JP2003255107A - Hybrid thin film, antireflection film and optical member comprising the same, and method for restoring defogging performance of hybrid thin film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hybrid thin film excellent in wear resistance and defogging performance, to provide an antireflection film and an optical member comprising the above film, and to provide a method for restoring the defogging performance of the hybrid thin film, a method for manufacturing the hybrid thin film and a method for manufacturing the optical member. <P>SOLUTION: The hybrid thin film having defogging performance is obtained by vapor depositing an organic compound having a hydrophilic group and a reactive group along with silicon dioxide or with silicon dioxide and aluminum oxide. The antireflection film has the above hybrid thin film as the outermost layer of the antireflection film. The optical member comprises a plastic substrate and an antireflection film and has the above hybrid thin film applied as the outermost layer of the antireflection film on a basis of the substrate. In the method for restoring defogging performance of the hybrid thin film, the defogging performance is restored by washing the hybrid thin film of the optical member. The present invention also presents the method for manufacturing the hybrid thin film and the method for manufacturing the optical member. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hybrid thin film, an antireflection film and an optical member using the same, a method of restoring the antifogging performance of the hybrid thin film, a method of manufacturing the hybrid thin film and a method of manufacturing the optical member, and more particularly, The present invention relates to a hybrid thin film having excellent wear resistance and antifogging property, an antireflection film and an optical member using the same, a method for restoring the antifogging performance of the hybrid thin film, a method for manufacturing the hybrid thin film, and a method for manufacturing the optical member.

[0002]

2. Description of the Related Art Conventionally, an optical member having an antireflection film formed by applying an inorganic vapor deposition material has been known. It is also known that this optical member has poor antifogging characteristics. In order to solve this problem, a thin film having an antifogging property and an antireflection property has been proposed. For example, in Patent Document 1,
A spectacle lens has been proposed in which a coating material containing a porous inorganic oxide and a specific siloxane oligomer is applied on a spectacle lens substrate to form a thin film having antifogging properties and antireflection properties. However, the antifogging lens proposed in the publication is not sufficient in abrasion resistance as compared with an antireflection film made of a vapor deposition material which is usually used for spectacle lenses. Furthermore, the antireflection performance is not sufficient.

[Patent Document 1] Japanese Patent Publication No. 10-510860

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and its object is to provide a hybrid thin film having excellent wear resistance and antifogging performance, and an antireflection film using the same. Another object of the present invention is to provide an optical member, a method for restoring anti-fogging performance of a hybrid thin film, a method for manufacturing a hybrid thin film, and a method for manufacturing an optical member.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that an organic compound having a hydrophilic group and a reactive group, silicon dioxide, or silicon dioxide and aluminum oxide. By using the hybrid thin film obtained by vapor-depositing a film, an optical member having excellent wear resistance and antifogging performance can be obtained, and when the contact angle of the hybrid thin film with water is less than 10 degrees, the hybrid thin film has an antifogging property. The inventors have found that they exhibit performance and completed the present invention. That is, the present invention provides a hybrid thin film having an antifogging property obtained by vapor-depositing an organic compound having a hydrophilic group and a reactive group, and silicon dioxide, or silicon dioxide and aluminum oxide, and the hybrid thin film as an outermost layer of an antireflection film. An optical member comprising an antireflection film provided with an antireflection film, and a plastic substrate, and an antireflection film provided with the hybrid thin film on the plastic substrate, wherein the substrate side is used as a reference for reflection. An optical member provided with the hybrid thin film as the outermost layer of an anti-foaming film, a method for restoring the anti-fog performance of a hybrid thin film that restores the anti-fog performance by washing the hybrid thin film in the optical member, and an organic compound having a hydrophilic group and a reactive group. Method for producing the hybrid thin film, which comprises depositing a compound and silicon dioxide, or silicon dioxide and aluminum oxide And based on the base material side,
The present invention provides a method for manufacturing the optical member, wherein the hybrid thin film is applied as the outermost layer of the antireflection film.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The hybrid thin film of the present invention comprises an organic compound having a hydrophilic group and a reactive group, silicon dioxide,
Alternatively, it is formed by vapor deposition of silicon dioxide and aluminum oxide. As described above, the hybrid thin film of the present invention contains a hydrophilic organic compound having a hydrophilic group in the silicon dioxide layer or the mixed layer of silicon dioxide and aluminum oxide, so that the organic compound is substantially It plays the role of a hydrophilic group in the surfactant (surfactant), while silicon dioxide or a mixture of silicon dioxide and aluminum oxide is inferior in hydrophilicity to the organic compound, so that it is pseudo hydrophobic in the surfactant. By acting as a base, the hybrid thin film exhibits an anti-fogging function by having properties similar to those of the layer substantially composed of the surfactant. Further, since the hybrid thin film is formed by vapor deposition, it is easy to control the film thickness, and since a reactive organic compound is added to silicon dioxide for vapor deposition to form a cross-linked structure, abrasion resistance is improved.

The hybrid thin film of the present invention is preferably vapor-deposited by an ion assisted method of forming a film in a gas atmosphere. The ion assist method is conventionally known, for example, M. F.
lindner et al., Society of Vacuum Coaters Albuquer
que, NM, USA p 237-241, 1995 and the like. Preferable processing conditions in the ion assist method are an acceleration voltage of 50 V to 150 V and an acceleration current of 30 mA.
It is in the range of 100 mA. It is preferable to use argon (Ar) or an argon / oxygen mixed gas as the ionized gas when carrying out the ion assist method from the viewpoint of reactivity during film formation and oxidation prevention. As a method for forming the hybrid thin film in the present invention, it is preferable that the organic compound and silicon dioxide, or silicon dioxide and aluminum oxide are separately vapor-deposited and vapor-deposited at the same time. Further, in order to control the vapor deposition amount of the organic compound, it is preferable to use one obtained by diluting the organic compound with a solvent and impregnating and diluting a diluting solution in a biocolumn filter. In this case, the solvent is not particularly limited, but dimethyl ether when an organic compound of a terminal amine type is used, ethyl acetate when an organic compound of a terminal epoxide type is used, and trimethylethylsilane or diethyl ether when a polysiloxane type organic compound of low polarity is used. In the case of a highly polar polyether organic compound, methanol is preferably used.

The formation of a hybrid thin film has high viscosity,
For compounds whose boiling point is difficult or impossible to measure, it is preferable to heat a porous material as a container and deposit the organic compound on the film-forming target by vapor deposition. The film thickness can be controlled by dissolving an organic substance in a solvent and adjusting the amount of this solution. Moreover, it is possible to obtain an appropriate vapor deposition rate by impregnating the porous material with the solution and heating it. As the porous material, more specifically, it is preferable to use a sintered filter obtained by sintering a metal powder having high thermal conductivity such as copper. The pore size of the porous material is usually 4 in order to obtain an appropriate deposition rate.
The thickness is preferably 0 to 200 μm, and more preferably 80 to 120 μm. The heating temperature of the container is usually 200 to 300 ° C., preferably 200 to 240 ° C., from the viewpoint of obtaining an appropriate vapor deposition rate. The heating device is not particularly limited, but for example, a halogen heater, a resistance heating device, a ceramic heater or the like can be used. The heating device preferably has a shutter mechanism for film formation control. Also,
At the time of heating, it is preferable to surround the heating device in order to prevent the film-forming material from being contaminated due to the scattering of the film-forming material. In order to stably supply the film-forming substance during film-forming, it is preferable to provide a film-forming amount adjusting chamber that covers the biocolumn filter and has a small-diameter hole. The shape of the holes is preferably elliptical in order to improve the distribution directivity of the organic compound to be formed into a film. Further, the viscosity is relatively low (for example, 1.
5 × 10 ⁻⁵ m ² / s (15 cst) or less), for those whose boiling point is known, an external tank is heated to 50 ° C. to 150 ° C., introduced as a monomer gas into a vacuum chamber, and the organic compound is used. It is preferable to form a film on the film-forming target by vapor deposition. In this case, the film thickness and the addition amount can be controlled by directly adjusting the flow rate of the organic compound from the external tank.

The organic compound used in the hybrid thin film has a ratio of the number of oxygen atoms to the number of moles of the organic compound in the organic compound of 18 to 40% in order to impart better antifogging properties. Is preferred. The number average molecular weight of the organic compound is 15
It is preferably 0 to 1500 g / mol. The content of the structure derived from the organic compound in the hybrid thin film of the present invention is preferably 0.02 to 70% by weight based on the total weight of the thin film.

The organic compound used in the hybrid thin film of the present invention preferably has a structure represented by the following general formulas (Ia) to (V). (Re-) nHy, (Re-L-) nHy (Ia), (Ib) Re (-Hy) m, Re (-L-Hy) m (IIa), (IIb) (Re-) n L (- Hy) m (III) (Re-) nHy (-L) o (IV) (L-) oRe (-Hy) m (V) (In the formula, Re is a reactive group, Hy is a hydrophilic group, and L is a carbon number. 1 to
3 represents a (non-hydrophilic and non-reactive) linking group which is a hydrocarbon group of 3, n is 1 or 2, m is an integer of 1 or more, and o is 1 or 2. ) The hydrophilic group in the organic compound used in the hybrid thin film of the present invention is defined as follows. That is, when the solubility in water (25 ° C.) of a compound derived by binding a certain group to a methyl group exceeds 90% (v / V), the group is called a hydrophilic group. Examples of preferable hydrophilic groups include -SO ₃ H, -SO ₃ M,-
OSO ₃ H, -OSO ₃ M, -COOM, -NR ₃ X, -COOH, -NH ₂ , -C
N, -OH, -NHCONH2, - ( OCH 2 CH 2) p -, - CH 2 O CH3,
-OCH3, -COOCH3, -CS, -CON (where R: carbon number 1-2)
Alkyl group, M: alkali metal or NH ₄ , X: halogen, p is an integer of 1 or more) and the like. The organic compound containing the hydrophilic group is preferably a hydrophilic compound. The hydrophilic compound is determined by measuring the contact angle to water between the surface of the thin film obtained by curing the organic compound and water droplets, and the contact angle is 10
When it is less than the degree, it is said to be a hydrophilic compound. Also,
More preferably, the organic compound has a higher hydrophilicity than silicon dioxide and / or aluminum oxide. in this case,
The hydrophilicity of each component is also determined and compared based on the contact angle between the thin film made of each pure substance and the water droplet.
The reactive group in the organic compound used in the hybrid thin film of the present invention is defined as the group itself or a group capable of reacting with silicon dioxide and / or aluminum oxide in the hybrid thin film. Examples of preferred reactive groups include
Epoxy group, methacrylic group, acrylic group, amino group, thiol group, trialkoxysilyl group having 3 to 15 carbon atoms,
Examples thereof include a hydroxyl group.

The organic compound used in the hybrid thin film of the present invention includes a compound having a polyether main chain structure and having a reactive group at both ends of the main chain, a repeating unit of hydroxymethylene, and A compound having a reactive group at both ends of the repeating unit, a compound having a repeating unit of carboxymethylene and a reactive group at both ends thereof, and the like are preferable.

Examples of the compound having the polyether main chain structure and having reactive groups at both ends of the main chain include compounds represented by the following general formula (1).

[Chemical 3] (In the formula, R ₁ and R ₂ are each independently an epoxy group,
An organic group containing at least one kind of group selected from a methacrylic group, an acryl group, an amino group, a thiol group, a trialkoxysilyl group having 3 to 15 carbon atoms, a hydroxyl group or these (the organic group is the functional group described above. It is preferable that at least one of them is composed of a hydrocarbon group having 1 to 3 carbon atoms. N is an integer of 1 or more and has a number average molecular weight of 15
It is an integer in the range of 0 to 1500 g / mol. )

As the compound having the repeating unit of hydroxymethylene and having reactive groups at both ends of the repeating unit, a compound represented by the following general formula (2) has the repeating unit of carboxymethylene. However, examples of the compound having a reactive group at both ends thereof include a compound represented by the following general formula (3).

[Chemical 4] (In the formula, R ₃ , R ₄ , R ₅ and R ₆ are each independently an epoxy group, a methacrylic group, an acryl group, an amino group, a thiol group, a trialkoxysilyl group having 3 to 15 carbon atoms, a hydroxyl group or these. Represents an organic group containing at least one kind of group selected from the group, and m and k are each 2
With the above integer, the number average molecular weight is 225 to 1500 g / mo.
It is an integer that becomes l. The organic compound used in the hybrid thin film of the present invention may be a combination of the above-mentioned organic compounds.

If desired, a crosslinking agent may be added to the organic compound used in the hybrid thin film of the present invention. As the cross-linking agent, a quaternary silane such as tetraalkoxysilane (alkoxy group having 1 to 2 carbon atoms) or tetraaminosilane can be used. The preferable addition amount of the crosslinking agent is 1 to 20 with respect to the total amount of the organic compound used.
% By weight.

The hybrid thin film of the present invention can be used as a low refractive index layer in an antireflection film having a multilayer structure. In the multilayer antireflection film, if the hybrid thin film is applied to the outermost layer based on the base material side, an antireflection film and an optical member having excellent wear resistance, antifogging performance and antireflection performance can be obtained. The film thickness of the hybrid thin film of the present invention is not particularly limited, but is preferably 5 to 100 nm. When the hybrid thin film is used as the low refractive index layer which is the outermost layer of the multilayer antireflection film, the optical film thickness (λ /
It is also possible to use the same optical film thickness as in 4) (λ indicates the wavelength of irradiation light). In that case, the hybrid thin film preferably has a refractive index of 1.42 to 1.48.

Further, the hybrid thin film of the present invention can be provided in the layer closest to the substrate side in order to improve impact resistance. When the hybrid thin film is provided in the layer closest to the base material side, it is possible to provide an underlayer to improve the adhesion between the hybrid thin film and the base material. As the underlayer, a metal having a catalytic action when forming a hybrid thin film,
For example, nickel (Ni), silver (Ag), platinum (P
t), at least one layer selected from niobium (Nb) and titanium (Ti) can be applied.
A particularly preferable underlayer is a metal layer made of niobium in order to impart better impact resistance. When the metal layer is used as the underlayer, impact resistance is improved. Further, in order to secure the adhesion between the plastic substrate and the underlayer and make the initial film formation state of the vapor deposition material uniform, an ion gun pretreatment may be performed before forming the underlayer. Oxygen, argon (Ar), or the like can be used as the ionized gas in the ion gun pretreatment, and the preferable range for the output is an acceleration voltage of 50 V to 50% from the viewpoint of obtaining particularly good adhesion and wear resistance.
The voltage is 200 V and the acceleration current is 50 mA to 150 mA.

Antireflection other than the hybrid thin film of the present invention
The film is preferably formed by a vapor deposition method, and if necessary,
Physical vapor deposition method (PVD method), chemical vapor deposition method (CVD
Method), sputtering method, ion plating method, plating method
It can also be formed by a plasma CVD method or the like. Anti-reflection
The layers other than the hybrid thin film in the stop membrane are not particularly limited.
However, in order to obtain a good antireflection effect, a low refractive index layer
Then SiO₂Layer or SiO₂And Al ₂O₃Mixed layer with high
Nb as a refractive index layer₂O_FiveLayer or TiO₂With layers
It is preferable.

The optical member of the present invention comprises a plastic base material and an antireflection film obtained by applying the hybrid thin film of the present invention on the plastic base material. The material of the plastic substrate used in the optical member of the present invention is not particularly limited, and examples thereof include methyl methacrylate homopolymer, copolymers of methyl methacrylate and one or more other monomers. , Diethylene glycol bisallyl carbonate homopolymer, copolymers of diethylene glycol bisallyl carbonate with one or more other monomers, sulfur-containing copolymers, halogen copolymers, polycarbonates , Polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, polythiourethane and the like.

The optical member of the present invention may have a cured coating between the plastic substrate and the antireflection film provided with the hybrid thin film, or between the plastic substrate and the underlayer. Good. As the cured film, usually, metal oxide colloidal particles and the following general formula (I) (R ₇ ) _a (R ₈ ) _b Si (OR ₉ ) _{4- (a + b)} (I) (wherein , R ₇ and R ₈ each independently have 1 to 8 carbon atoms.
Alkyl group, C2-C8 alkenyl group, C6
To an aryl group having from 8 to 8 carbon atoms, an acyl group having from 1 to 8 carbon atoms, a halogen atom, a glycidoxy group, an epoxy group, an amino group, a mercapto group, a methacryloxy group and a cyano group, and R ₉ is a carbon number. 1 to 8 represents an organic group selected from an alkyl group, a C1-8 acyl group, and a C6-8 aryl group, and a and b are each independently an integer of 0 or 1.) A composition comprising the organosilicon compound represented may be used.

Examples of the metal oxide colloidal particles include tungsten oxide (WO ₃ ) and zinc oxide (Zn oxide).
O), silicon oxide (SiO ₂ ), aluminum oxide (A
l ₂ O ₃ ), titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), tin oxide (SnO ₂ ), beryllium oxide (BeO), antimony oxide (Sb ₂ O ₅ ), etc., and they may be used alone or in combination. The above can be used together.

Preferred examples of the organosilicon compound represented by the general formula (I) include methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate and t-butyl. Silicate, tetraacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyl Oxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycid Xyethyltrimethoxysilane, β
-Glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane,
γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane,
γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) ) Methyltriethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,3
4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-
Epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethyl Methyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane,
α-glycidoxypropylmethyldimethoxysilane, α
-Glycidoxypropylmethyldiethoxysilane, β-
Glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane , Γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropyl Vinyldimethoxysilane, γ-glycidoxypropyl vinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane Amine, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ -Chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxy Silane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) γ-ami Propyl methyl dimethoxy silane, .gamma.-aminopropyl methyl dimethoxysilane, N-(beta-aminoethyl) gamma
-Aminopropyltriethoxysilane, N- (β-aminoethyl) γ-aminopropylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxy Silane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxy Examples thereof include silane, methylvinyldimethoxysilane, and methylvinyldiethoxysilane.

In order to form the above-mentioned cured film, a method of applying a coating composition to a substrate can be mentioned. The coating composition can be prepared by a conventionally known method. If desired, various curing agents, various organic solvents and surfactants may be contained for the purpose of improving wettability at the time of application and improving the smoothness of the cured film. Preferred curing catalysts are amines such as allylamine and ethylamine, various acids or bases such as Lewis acid or Lewis base, carboxylic acid, chromic acid, hypochlorous acid, boric acid, perchloric acid, bromic acid and selenious acid. , Salts of thiosulfuric acid, orthosilicic acid, thiocyanic acid, nitrous acid, aluminic acid, carbonic acid and the like, alkoxides of metals such as aluminum, zirconium and titanium, and chelate compounds of these metals. Further, an ultraviolet absorber, an antioxidant, a light stabilizer, an antiaging agent and the like can be added as long as they do not affect the physical properties of the coating composition and the cured film. As a coating method of the coating composition, a commonly used method such as a dipping method, a spin coating method and a spray method can be applied, but the dipping method and the spin coating method are preferable from the viewpoint of surface accuracy (smoothness of the film surface). . Curing of the coating composition is performed by hot air drying or irradiation with active energy rays, and the curing condition is usually in hot air at 70 to 200 ° C, preferably at 90 to 150 ° C. As the active energy ray, far infrared rays and the like can be mentioned, and damage due to heat can be suppressed to a low level.

Although the optical member of the present invention has antifogging performance, the antifogging performance is not maintained permanently. When the anti-fog performance deteriorates, the anti-fog performance can be restored by washing the hybrid thin film. The cleaning method is preferably performed by plasma treatment. Plasma treatment refers to a method in which an object is irradiated with excited molecules, radicals, or ions generated as a result of molecular dissociation by plasma discharge. The plasma irradiation time is not particularly limited, but is preferably 5 seconds to 60 seconds.

[0023]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The physical properties of the optical members obtained in the examples were evaluated as follows. (1) Luminous Transmittance The luminous transmittance Y of a plastic lens was measured with a Hitachi spectrophotometer U-3410 using a plastic lens having antireflection films on both surfaces as a sample. (2) Luminous reflectance The luminous reflectance Y of a plastic lens was measured using a Hitachi spectrophotometer U-3410 using a plastic lens having antireflection films on both surfaces as a sample. (3) 100 squares of 1 mm x 1 mm were made with a razor on the surface of the adhesive plastic lens, and cellophane tape (trademark: cellophane tape, sold by Nichiban Co., Ltd.) was pasted on the square and the tape was removed at a stretch and left. It was evaluated by the number of squares. In the table, the number of remaining squares / 100 is shown. (4) Steel wool standard (# 0
000) (manufactured by Nippon Steel Wool Co., Ltd.) 1 kgf
/ Cm ² load, rub for 10 strokes (reciprocating),
The surface condition was evaluated according to the following criteria. UA: Almost no scratches A: Several small scratches B: Many small scratches, several thick scratches C: Many small scratches, many thick scratches D: Almost film peeling (5) Anti-fogging 5 ° C refrigerator After storing the sample for 20 minutes, immediately leave it in a constant temperature machine with humidity of 90% and room temperature of 40 ° C for 10 seconds,
Then, the degree of haze was evaluated through the sample.
The evaluation criteria are as follows. Level 4: You can read a book through the sample lens Level 3: You can walk through the sample lens during the day Level 2: You can somehow see the scenery through the sample lens Level 1: No scene through the sample lens Levels 1 and 2 are: It can be regarded as not having anti-fog property. (6) Water contact angle The water contact angle of the plastic lens surface was measured using an automatic surface tensiometer K12 (Kruess Co.) according to the Wilhelmy method. (7) Organic substance content in the hybrid layer The organic substance content in the thin film hybrid layer is obtained by grasping the refractive indices of the inorganic substance and the organic substance in advance and measuring the film thickness and the reflectance of the hybrid layer. It was The organic substance content in the hybrid layer was determined by the interpolation method using the refractive index of the hybrid layer based on the refractive indices of the inorganic substance layer and the organic substance layer.

Examples 1 and 2 In a glass container, colloidal silica (Snotex-
40, manufactured by Nissan Kagaku Co., Ltd.), 81.6 parts by weight of an organosilicon compound, methyltrimethoxysilane, 176 parts by weight of an organosilicon compound, γ-glycidoxypropyltrimethoxysilane, and 0.5N hydrochloric acid.2. 0 parts by weight, acetic acid 2
A liquid obtained by adding 0 parts by weight and 90 parts by weight of water was stirred at room temperature for 8 hours and then left at room temperature for 16 hours to obtain a hydrolysis solution.
To this solution, 120 parts by weight of isopropyl alcohol, n
-Butyl alcohol 120 parts by weight, aluminum acetylacetone 16 parts by weight, silicone-based surfactant (polyalkylene oxide-methyl siloxane copolymer type,
Product name: Y7006, manufactured by Nippon Unicar Co., Ltd.) 0.2
Parts by weight, ultraviolet absorber (2-2 (hydroxy-4-octyloxyphenyl) benzotriazole, trade name: SE
ESORB 707R, manufactured by SHIPORRO) 0.1
A part by weight was 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. A plastic lens substrate (material: diethylene glycol bisallyl carbonate, refractive index 1.50, center thickness 2.0 mm, lens dioptric power 0.00) pretreated with an alkaline aqueous solution is dipped in the coating solution and dipped. After completion, pulling speed 2
Plastic lens pulled up at 0 cm / min at 120 ° C
And heated for 2 hours to form a cured film (hard coat A layer). Then, an ion gun pretreatment was performed using Ar gas under the conditions of the ion accelerating voltage and the irradiation time shown in Table 1.
Next, a multilayer antireflection film including the first to seventh layers was formed on the hard coat A layer under the conditions shown in Table 1 to obtain a plastic lens. In Table 1, as an organic compound having a hydrophilic group and a reactive group, in Example 1, the organic substance A (polyethylene glycol glycidyl ether E-400) was used.
(Manufactured by Nippon Oil & Fats Co., Ltd.), and in Example 2, the organic substance B (polyethylene glycol monoacrylate AE-) was used.
400 (manufactured by NOF CORPORATION) was used. Further, when forming the multilayer antireflection film, ion assist was performed using an ion gun in forming the hybrid thin film of the seventh layer. The condition is that Ar gas is used and the acceleration voltage is 70
V, acceleration current 70 mA. In addition, the organic substance A was heated to 80 ° C. in an external tank and was heated to 6.7 × 10 ⁻³ Pa (5 × 10 ³ Pa).
^-5 Torr) was supplied into the chamber, and the inorganic components were simultaneously supplied by vapor deposition with an electron gun to form a film. In addition, the vapor deposition of the inorganic substance and the vapor deposition of the organic substance were binary vapor deposition, and the conditions were set so that the vapor deposition was almost simultaneous. The above-mentioned (1) to (5) were evaluated for the obtained plastic lens, and the results are shown in Table 1. In the table, λ is the wavelength of the irradiation light, and λ = 500 nm
Indicates. The refractive index of the hybrid layer was determined at λ = 500 nm.

Example 3 A hard coat A was formed in the same manner as in Example 1. Next, on the hard coat A layer, the first layer was formed under the conditions shown in Table 2.
A multilayer antireflection film consisting of ~ 7 layers was formed to obtain a plastic lens. In Table 2, as an organic compound having a hydrophilic group and a reactive group, in Example 2, the organic substance C (N-
(3-trimethoxysilylpropyl) gluconamide (manufactured by Chisso Corporation)) was used. When forming the multilayer antireflection film, ion assist was performed using an ion gun in forming the hybrid thin film of the seventh layer.
The conditions are an Ar gas, an acceleration voltage of 80 V, and an acceleration current of 80 mA. The organic substance C was a biocolumn (stainless steel filter; diameter 18 mm, thickness 3 mm, pore size 80 to 100 μm), which was made into a 50% solution using ethyl acetate as a solvent and then 0.5 ml was added. The degree of vacuum is 6.7 × 10 ⁻³ Pa (5 × 10 ⁻⁵ Tor
In r), it was heated to 150 to 200 ° C. and supplied, and at the same time, the inorganic substance was evaporated by an ion gun to form a film. In addition, the vapor deposition of the inorganic substance and the vapor deposition of the organic substance were binary vapor deposition, and the conditions were set so that the vapor deposition was almost simultaneous. About the obtained plastic lens (1)-
(5) was evaluated and the results are shown in Table 2. In the table, λ is the wavelength of the irradiation light, and λ = 500 nm. The refractive index of the hybrid layer was determined at λ = 500 nm. In addition,
In Tables 1 and 2, the item of the ion gun set value indicated by "-" indicates that the layer is formed by a method other than the ion assist method, that is, a general vapor deposition method.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

As shown in Tables 1 and 2, the plastic lenses of Examples 1 to 3 have a luminous reflectance of 0.72 to 0.8.
It is extremely small at 1%, and the luminous transmittance is 99.0-99.1.
It was as high as%. Further, the adhesion, abrasion resistance and antifogging property were also good. Further, the contact angles of the lenses with respect to water in Examples 1 to 3 were 5 degrees in Example 1, 4 degrees in Example 2, and 5 degrees in Example 3.

Example 4 When the outermost layer produced by Examples 1 to 3 is a hybrid thin film and the anti-fog plastic lens has an anti-fog performance, the anti-fog performance is lowered by rubbing 200 times with a chamois under a load of 100 g. The antifogging performance was reduced to level 2 on the evaluation standard, and the contact angle of the lens with water was 16 in Example 1.
15 degrees in Example 2 and 16 degrees in Example 3. The anti-fog plastic lens thus constructed is set up in the chamber of the small plasma generator,
Reduce the pressure to 3 Pa (1 Torr). Then air 70c
c / min. (Volume conversion value at 25 ℃) Supply, RF
Atmospheric plasma treatment was performed at (high frequency) power of 200 W for 15 seconds. By this treatment, with respect to all the plastic lenses of Examples 1 to 3, the antifogging performance was reproduced without impairing other physical properties, the evaluation level was improved to Level 4, and the contact angle of the lens with water was 5 degrees, Example 2
Was 4 degrees and Example 3 was 5 degrees. In addition, the above-mentioned Example 1
3 to 3 by changing the combination of the respective layers forming the antireflection film,
4, a more preferred embodiment can be obtained.

[0032]

As described in detail above, by using the hybrid thin film of the present invention, good transparency can be obtained,
It has excellent abrasion resistance and antifogging performance, and has a small reflectance, so it can be sufficiently used as an antireflection film, and is useful as an antireflection film and an optical member. Further, according to the antifogging performance restoring method of the present invention, even if the antifogging performance of the hybrid thin film is deteriorated, it can be easily restored.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C23C 14/08 G02B 1/10 A G02B 1/10 Z (72) Inventor Kenichi Shinde In Shinjuku-ku, Tokyo 2-7-5 Ochiai F-term inside HOYA Co., Ltd. EJ082 EJ42 EJ422 EJ82 EJ822 JA07A JK09 JL07 JL07A JM02A JN06B JN18A YY00A 4K029 BA44 BA46 BA62 BB00 BB02 BC00 BC07 BD00 EA00 EA01

Claims (21)

[Claims] 1. A hybrid thin film having an antifogging property, which is formed by vapor-depositing an organic compound having a hydrophilic group and a reactive group, and silicon dioxide, or silicon dioxide and aluminum oxide. 2. The hybrid thin film according to claim 1, wherein the hybrid thin film is formed by an ion assist method. 3. The organic compound is a hydrophilic compound,
The hybrid thin film according to claim 1, wherein the silicon dioxide or silicon dioxide and aluminum oxide is inferior in hydrophilicity to the organic compound. 4. The ratio of the number of oxygen atoms to the number of moles of the organic compound in the organic compound is 18
The hybrid thin film according to any one of claims 1 to 3, having a content of -40%. 5. The content of the structure derived from the organic compound in the hybrid thin film is 0.02 to 70% by weight, based on the total amount of the hybrid thin film. Hybrid thin film. 6. The number average molecular weight of the organic compound is 15
The hybrid thin film according to any one of claims 1 to 5, which has a weight of 0 to 1500 g / mol. 7. The hybrid thin film according to claim 1, wherein the organic compound is a compound having a polyether main chain structure and having reactive groups at both ends of the main chain. 8. The reactive group is an epoxy group, a methacrylic group, an acrylic group, an amino group, a thiol group, or a carbon number of 3 to 1.
The hybrid thin film according to any one of claims 1 to 7, which is at least one kind of group selected from the trialkoxysilyl group of 5 and the hydroxyl group. 9. The hybrid thin film according to claim 7, wherein the organic compound is a compound represented by the general formula (1). [Chemical 1] (In the formula, R ₁ and R ₂ are each independently an epoxy group,
A methacrylic group, an acrylic group, an amino group, a thiol group, a trialkoxysilyl group having 3 to 15 carbon atoms, a hydroxyl group, or an organic group containing at least one group selected from these groups is shown. Further, n is an integer of 1 or more, and is an integer having a number average molecular weight in the range of 150 to 1500 g / mol. ) 10. The organic compound has a repeating unit of hydroxymethylene or carboxymethylene and has a reactive group at both ends of the repeating unit.
7. The hybrid thin film according to any one of 6 above. 11. The reactive group is an epoxy group, a methacrylic group, an acryl group, an amino group, a thiol group, or a carbon number of 3 to 3.
The hybrid thin film according to claim 10, which has 15 trialkoxysilyl groups or hydroxyl groups. 12. The hybrid thin film according to claim 10, wherein the organic compound is a compound represented by the general formula (2) or the general formula (3). [Chemical 2] (In the formula, R ₃ , R ₄ , R ₅ and R ₆ are each independently an epoxy group, a methacrylic group, an acryl group, an amino group, a thiol group, a trialkoxysilyl group having 3 to 15 carbon atoms, a hydroxyl group or these. Represents an organic group containing at least one kind of group selected from the group, and m and k are each 2
With the above integer, the number average molecular weight is 225 to 1500 g / mo.
It is an integer that becomes l. ) 13. The refractive index of the hybrid thin film is:
It is 1.42-1.48, 1 in any one of Claims 1-12.
The hybrid thin film according to the item. 14. The hybrid thin film has a thickness of 5 n.
The hybrid thin film according to claim 1, having a thickness of m to 100 nm. 15. The outermost layer of the antireflection film according to claim 1.
15. An antireflection film on which the hybrid thin film according to any one of 14 is applied. 16. An optical member comprising a plastic base material and an antireflection film formed by applying the hybrid thin film according to claim 15 on the plastic base material, wherein reflection is performed with reference to the base material side. An optical member provided with the hybrid thin film according to claim 1 as an outermost layer of a protective film. 17. The optical member according to claim 16, which has a cured film between the plastic substrate and the antireflection film provided with the hybrid thin film. 18. A method for restoring the antifogging performance of a hybrid thin film, which comprises restoring the antifogging performance by washing the hybrid thin film in the optical member according to claim 16 or 17. 19. The method for restoring the antifogging performance of a hybrid thin film according to claim 18, wherein the cleaning is performed by plasma treatment. 20. The method for producing a hybrid thin film according to claim 1, wherein an organic compound having a hydrophilic group and a reactive group, and silicon dioxide, or silicon dioxide and aluminum oxide are vapor-deposited. 21. The production of an optical member according to claim 16 or 17, wherein the hybrid thin film according to any one of claims 1 to 14 is applied as the outermost layer of the antireflection film on the basis of the base material side. Method.