nb) and titanium (Ti). method of any one Kouki mounting of the optical member according to claim 7, wherein applying the undercoat layer.   The method for producing an optical member according to any one of claims 1 to 8, wherein the plastic substrate is a substrate made of diethylene glycol bisallyl carbonate as a raw material.   The method for producing an optical member according to any one of claims 1 to 9, wherein the plastic substrate is a substrate made of a compound having an epithio group as a raw material.   The method for producing an optical member according to any one of claims 1 to 10, wherein a primer layer and a cured layer are sequentially applied between the plastic substrate and the antireflection film in order from the plastic substrate.

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