JP4759377B2 - Method for manufacturing thin film and optical member - Google Patents

Description

  The present invention relates to a method for manufacturing a thin film and an optical member, and more particularly, to a method for manufacturing a thin film and an optical member in which a lens is not colored and has good antistatic properties and water repellency.

  2. Description of the Related Art Conventionally, an optical member is known in which a plastic substrate is provided with an antireflection film formed by depositing an inorganic substance or the like. Such an optical member has excellent antireflection properties and scratch resistance. However, since the optical member having such an antireflection film is a plastic substrate, the antistatic effect is not sufficient. As a method for solving the problem, for example, it is known to sequentially provide a hard coat layer and an antistatic hard coat layer having conductivity and hard coat properties on a plastic substrate (see, for example, Patent Document 1). ). It is also known to impart an antistatic effect by introducing an optical thin film made of a conductive metal oxide obtained by reacting an indefinite amount of oxygen with a metal into the antireflection film (for example, patents) Reference 2). Furthermore, a method of manufacturing a thin film by evaporating a thin film forming material obtained by adding a conductive substance such as carbon paste into a water repellent material using an electron gun is known (see, for example, Patent Document 3).

However, although the antistatic hard coat layer disclosed in Patent Document 1 has a sufficient antistatic effect, it has a problem that the absorption of visible light is large and the lens is colored. Further, the optical member disclosed in Patent Document 2 has a problem in surface scratch resistance, although it has a sufficient antistatic effect. In addition, the thin film manufacturing method disclosed in Patent Document 3 can stably apply a water-repellent film using an electron gun because the conductive material is contained in the water-repellent material. However, the antistatic effect is not sufficient. If the electron gun power is increased to evaporate the thin film forming material so as to provide an antistatic effect, the antistatic effect becomes uneven on the lens surface. Even in this case, the antistatic effect of the thin film was not sufficient.
JP 2002-329598 A European Patent Publication No. 0834092 JP-A-11-310869

  The present invention has been made to solve such a problem, and an object thereof is to provide a method for producing a thin film and an optical member in which a lens is not colored and has good antistatic properties and water repellency.

  As a result of intensive studies to solve the above problems, the present inventors have (a) a water repellent having a perfluoroalkyl group, (b) a silane coupling agent, an organic group on the side chain and / or both ends. A water repellent solution obtained by mixing a mixture of a modified silicone oil introduced with a group and a perfluoroether compound, and (c) at least one conductive material selected from fullerenes, carbon nanotubes and graphite compounds The inventors have found that the above-mentioned object can be achieved by forming a thin film by a vacuum vapor deposition method, and have completed the present invention.

  That is, the present invention relates to (a) a water repellent having a perfluoroalkyl group, (b) a silane coupling agent, a modified silicone oil having an organic group introduced into the side chain and / or both ends, and a perfluoroether compound. Production of a thin film by forming a thin film by a vacuum deposition method using a mixture and (c) a water repellent solution obtained by mixing at least one conductive material selected from fullerenes, carbon nanotubes and graphite compounds And an optical member manufacturing method for forming a multilayer antireflection film on an optical substrate by further forming a thin film on the multilayer antireflection film by the above-described thin film manufacturing method of the present invention. It is to provide.

  According to the production method of the present invention, the lens is not colored, and a thin film having good antistatic properties and water repellency and an optical member having the thin film are obtained.

In the method for producing a thin film of the present invention, (a) a water repellent having a perfluoroalkyl group, (b) a silane coupling agent, a modified silicone oil and a perfluoroether having an organic group introduced into the side chain and / or both ends A thin film is formed by vacuum deposition using a mixture with a compound and (c) a water repellent solution obtained by mixing at least one conductive material selected from fullerenes, carbon nanotubes and graphite compounds. .
In the method for producing an optical member of the present invention, a thin film is further formed on the multilayer antireflection film formed on the optical substrate by the above-described thin film production method of the present invention.

The (a) water repellent having a perfluoroalkyl group used in the present invention is not particularly limited as long as it has water repellency and oil repellency, and JP-A 61-130902 and JP-A 58-172246. JP, 58-122979, JP 58-172242, JP 60-40254, JP 50-6615, JP 60-22470, JP 62. No. 148902, JP-A-9-157582, JP-A-9-202648, JP-A-9-263728. 1-100 are preferable and, as for carbon number of a perfluoroalkyl group, 5-20 are more preferable.
Specific examples of the water repellent having a perfluoroalkyl group include compounds represented by the following general formulas (I) to (IV).

[In the formula, Rf is a linear perfluoroalkyl group having 1 to 16 carbon atoms (as an alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), and X is A hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.), R1 is a hydrolyzable group (for example, amino group, alkoxy group) Group) or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), m is an integer of 1-50 (preferably 1-30), n is an integer of 0-2 (preferably 1-2), p Is an integer of 1 to 10 (preferably 1 to 8). ]

C _q F _{2q + 1} CH ₂ CH ₂ Si (NH ₂ ) ₃ (II)
(However, q is 1 or more, preferably an integer of 2 to 20).
Examples of the compound represented by the general formula (II) include n-trifluoro (1,1,2,2-tetrahydro) propylsilazane (n-CF ₃ CH ₂ CH ₂ Si (NH ₂ ) ₃ ), n-heptafluoro ( 1,1,2,2-tetrahydro) Penchirushirazan _{(n-C 3 F 7 CH} 2 CH 2 Si (NH 2) 3), n- Nonafuroro (1,1,2,2-tetrahydro) hexyl disilazane (n- _{C 4 F 9 CH 2 CH 2} Si (NH 2) 3), n- Toridekafuroro (1,1,2,2-tetrahydro) octyl disilazane _{(n-C 6 F 13 CH} 2 CH 2 Si (NH 2) 3) N-heptadecafluoro (1,1,2,2-tetrahydro) decylsilazane (n-C ₈ F ₁₇ CH ₂ CH ₂ Si (NH ₂ ) ₃ ) and the like.

C _{q ′} F _{2q ′ + 1} CH ₂ CH ₂ Si (OCH ₃ ) ₃ (III)
(However, q ′ is 1 or more, preferably an integer of 1 to 20)
Examples of the compound represented by the general formula (III), 2- (perfluorooctyl) ethyltrimethoxysilane _{(n-C 8 F 17 CH} 2 CH 2 Si (OCH 3) 3) or the like can be exemplified.

[In the formula, Rf ′ is a divalent linear oxyperfluoroalkylene group represented by — (C _k F _2k ) O— (k is an integer of 1 to 6), and each R is independently Is a monovalent hydrocarbon group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, etc.), and X ′ can be independently hydrolyzed. A group (for example, amino group, alkoxy group, etc.) or a halogen atom (for example, fluorine, chlorine, bromine, iodine, etc.), n ′ is independently an integer of 0-2 (preferably 1-2), m 'Is independently an integer of 1 to 5 (preferably 1 to 2), and a and b are independently 2 or 3. ]

As commercially available water repellents having a perfluoroalkyl group, KP801M (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KY130 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), X-71-130 Preferable examples include water repellents (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Optur DSX (trade name, manufactured by Daikin Industries, Ltd.).
The amount of the component (a) contained in the water repellent solution used in the present invention is preferably 30 to 90% by weight, more preferably 35 to 80% by weight of the total of the components (a) to (c).

  The component (b) used in the present invention is a mixture of a silane coupling agent, a modified silicone oil in which an organic group is introduced into the side chain and / or both ends, and a perfluoroether compound. Used to ensure thickness. By using the component (b), unlike a conventional water repellent layer, it becomes possible to ensure a thick film thickness without reducing transparency. Increasing the film thickness increases the content of the conductive substance (component (c)) in the thin film, so that an antistatic effect and improved durability can be ensured.

As the silane coupling agent which is component (b), a compound represented by the following general formula (V) is preferably used.
R ¹ _n Si (OR ² ) _4-n (V)
(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms with or without a functional group, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number. 7-10 aralkyl or an acyl group having 2 to 10 carbon atoms, n represents represents 0, 1 or 2, when R ¹ is plural, R ¹ is may be the same with or different from each other, a plurality R ² O may be the same or different.
Of these, aminopropyltrialkoxysilanes such as aminopropyltrimethoxysilane and aminopropyltriethoxysilane are preferably used.

（式中、ｍおよびｎはそれぞれ独立して１以上の整数を表し、“有機基”は

から選ばれる変性基を表し、ｎが２以上の整数の場合、２以上の“有機基”は同一でも異なっていてもよく、Ｒは、炭素数１〜１０の炭化水素基を表し、Ｒ’は、炭素数１〜１０の炭化水素基を表す）。 The modified silicone oil represented by the following general formulas (VI) and (VII) is preferably used as the modified silicone oil in which organic groups are introduced into the side chain and / or both ends as the component (b).
Formula (VI): Side chain modified silicone oil in which organic group is introduced into part of polysiloxane side chain

(In the formula, m and n each independently represent an integer of 1 or more, and “organic group”

In the case where n is an integer of 2 or more, two or more “organic groups” may be the same or different, R represents a hydrocarbon group having 1 to 10 carbon atoms, R ′ Represents a hydrocarbon group having 1 to 10 carbon atoms).

（式中、ｎは１以上の整数を表し、２つの“有機基”は同一でも異なっていてもよく、それぞれ独立して

から選ばれる変性基を表し、Ｒは、炭素数１〜１０の炭化水素基を表し、ａは１〜６の整数、ｂは１〜６の整数を表す）。
上記変性シリコーンオイルのうち、エポキシ変性シリコーンオイルが好ましく用いられる。 Formula (VII): Both-end modified silicone oil having organic groups introduced at both ends of polysiloxane

(In the formula, n represents an integer of 1 or more, and two “organic groups” may be the same or different.

R represents a hydrocarbon group having 1 to 10 carbon atoms, a represents an integer of 1 to 6, and b represents an integer of 1 to 6).
Of the modified silicone oils, epoxy-modified silicone oils are preferably used.

As the perfluoroether compound, a compound represented by the following general formula (VIII) is preferably used.
C _n F _{2n + 1} OC _{n ′} H _{2n ′ + 1} (VIII)
(In the formula, n and n ′ independently represent an integer of 1 or more).
Preferred perfluoroether compounds include perfluorobutyl ether, methyl perfluorobutyl ether, butyl perfluoromethyl ether, propyl perfluoroethyl ether, and the like.

The amount of the component (b) contained in the water repellent solution used in the present invention is preferably 9.5 to 69.5% by weight, and 18.5 to 50% by weight of the total of the components (a) to (c). More preferred. The weight ratio (b) / (a) between the component (b) and the component (a) is preferably 0.7 to 1.1.
The ratio of the silane coupling agent and the modified silicone oil is preferably in the range of 1: 3 to 3: 1 by weight. Moreover, the usage-amount of a perfluoro ether compound has preferable 0.1-0.8 weight part with respect to 1 weight part of total amounts of a silane coupling agent and modified silicone oil.

The component (c) used in the present invention is at least one conductive material selected from fullerenes, carbon nanotubes, and graphite compounds. Fullerenes, Cz (z is an integer of 60 to 120, preferably an integer of 60 to 95) is at least one selected from compounds and their derivatives of the spherical structure or soccer ball structure, in particular C ₆₀ Fullerene, C ₇₂ fullerene and derivatives thereof are preferred. Specific examples of these fullerenes include C ₆₀ H ₆₀ , C ₆₀ H ₂ , C ₆₀ HBr, C ₆₀ (CH ₃ ) ₂ , C ₆₀ H (OH), C ₆₀ H (NH ₂ ), C ₆₀ (CN ) ₂ and compounds of the following formulas (IX), (X), (XI).

Ｘ＝ＣＨ₂：３’Ｈ−シクロプロパ［１，９］（Ｃ₆₀−Ｉ_h）［５，６］フラーレン；
Ｘ＝ＣＨＢｒ：３’−ブロモ−３’Ｈ−シクロプロパ［１，９］（Ｃ₆₀−Ｉ_h）［５，６］フラーレン；
Ｘ＝Ｏ：オキシレノ［１，９］（Ｃ₆₀−Ｉ_h）［５，６］フラーレン；
Ｘ＝ＮＨ：１’Ｈ−アジレノ［１，９］（Ｃ₆₀−Ｉ_h）［５，６］フラーレン、

X = CH _2: 3'H- cyclopropa _{[1,9] (C 60 -I h} ) [5,6] fullerene;
X = CHBr: 3'-Bromo -3'H- cyclopropa _{[1,9] (C 60 -I h} ) [5,6] fullerene;
X = O: oxireno _{[1,9] (C 60 -I h} ) [5,6] fullerene;
X = NH: 1′H-azireno [1,9] (C ₆₀ -I _h ) [5,6] fullerene,

シクロブタ［ｂ］ナフタレノ［１’^，２’：１，９］（Ｃ₆₀−Ｉ_h）［５，６］フラーレン

Cyclobuta [b] naphthaleno [1 ′ ^, 2 ′: 1,9] (C ₆₀ -I _h ) [5,6] fullerene

Ｘ＝ＣＨ₂：１（２）ａ−ホモ（Ｃ₆₀−Ｉ_h）［５，６］フラーレン；
Ｘ＝Ｏ：１ａ−オキサ−１（２）ａ−ホモ（Ｃ₆₀−Ｉ_h）［５，６］フラーレン；
Ｘ＝ＮＨ：１ａＨ−１ａ−アザ−１（２）ａ−ホモ（Ｃ₆₀−Ｉ_h）［５，６］フラーレン
以上の例におけるＣ₆₀はＣ₇₀であっても良い。なお、以上の具体例は、ＩＵＰＡＣ ２００２縮合命名法 によって命名している。

X = CH ₂ : 1 (2) a-homo (C ₆₀ -I _h ) [5,6] fullerene;
X = O: 1a- oxa -1 (2) a- homo _{(C 60 -I h) [5,6} ] fullerene;
X = NH: 1aH-1a- aza -1 (2) a- homo _{(C 60 -I h) [5,6} ] C 60 in the above example fullerenes may be C _70. The above specific examples are named by the IUPAC 2002 condensation nomenclature.

  The carbon nanotube (Carbon nanotube, hereinafter sometimes abbreviated as CNT) of component (c) used in the present invention is a single-layer or multi-layer coaxial tube made of a six-membered ring network (graphene sheet) made of carbon. A single-walled one is called a single wall nanotube (SWNT), and a multi-walled one is called a multi-wall nanotube (MWNT). In particular, the double-walled one is also called double-wall nanotube (DWNT). In the present invention, SWTN and DWNT are preferable among these.

  The (c) component graphite compound used in the present invention is a compound having a graphite structure, and examples thereof include carbon graphite (graphite), fluorinated graphite, and expanded graphite. Carbon graphite (graphite) is a well-known one, and is an allotrope of carbon, in which a benzene ring extends on a two-dimensional plane, and this planar structure has several steps. The plane and the plane are connected by van der Waals coupling, and the plane and the plane are slightly shifted and overlapped. Further, fluorinated graphite is a fluoride of the above carbon graphite, and expanded graphite is produced by chemically treating natural flake graphite and is flame retardant.

  In the present invention, it is preferable that secondary particle processing is performed on commercially available fullerenes, carbon nanotubes, and graphite compounds using an automatic mortar to adjust the particle size. The particle diameter after each adjustment is preferably 80 μm or less, more preferably 50 μm or less, and particularly preferably 20 to 50 μm. If it is 20 μm or more, there is no generation of secondary aggregates, and if it is 80 μm or less, the affinity with the surfactant (dispersant) is good, and carbons do not remain at the time of chip injection. Moreover, in order to set it as the said particle size, 100 rpm or less is preferable and the stirring speed of an automatic mortar is the range of 100-50 rpm. The stirring time is usually 60 minutes or less and preferably 20 to 60 minutes.

The amount of the component (c) contained in the water repellent solution used in the present invention is preferably 0.5 to 30% by weight, and more preferably 1.5 to 15% by weight.

  In addition to the components (a) to (c), the water repellent solution used in the present invention may contain a solvent, a silicon-free perfluoropolyether, and the like. Examples of the solvent include fluorine-based solvents such as m-xylene hexafluoride.

As the silicon-free perfluoropolyether (hereinafter sometimes referred to as “PFPE”), those having various structures can be used. As an example, the following general formula (XII)
-(R'O)-(XII)
(In the formula, R ′ is a perfluoroalkylene group having 1 to 3 carbon atoms.)
The polyether containing the unit represented by these is mentioned. The weight average molecular weight is preferably 1000 to 10,000, more preferably 2000 to 10,000. Specific examples of R ′ include groups such as CF ₂ , CF ₂ CF ₂ , CF ₂ CF ₂ CF ₂ , and CF (CF ₃ ) CF ₂ . These PFPEs are liquid at room temperature and are called so-called fluorine oil.
Examples of commercially available products of PFPE include trade name demnum series (S-20 (average molecular weight 2700), S-65 (average molecular weight 4500), S-100 (average molecular weight 5600), S, manufactured by Daikin Industries, Ltd.) -200 (average molecular weight 8400)), product name Varielta series manufactured by NOK Kluber, product name Fomblin series manufactured by Asahi Glass Co., Ltd., product name KRYTOX series manufactured by DuPont, product name manufactured by Dow Corning Examples include Moricot HF-30 oil.

It is desirable to mix each component contained in the water repellent solution described above while stirring, and the rotation speed of stirring is preferably 200 to 1000 rpm. The stirring time is preferably 2 minutes to 24 hours. Moreover, as a preparation procedure of the water repellent solution, it is desirable to use the procedure shown in Table 1 below. In addition, you may increase / decrease each raw material usage-amount suitably.

The thin film of the present invention is formed by a vacuum deposition method. In addition, in order to improve the film strength and the adhesion between the thin film and the substrate, it is preferable to perform a film formation pretreatment with an ion gun, a plasma gun, or the like.
As a heating source at the time of film formation, any of an electron gun, a halogen heater, resistance heating, a ceramic heater, and the like can be used, but an electron gun is preferable.
The water repellent solution in the present invention may be put in a container and heated as it is, but it is more preferable to impregnate a porous material from the viewpoint that a large number of uniform deposited films can be obtained. As the porous material, it is preferable to use a sintered filter obtained by sintering metal powder having high thermal conductivity such as copper or stainless steel. That is, it is preferable to impregnate a sintered filter made of a porous material with the water repellent solution and heat the sintered filter in a vacuum to form a thin film. Moreover, 40-200 micrometers is preferable and 80-120 micrometers is more preferable from a viewpoint that the moderate vapor deposition rate is obtained for the mesh of a porous material.

In the present invention, the water repellent solution is preferably vapor-deposited on the substrate and the antireflection film formed thereon by heat vapor deposition in which the raw material is heated and vapor-deposited under reduced pressure. The degree of vacuum in the vacuum evaporation apparatus in that case is not particularly limited, but from the viewpoint of obtaining a homogeneous water-repellent film, 1.33 × 10 ⁻¹ to 1.33 × 10 ⁻⁶ Pa (10 ^{− 3} to 10 ⁻⁸ Torr), preferably 6.66 × 10 ^{−1 to} 8.00 × 10 ⁻⁴ Pa (5.0 × 10 ^{−3 to} 6.0 × 10 ⁻⁶ Torr).

  The temperature at which the water repellent solution is heated varies depending on the types of the components (a) to (c) and the vacuum conditions for vapor deposition, but the deposition start temperature of the components (a) to (c) at a desired degree of vacuum. From the above, it is preferable to carry out in a range not exceeding the decomposition temperature of the components (a) to (c). Here, the deposition start temperature refers to the temperature at which the vapor pressure of the solution containing the components (a) to (c) becomes equal to the degree of vacuum, and the decomposition temperature refers to (a) to (c) per minute. The temperature at which 50% of the components are decomposed (under a condition in which no substance reactive with the components (a) to (c) exists in a nitrogen atmosphere).

  Moreover, the vapor deposition rate of the water repellent solution is preferably 4 to 7 nm / min, and the method for achieving the vapor deposition rate is preferably a method of irradiating the water repellent solution with an electron beam. As a method for generating an electron beam, an electron gun conventionally used in a vapor deposition apparatus can be used. If an electron gun is used, the entire water repellent solution can be uniformly irradiated with energy, and a uniform water repellent film can be easily formed. 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 the acceleration voltage is about 6 kV and the applied current is preferably about 5 to 80 mA.

  The optical substrate of the optical member of the present invention is not particularly limited. For example, methyl methacrylate homopolymer, copolymer of methyl methacrylate and one or more other monomers, diethylene glycol bisallyl carbonate homopolymer, diethylene glycol bis Plastic optical substrates such as copolymers of allyl carbonate with one or more other monomers, sulfur-containing copolymers, halogen-containing copolymers, polycarbonate, polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, etc. Or an optical substrate made of inorganic glass. The substrate may have a hard code layer on the substrate. Examples of the hard code layer include a cured film containing an organosilicon compound, an acrylic compound, and the like.

The antireflection film (deposited film) formed on the optical substrate is, for example, ZrO ₂ , SiO ₂ , TiO ₂ , Ta ₂ O used to reduce reflection on the surface of the optical substrate such as a lens. ₅ , a single layer or a multilayer film formed from Y ₂ O ₃ , MgF ₂ , Al ₂ O ₃ or the like, and a colored film formed from CrO ₂ or the like. In addition, 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.

As a specific example of the layer configuration of the antireflection film, a film composed of the following seven layers in order from the substrate side to the air side is preferably exemplified.
First layer: a hybrid layer formed using an organic silicon compound that is liquid at normal temperature and pressure and / or a silicon-free organic compound that is liquid at normal temperature and pressure and an inorganic material containing silicon dioxide as a deposition material. Layer: Layer containing at least 50% by weight of tantalum oxide Third layer: Organosilicon compound that is liquid under normal temperature and normal pressure and / or silicon-free organic compound that is liquid under normal temperature and pressure and silicon dioxide Hybrid layer formed using an inorganic substance as a deposition material Layer 4: Layer containing at least 50% by weight of tantalum oxide Layer 5: Organosilicon compound that is liquid at room temperature and pressure and / or Liquid at room temperature and pressure A hybrid layer formed using a silicon-free organic compound and an inorganic substance containing silicon dioxide as a deposition material. Sixth layer: tantalum oxide Layer containing at least 50% by weight Seventh layer: An organic silicon compound that is liquid under normal temperature and pressure and / or a silicon-free organic compound that is liquid under normal temperature and pressure, and an inorganic substance containing silicon dioxide Hybrid layer formed as an evaporation source

  Examples of the organosilicon compound in the antireflection film include compounds represented by the following general formulas (a) to (d).

General 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 a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms (including both saturated and unsaturated), —OR ¹ group, —CH ₂ OR ² group, and —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 are hydrogen atoms or carbon atoms having 1 to 6 carbon atoms) Represents a hydrogen group (including both saturated and unsaturated groups) Examples of the hydrocarbon group represented by X _{1 to} X ₈ and R ^{1 to} R ⁸ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, An n-butyl group etc. are mentioned.

  Examples of the silicon-free organic compound in the antireflection film include compounds represented by the following general formulas (e) to (g).

General formula (e): Silicon-free organic compound having an epoxy group at one end and containing carbon and hydrogen as essential components

General formula (f): silicon-free organic compound having an epoxy group at both ends and containing carbon and hydrogen 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 a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may contain oxygen, and R ¹⁰ has 1 to 1 carbon atoms which may contain oxygen. 7 represents a divalent hydrocarbon group. In the general formula (g), X _{9 to} X ₁₂ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms, a hydrogen atom as an essential component, and oxygen and An organic group containing at least one of nitrogen as an essential component is represented.
Examples of the hydrocarbon group represented by R ⁹ and X _{9 to} X ₁₂ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
Examples of the divalent hydrocarbon group represented by R ¹⁰ include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and an n-butylene group.
Examples of the organic group represented by X _{9 to} X ₁₂ include an amino group, an epoxy group, a carboxyl group, and a polyether group.
The optical member obtained by the production method of the present invention is preferably a plastic lens.

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 Y The luminous transmittance Y of a plastic lens was measured using Hitachi spectrophotometers U-4100 and U-3410 using a plastic lens having an antireflection film on both sides as a sample.

(2) Luminous reflectance Z Luminous reflectance Z of a plastic lens was measured using Hitachi spectrophotometers U-4100 and U-3410 using a plastic lens having an antireflection film on both sides as a sample.

(3) Impact resistance A lens having a lens center thickness of 1.0 mm or 2.0 mm (denoted as CT) and a lens power of 0.00D (diopter) was prepared to produce FDA (Food and Drug). The drop ball test specified in Administration was conducted and evaluated according to the following criteria.
○: Pass ×: Fail In addition, the weight of the ball was 16 g. The criteria for the acceptance was that after the drop ball test, when the lens was wrinkled or cracked, it was rejected, and when the lens appearance was not changed from that before the drop ball test.

(4) Adhesion 100 squares of 1 mm x 1 mm were made with a razor on the surface of the plastic lens, cellophane tape (manufactured and sold by Nichiban Co., Ltd.) was pasted on the squares, the tape was peeled off at once, and the residual rate of the squares (remaining The number of squares / 100) was evaluated.

(5) Abrasion resistance The surface of the plastic lens was subjected to a load of 1 kgf / cm ² (0.1 Mpa) with steel wool (standard # 0000, manufactured by Nippon Steel Wool Co., Ltd.) and rubbed for 10 strokes depending on the surface condition. Evaluation was made according to the following 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% by weight NaOH aqueous solution at 20 ° C for 1 hour, and evaluated according to the following criteria depending on the surface condition.
UA: Almost no change A: Several point-shaped film baldnesses B: Point-shaped film baldness on the entire surface C: Point-shaped film baldness on the entire surface, several sheet-shaped film baldness D: Almost all surface film baldness

(8) Bayer value Using a wear tester BTE Abrasion Tester (trade name, manufactured by COLTS, USA) and a haze value measuring device (Murakami Color Research Laboratory Co., Ltd.), the Bayer value varies depending on the difference in haze value from the reference lens. The value was measured.
(Number of samples, measuring method)
(a) Prepare three reference lenses (CR39 base material) and three sample lenses.
(b) Measurement of haze value before wear test.
(c) Abrasion test with BTE Abrasion Tester. (Surface wear due to sand 600 round trips)
(d) Measurement of haze value after abrasion test.
(e) Bayer value calculation (assuming average value for 3 sheets)
(Bayer value = change in transmittance of reference lens / change in transmittance of sample lens)

(9) Charging voltage Using tissue paper, the convex surface of the plastic lens was rubbed 100 times by hand, and the charging voltage at that time was measured using an electrostatic meter FMX-002 (manufactured by Simco Japan (trade name)). Since the charging voltage changes with time, after rubbing 100 times, the charging voltage after 5, 10, 20, 40, 80, 160, 320 seconds is measured, and the result is fitted with V ₁ = V ₀ exp (−at). did. Here, V ₁ , V ₀ , 1 / a, and t are a charging voltage (V), an estimated initial charging voltage (V), a 1 / a delay period (second), and an elapsed time (second), respectively.
From this result, the presence or absence of an antistatic effect was judged according to the following criteria.
V ₀ ≦ 300 V and 1 / a ≦ 50 seconds: antistatic effect V ₀ > 300 V, or 1 / a> 50 seconds: no antistatic effect

(10) Measurement of treatment liquid (water repellent solution) conductivity The resistance value of the treatment liquid (water repellent solution) dropped on the glass was measured with a tester to measure the conductivity of the treatment liquid. 0.2 cc of the treatment liquid was dropped on a slide glass, spread into a circle having a diameter of 10 mm, and the resistance value was measured at a tester probe spacing of about 5 mm before drying.
The antistatic effect of the treatment liquid was judged according to the following criteria.
Measurement value: 10 MΩ or less: sufficient antistatic effect is obtained.
Measured value> 10 MΩ: Antistatic effect is insufficient.

(11) Water repellency The water contact angle was measured with a Kyowa Interface Science contact angle meter.

A water repellent solution was prepared as follows. The properties of the raw materials used for the preparation of the water repellent solution are shown below.
(A) component: water repellent having a perfluoroalkyl group KY130: manufactured by Shin-Etsu Chemical Co., Ltd. water repellent (b) component: silane coupling agent, modified silicone oil, perfluoroether compound KBE903: Shin-Etsu Chemical ( Silane coupling agent (containing amino group)
KF101: Modified silicone oil (side-chain epoxy-modified) manufactured by Shin-Etsu Chemical Co., Ltd.
KF105: Shin-Etsu Chemical Co., Ltd. modified silicone oil (both ends epoxy modified)
HFE7100: Sumitomo 3M Limited perfluoroether compound HFE7200: Sumitomo 3M Limited perfluoroether compound

ＫＦ１０５：

ＨＦＥ７１００：Ｃ₄Ｆ₉ＯＣＨ₃
ＨＦＥ７２００：Ｃ₃Ｆ₇ＯＣ₂Ｈ₅ Structural formulas of the silane coupling agent, modified silicone oil, and perfluoroether compound are shown below.
_{KBE903: (C 2 H 5 O} ) 3 SiC 3 H 6 NH 2
KF101:

KF105:

HFE7100: C ₄ F ₉ OCH _{3
HFE7200: C 3 F 7 OC 2} H 5

(C) Component: Conductive substance CNT: Carbon nanotube made by Honjo Chemical (initial particle size: 2 to 20 nm)
C60 and C70: Kanto Science Carbon Cluster (initial particle size: 5 nm)
CBG: Conductive carbon black # 3855 (initial particle size: 24 nm) manufactured by Tokai Carbon
These conductive materials were adjusted to a particle size of 20 to 50 μm using an automatic mortar.

Production Example 1 (Preparation of treatment liquid)
1. 1.0 g of pulverized CNT (CBG or C60 / C70) was put into a glass container in which a stirrer was inserted. Here, the notation “CNT (CBG or C60 / C70)” indicates that CBG or C60 and / or C70 may be used instead of CNT, and the same effect is obtained.
2. Next, 4 g of KBE903 was poured into the glass container and stirred for 120 seconds. The rotation speed of the stirring bar was 500 rpm.
3. Next, 4 g of KF105 was poured into the container and stirred for 24 hours.
The mixture of 1 to 3 is referred to as filler A.
4. After stirring for 120 minutes, 3.5 g of filler A was injected into 7.0 g of water repellent KY130 prepared in a separate container, and stirred for 120 seconds.
5. Next, 3 g of HFE7200 as a perfluoroether compound was poured into the glass container and stirred for 24 hours to prepare a treatment liquid (water repellent solution). The carbon ratio (content of CNT (CBG or C60 / C70)) in the solid content was 7.91% by weight.
The above procedure is shown in Table 1.

Examples 1-5 and Comparative Examples 1-4
As described in Table 2-1 / 5 to 5/5 and Table 3-1 / 4 to 4/4, cured films A to B are formed on the plastic lens base materials A to D (Step 1). After the pretreatment ion irradiation (step 2), an antireflection film consisting of the first to seventh layers is provided (step 3), after the pretreatment ion irradiation (step 4), a thin film (water repellent + charged) Prevention layer) was formed (Step 5) to obtain a plastic lens having a water repellent and antistatic layer.

The types of materials used in the examples and comparative examples, manufacturing methods, and various treatment methods are as follows.
Plastic lens substrate A: Diethylene glycol bisallyl carbonate, refractive index 1.50, center thickness 2.0 mm, lens power 0.00
Base material B: EYRY base material (trade name, manufactured by HOYA Co., Ltd., polymer using a compound having an epithio group) Refractive index 1.70, center thickness 1.0 mm, lens power 0.00
Base material C: EYNOA base material (trade name, manufactured by HOYA Co., Ltd., polythiourethane resin) Refractive index 1.67, center thickness 1.0 mm, lens power 0.00

In Example 2, a primer layer was applied between the substrate and the cured coating. The method for forming the primer layer is as follows.
Polyester type polyol (Sumitomo Bayer Urethane Co., Ltd., using Desmophen A-670 (trade name)) 6.65 parts by weight, Block type polyisocyanate (Sumitomo Bayer Urethane Co., Ltd., using BL-3175 (trade name)) 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 (using Sumitomo 3M, Florard FC-430 (trade name)) as a leveling agent, and diacetone alcohol as a solvent The mixture consisting of 95.71 parts by weight was sufficiently stirred until it became uniform. The liquid primer thus obtained was applied on an alkali pretreated plastic lens substrate by a dipping method (pickup speed: 24 cm / min) and cured by heating at 100 ° C. for 40 minutes to form a primer layer having a thickness of 2 to 3 μm. Formed.

Step 1: Formation of cured film (1-1) Production of coating composition A Under an atmosphere of 5 ° C., 45 parts by weight of modified stannic oxide-zirconium oxide-tungsten oxide-silicon oxide complex methanol sol and γ-glyce Sidoxypropyltrimethoxysilane (15 parts by weight) and tetraethoxysilane (3 parts by weight) were mixed and stirred for 1 hour. Thereafter, 4.5 parts by weight of 0.001 mol / L hydrochloric acid was added and stirred for 50 hours. Thereafter, 25 parts by weight of propylene glycol monomethyl ether, 9 parts by weight of diacetone alcohol, 1.8 parts by weight of aluminum trisacetylacetonate, and 0.05 parts by weight of aluminum perchlorate were sequentially added as a solvent and stirred for 150 hours. The obtained solution was filtered with a 0.5 μm filter to obtain a coating composition A.

(1-2) Production of cured film A The substrate A was immersed in an aqueous solution of sodium hydroxide at 60 ° C. and 10% by weight for 300 seconds, and then washed with ion-exchanged water for 300 seconds while applying an ultrasonic wave of 28 kHz. did. Finally, a series of steps for drying in a 70 ° C. atmosphere was used as a substrate pretreatment.
The pretreated substrate A is dipped in the coating composition A for 30 seconds by the dipping method, pulled up at 30 cm / min, and then cured by curing the coating composition A at 120 ° C. for 60 minutes. Membrane A was prepared.

(1′-1) Preparation of Coating Composition B While stirring 100 parts by weight of γ-glycidoxypropyltrimethoxysilane, 1.4 parts by weight of 0.01 mol / L hydrochloric acid and 23 parts by weight of water were added. The mixture was stirred for 24 hours to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane. Next, 200 parts by weight of a composite fine particle sol mainly composed of titanium oxide, zirconium oxide, and silicon oxide, 100 parts by weight of ethyl cellosolve, 0.5 parts by weight of a silicone-based surfactant, and 3.0 parts by weight of aluminum acetylacetonate Were mixed, added to the hydrolyzate of γ-glycidoxypropyltrimethoxysilane, sufficiently stirred, and then filtered to obtain a coating composition B.

(1'-2) Preparation of cured film B Substrate B or substrate C pretreated with an alkaline aqueous solution was immersed in coating composition B for 30 seconds by dipping and pulled up at 20 cm / min, followed by coating. The composition B was cured under the conditions of 120 ° C. and 120 minutes to prepare a cured film B.

Process 2: Ion gun treatment (pretreatment) of cured film
On the cured film, ion irradiation was performed with an ion gun as pretreatment under the conditions of ion acceleration voltage, irradiation time, and gas atmosphere described in the table.

Step 3: Preparation of antireflection film Pretreatment After ion irradiation, an antireflection film comprising the first to seventh layers was formed.
Note that the conditions were set so that the hybrid layer was deposited almost simultaneously as binary deposition of inorganic material and organic material. 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.

In the table, CM1 represents an organosilicon compound, and CM2 represents a silicon-free organic compound. The organic compounds described in the table are as follows.
Epolite 70P (propylene glycol diglycidyl ether, molecular weight of about 188, manufactured by Kyoeisha Chemical Co., Ltd.)
Denacol EX920 (polypropylene glycol diglycidyl ether, molecular weight of about 300, manufactured by Nagase ChemteX Corporation)
Epiol P200 (polypropylene glycol glycidyl ether, average molecular weight of about 304, manufactured by NOF Corporation)

Process 4: Anti-reflective film ion gun treatment (pretreatment)
On the antireflection film, ion irradiation was performed with an ion gun as pretreatment under the conditions of ion acceleration voltage, irradiation time, and gas atmosphere described in the table.

Step 5: Formation of thin film (water repellent + antistatic layer) First, a film-forming chip was prepared using the treatment liquid prepared in Production Example 1. Chips are prepared by injecting the above treatment liquid into an SUS biocolumn using a dispenser at an injection volume of 0.3 cc and drying at room temperature (or dry oven) at 80 ° C. for about 2 hours. I got a chip.
Using the obtained chip, an EB (electron gun) was used, and a thin film was formed on the antireflection film by vacuum deposition. The film forming conditions are as follows.
Vapor deposition equipment: BMC-1050-HP (manufactured by Syncron Co., Ltd.)
Film forming condition: Degree of starting vacuum 2 × 10 ⁻³ Pa
EB output during film formation: 20 mA
In addition, DOTITE D-550 (made by Fujikura Kasei Co., Ltd. (product name)) used in the comparative example is a silver-based conductive paste, and DOTITE XC-12 (made by Fujikura Kasei Co., Ltd. (product name)) is a carbon-based conductive material. KP801P is a water repellent manufactured by Shin-Etsu Chemical Co., Ltd.

The plastic lens having the thin film obtained as described above was subjected to the tests (1) to (11). The results are shown in Table 4 -1/2 to 2/2.
As shown in Table 4, the electrical conductivity of the processing solutions for the plastic lenses of Examples 1 to 5 is 10 MΩ or less and the initial charging voltage is 300 V or less, and has excellent antistatic performance. The contact angle was 107 ° C. or higher.

  As described above in detail, according to the production method of the present invention, the lens is not colored, and a thin film and an optical member having good antistatic properties and water repellency can be obtained. For this reason, it is extremely useful as a plastic lens or the like.

Claims (14)

(A) a water repellent having a perfluoroalkyl group, (b) a mixture of a silane coupling agent, a modified silicone oil having an organic group introduced into the side chain and / or both ends, and a perfluoroether compound, and (c) A method for producing a thin film, wherein a thin film is formed by a vacuum deposition method using a water repellent solution obtained by mixing at least one conductive material selected from fullerenes, carbon nanotubes, and graphite compounds. 2. The method for producing a thin film according to claim 1, wherein the perfluoroether compound is represented by the following general formula (VIII).
C _n F _{2n + 1} OC _{n ′} H _{2n ′ + 1} (VIII)
(In the formula, n and n ′ independently represent an integer of 1 or more). The method for producing a thin film according to claim 1 or 2, wherein the silane coupling agent is represented by the following general formula (V).
R ¹ nSi (OR ² ) _4-n (V)
(In the formula, R ¹ is a monovalent hydrocarbon group having 1 to 20 carbon atoms with or without a functional group, R ² is an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a carbon number. 7-10 aralkyl or an acyl group having 2 to 10 carbon atoms, n represents represents 0, 1 or 2, when R ¹ is plural, R ¹ is may be the same with or different from each other, a plurality R ² O may be the same or different. The method for producing a thin film according to claim 3, wherein the silane coupling agent is aminopropyltrialkoxysilane. The method for producing a thin film according to claim 4, wherein the aminopropyltrialkoxysilane is aminopropyltrimethoxysilane or aminopropyltriethoxysilane. The manufacturing method of the thin film in any one of Claims 1-5 by which the modified silicone oil which introduce | transduced the organic group into the said side chain and / or both terminal is represented by the following general formula (VI) or (VII).

The fullerenes, Cz (z is an integer of 40 to 120) The method of manufacturing a thin film according to any one of claims 1 to 6 at least one selected from compounds having the spherical structure of. The method for producing a thin film according to claim 7, wherein the fullerene is at least one selected from compounds having a spherical structure of C ₆₀ and C ₇₂ . The method for producing a thin film according to claim 1, wherein the carbon nanotubes are at least one kind selected from multi-walled carbon nanotubes (MWNT) and single-walled carbon nanotubes (SWNT). The method for producing a thin film according to claim 1, wherein the graphite compound is at least one selected from carbon graphite, fluorinated graphite, and expanded graphite. The method for producing a thin film according to claim 1, wherein the fullerenes, the carbon nanotubes, and the graphite compound each have a particle size of 80 μm or less. The method for producing a thin film according to claim 1, wherein the water repellent solution is impregnated into a sintered filter made of a porous material, and the sintered filter is heated in vacuum to form a thin film. Modified silicone oil in which (a) a water repellent having a perfluoroalkyl group, (b) a silane coupling agent, and side groups and / or organic groups are introduced into both ends on a multilayer antireflection film formed on an optical substrate And a mixture of a perfluoroether compound and (c) a water repellent solution formed by mixing at least one conductive material selected from fullerenes, carbon nanotubes, and graphite compounds, by a vacuum deposition method. A method for producing an optical member for forming a thin film. The method of manufacturing an optical member according to claim 13, wherein the optical member is a plastic lens.