JP2016071338A - Optical element and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical element that is capable of obtaining an anti-fogging property excellent in anti-fogging sustainability and scratch resistance and that is also excellent in heat resistance.SOLUTION: An optical element includes a transparent substrate (11) and an optical inorganic vapor deposition film (13) in a single or multiple layers on a surface or both surfaces of the transparent substrate (11), and further includes an anti-fogging function film (15) on an upper surface of the optical inorganic vapor deposition film (13). The optical inorganic vapor deposition film (13) is heat-resistant and includes an outermost layer (SiOoutermost layer) formed of a silica (SiO). The anti-fogging function film (15) is formed of a coating film of a (meth)acrylic polymer having an alkoxysilyl group (-Si(OR), in which R is an alkyl group having 1 to 4 carbon atoms, and the same applies below). The optical inorganic vapor deposition film (13) and the anti-fogging function film (15) are bonded via dehydration condensation between an OH group formed on the SiOoutermost layer and an OH group formed by hydrolysis of the -Si(OR).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a novel optical element provided with an optical inorganic vapor deposition film on the upper surface of a transparent substrate, and further to a novel optical element provided with an antifogging functional film, and a method for producing the same. Here, as an optical inorganic vapor deposition film, an antireflection film or a mirror film will be mainly described as an example, but in any case where a single layer or a multilayer optical inorganic vapor deposition film is formed to increase or decrease the reflectance, for example, It can also be applied to interference filters.

  Such optical elements are often cloudy in cold weather or in a high humidity atmosphere. This is due to condensation of moisture in the atmosphere when the surface of the optical element is at a temperature below the dew point. The haze in the optical element is reduced in the transparency of a transmissive optical element such as a lens, and the visibility of a reflected image is reduced in a non-transmissive optical element such as a mirror.

  For this reason, various antifogging methods are known. The main anti-fogging methods are: 1) apply a surfactant, 2) apply a water-absorbing material, 3) form a paint film containing a photocatalyst that increases hydrophilicity, 4) There is a method of forming a fine concavo-convex structure capable of holding a surfactant, and 5) providing a heating means such as a heater.

  For example, Patent Document 1 proposes the above-described antifogging method 1) in which an antifogging agent containing a specific amount of a fluorinated hydrocarbon surfactant is applied to a plastic lens to form an antifogging functional film ( Claim 1 etc.). However, since the anti-fogging method only applies a surfactant, the surfactant is likely to flow out by washing or the like, and lacks the durability of the anti-fogging function.

  In Patent Document 2, a coating composition containing colloidal silica, polyvinyl alcohol, and a water-containing organic solvent is used as a first layer on a plastic lens substrate for spectacles, and methyl silicate, acetylacetone aluminum, and water are formed on the first layer. The anti-fogging method of the above 2) for forming a hybrid anti-fogging coating layer having a coating composition containing an organic solvent as a second layer has been proposed (Claim 3 etc.). However, since the anti-fogging method contains a water-absorbing polymer, it lacks scratch resistance (durability).

  In Patent Document 3, a titanium oxide-silicon oxide composite film containing tetracoordinate titanium oxide having high catalytic activity is formed on a plastic lens substrate having a hard coat (film) (summary, claim 8, etc.). In Patent Document 4, in an optical component having an organic antireflection layer composed of a medium refractive index layer, a high refractive index layer, and a low refractive index layer from the substrate side, the composition containing anatase-type titanium oxide is increased. The above-described anti-fogging method 3) has been proposed in which a refractive index layer is formed (summary, claim 1 and the like), and titanium oxide is activated by light energy to make the surface hydrophilic. However, this anti-fogging method requires high-energy ultraviolet rays contained in sunlight to activate titanium oxide, which is a catalyst, and it is difficult to obtain anti-fogging properties in indoor environments, at night and in cloudy weather.

  Patent Document 5 proposes the above-described antifogging method 4) in which an inorganic hydrophilic hard layer that can be impregnated with a surfactant with a specific material is formed on a lens substrate, and the surfactant is applied (impregnated). (Claim 1, paragraphs 0041 and 0042). However, in the anti-fogging method, the anti-fogging sustainability is longer than that of the above-described 1) anti-fogging method, but a further long-term anti-fogging sustainability is required.

  In Patent Document 6, a heating element made of an electroless plating film having good adhesion to an optical substrate is provided on a transparent optical substrate made of glass or plastic, and heat generated when power is applied to the heating element is used. Thus, the above-mentioned anti-fogging method 5) for making the optical substrate anti-fogging has been proposed (claim 1 and the like). However, the anti-fogging method requires a power source, and is limited to a vanity table, a power source such as a bathroom mirror and a camera filter, or a device with a built-in battery, and is difficult to use in applications such as glasses.

Although not a patent document relating to the anti-fogging system, which outermost layer is cited in the following description as a preferred design example of the optical inorganic vapor-deposited film is a SiO ₂ is described in such Patent Documents 7 and 8 of the present invention Yes.

Patent Documents 9 and 10 describe specific acrylic polymers having an alkoxysilyl group (—Si (OR) ₃ ) cited in the following description as a suitable example of a film forming element (polymer) for an antifogging functional film. ing.

JP-A-5-107401 Japanese Patent Laid-Open No. 2005-234066 JP 2000-344510 A JP 2008-96701 A JP 2003-14903 A Japanese Patent Laid-Open No. 11-167001 JP 2005-234188 A International Publication 2012/157072 JP 2011-236403 A JP 2012-148436 A

  In view of the above, the present invention provides an antifogging property excellent in antifogging durability and scratch resistance even without ultraviolet rays or a power source, and an optical element excellent in heat resistance and a method for producing the same The purpose is to provide.

  As a result of diligent efforts to solve the above-described problems, the present inventors have conceived an optical element having the following configuration and a method for manufacturing the same.

The optical element according to the present invention is provided with a single-layer or multilayer optical inorganic vapor deposition film on one or both sides of a transparent substrate, and further provided with an antifogging functional film on the upper surface of the optical inorganic vapor deposition film,
The optical inorganic vapor-deposited film has a heat resistant specification and includes an outermost layer formed of silica (SiO ₂ ) (hereinafter referred to as “SiO ₂ outermost layer”).
The antifogging functional film comprises a coating film of a (meth) acrylic polymer having an alkoxysilyl group (—Si (OR) ₃ , where R: an alkyl group having 1 to 4 carbon atoms, the same shall apply hereinafter),
The optical inorganic vapor-deposited film and the anti-fogging functional film are bonded through dehydration condensation between an OH group on the outermost SiO ₂ layer and an OH group generated by hydrolysis of the alkoxysilyl group. Features.

A method for producing an optical element according to the present invention comprises a single-layer or multilayer optical inorganic vapor-deposited film on one or both sides of a transparent substrate, and an optical element further comprising an antifogging functional film on the upper surface of the optical inorganic vapor-deposited film. A manufacturing method comprising:
The optical inorganic vapor-deposited film having a heat resistant specification and the SiO ₂ outermost layer is vapor-deposited, and the anti-fogging functional film is coated with a paint having a (meth) acrylic polymer having an alkoxysilyl group as a film-forming element. When forming with a film,
A heat treatment is performed after the coating film is formed.

It is a model sectional view of an optical element to which the present invention is applied. It is a flowchart which shows an example of the manufacturing method of this invention.

  Hereinafter, embodiments according to the present invention will be described in detail.

  As shown in FIG. 1, the present invention comprises a single-layer or multilayer optical inorganic vapor deposition film (mainly antireflection film) 13 on one or both surfaces of a transparent substrate 11, and further has an antifogging function on the upper surface of the optical inorganic vapor deposition film. The optical element (eyeglass lens in the illustrated example) L provided with the film 15 is concerned. And the optical element of this invention is manufactured through each process as shown in FIG. Note that the activation process is not inevitable.

  Here, a plastic substrate (organic glass substrate) will be mainly described as an example, but the same applies to an inorganic glass substrate.

  Optical elements include optical lenses such as eyeglass lenses and camera lenses, light transmissive lenses such as front glass or front filter of various displays, optical prisms, and other non-planar mirrors, concave mirrors, convex mirrors, etc. Light transmissive materials can be mentioned.

  The transparent substrate may be organic glass or inorganic glass. However, in the case of organic glass, it is necessary to perform heat treatment of the antifogging functional film at a specific temperature, and thus heat resistance at the heat treatment temperature is necessary. Further, as will be described later, since a primer coat film, a hard coat film or a vapor deposition film is usually formed, heat resistance higher than the processing temperature is required.

Examples of the organic glass include polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene terephthalate (PET: polyester), polyurethane, aliphatic allyl carbonate resin, aromatic allyl carbonate resin, polythiourethane, episulfide resin, and norbornene resin. , Polyimide, polyolefin, and the like. Examples of commercially available products when the present invention is applied to eyeglasses and the like include “CR-39” (aliphatic allyl carbonate resin manufactured by PPGCO., N _D : 1.50), “MR-8”, and “MR-20”. (Mitsui Chemicals Co., Ltd., polythiourethane, n _D : 1.60), “MR-7” (Mitsui Chemicals, Inc. polythiourethane, n _D : 1.67), “MR-174” (Mitsui Chemicals, Inc.) A company-made episulfide resin, n _D : 1.74), and the like can be suitably used. Each of the above trade names is a trademark.

As the inorganic glass, general-purpose quartz glass may be used. However, when the present invention is applied to eyeglasses or the like, the following exemplified ones having a refractive index (n _D ) of 1.55 or more can be preferably used.

  Barium crown glass (BaK) 1.54-1.60, heavy crown glass (SK)> 1.54, extra heavy crown glass (SSK)> 1.60, light barium flint (BaLF)> 1.55, barium flint (BaF)> 1.56, heavy barium flint (BaSF)> 1.585.

  When the transparent substrate is organic glass, the hard coat film 17 is usually formed from the viewpoint of scratch resistance. When forming the hard coat film 17, it is desirable to interpose a primer coat film 19 between the transparent substrate 11 in order to improve impact resistance.

  (1) The hard coat (composition) for forming the hard coat film is not particularly limited as long as it can impart scratch resistance and the like to the glass surface, but the following silicone type (a) or acrylic type (b) It can be used suitably.

(A) Silicone hard coat:
For example, a catalyst and metal oxide fine particles are added to a hydrolyzate of an organoalkoxysilane, and the viscosity is adjusted so that it can be applied with a diluting solvent.

  Furthermore, a surfactant, an ultraviolet absorber and the like can be appropriately added to the liquid hard coat.

1) As the above organoalkoxysilane, those represented by the following general formula can be used.
R ¹ _a R ² _b Si (OR ³ ) _{4- (a + b)}
(However, R ¹ is an alkyl group having 1 to 6 carbon atoms, vinyl group, epoxy group, methacryloxy group, and phenyl group, and R ² is a hydrocarbon group having 1 to 3 carbon atoms, a halogenated hydrocarbon group, an aryl group. Group R ³ is an alkyl group having 1 to 4 carbon atoms, and a = 0 or 1, b = 0, 1 or 2.

  Specifically, tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, trimethylchlorosilane, glycidoxymethyltrimethoxysilane, α-glycidoxyethyltrimethoxysilane, β -Glycidoxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like can be mentioned. These can be used alone or in combination of two or more.

  2) Examples of the catalyst include trimellitic acid, trimellitic anhydride, itaconic acid, pyromellitic acid, pyromellitic anhydride and other organic carboxylic acids, nitrogen-containing organic compounds such as methylimidazole and dicyandiamide, metal alkoxides such as titanium alkoxide and zircoalkoxide, Metal complexes such as acetylacetone aluminum and acetylacetone iron, and alkali metal organic carboxylates such as sodium acetate and potassium acetate can be preferably used.

  3) Metal oxide fine particles include colloidal silica, colloidal titania, colloidal zirconia, colloidal cerium oxide (IV), colloidal tantalum oxide (V), colloidal tin oxide (IV), colloidal antimony oxide having an average particle diameter of 5 to 50 nm. (III), colloidal alumina, colloidal iron oxide (III) and the like can be suitably used, and these can be used alone or in combination of two or more or as composite fine particles.

  4) As the diluting solvent, polar solvents such as alcohols, ketones, esters, ethers and cellosolves can be suitably used.

  5) As a coating method, a conventional method such as a dipping method or a spin coating method is used. The curing conditions are preferably 80 to 140 ° C. × 1 to 4 hours.

(b) Acrylic hard coat:
For example, a polyfunctional acrylic oligomer having 3 or more acryloyloxy groups in one molecule, a monomer, a monomer having a target function, an oligomer, and a photopolymerization initiator as essential components, Adjust to a viscosity that can be applied. If necessary, additives such as polymerization inhibitors, leveling agents and ultraviolet absorbers, and modifiers such as thermoplastic resins and metal oxide fine particles can be added.

  1) As the polyfunctional acrylic oligomer / monomer, the following various acrylates having 3 or more acryloyloxy groups in one molecule can be preferably used.

    (I) Polyol acrylate ((meth) acrylate of polyhydric alcohol or polyether type polyhydric alcohol): trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate etc,

    (ii) Polyester (meth) acrylate (obtained by reacting three components of polybasic acid, polyhydric alcohol and (meth) acrylic acid): for example, phthalic acid, isophthalic acid, tetrahydrophthalic acid as polybasic acid As the polyhydric alcohol, trimethylolpropane, pentaerythritol, etc.

    (iii) Urethane acrylate (obtained by reacting a tri- or higher-valent polyol component, a tri- or higher-valent polyisocyanate or a polyol polyisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate), for example: polyol component As the polyisocyanate, trimethylolpropane and the like, HMDI burette or trimer, and hydroxyl group-containing polyfunctional (meth) acrylate as the polyol acrylate such as pentaerythritol triacrylate can be preferably used.

    (iv) Epoxy acrylate (obtained by reacting epoxy compound with (meth) acrylic acid and hydroxyl group-containing (meth) acrylate): glycerin triglycidyl ether triacrylate, tris (glycidyl ether ethyl) isocyanurate triacrylate, penta Erythritol tetraglycidyl ether tetraacrylate, phenol novolac polyglycidyl ether polyacrylate, trimethylolpropane polyglycidyl ether polyacrylate, etc.

    (V) Others: trisacryloyloxyisocyanurate, aminopolyacrylate, hexakismethacryloyloxyethylphosphazene, trisacryloyloxyethyl isocyanurate, and the like.

  2) As the photopolymerization initiator, various types exemplified below can be preferably used.

    (i) Monophenone series: 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2- Hydroxyethoxy) -phenyl (2-hydroxypropyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, etc.

    (ii) Benzoin series: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl methyl ketal, etc.

    (iii) Benzophenone series: benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxy Benzophenone, etc.

    (iv) Thioxanthone series: Thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthio Xanthone, 2,4-diisopropylthioxanthone, etc.

    (v) Special group: α-acyloxime ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ′, 4 “-Diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, etc.

  In addition, photopolymerization initiation aids such as triethanolamine, methyldiethanolamine, triisopropanolamine, 4,4′-dimethylaminobenzophenone (Michler ketone), 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, etc. are used in combination. You can also

  The concentration of the photopolymerization initiator is 0.5 to 10 parts, preferably 1 to 7 parts, relative to 100 parts of the curable resin.

3) As the polymerization inhibitor, the following can be preferably used.
Hydroquinone, methoquinone, p-benzoquinone, phenothiazine, mono-t-butylhydroquinone, catechol, pt-butylcatechol, benzoquinone, 2,5-di-t-butylhydroquinone, anthraquinone, 2,6-di-t- Butylhydroxytoluene, etc.

  4) As the leveling agent, hydrocarbon-based, silicone-based, and fluorine-based agents can be suitably used.

  5) As the ultraviolet absorber, hydroxybenzophenone series, salicylate series, benzotriazole series, hindered amine series, and the like can be suitably used.

  6) As the thermoplastic resin, polyurethane elastomer, polybutadiene elastomer, acrylonitrile / butadiene elastomer and the like can be suitably used.

  7) As the metal oxide fine particles and the diluting solvent, those similar to those exemplified for the silicone system can be used.

  The coating method is the same as in the case of the silicone system.

  The curing condition is 2 to 180 seconds under a high-pressure mercury lamp system or metal halide lamp system ultraviolet light source with a tube wall load of 80 to 160 W / cm.

  (2) The primer coat film is particularly preferably formed using a primer based on a thermoplastic elastomer excellent in impact resistance.

  Specifically, 1) a TPU primer composition in which metal oxide inorganic fine particles are added to a urethane-based thermoplastic elastomer (TPU), and 2) the entire or main component of the coating film-forming polymer is an ester-based thermoplastic elastomer (TPEE). The TPEE primer composition to which the same metal oxide inorganic fine particles as those added are added can be suitably used.

  1) TPU is composed of a soft segment composed of long-chain polyol and polyisocyanate, and a hard segment composed of short-chain polyol and polyisocyanate, and added in the form of an aqueous emulsion (emulsion). Is desirable.

  What was used for the above-mentioned hard coat can be used for metal oxide fine particles.

  2) TPEE is a multi-block copolymer using polyester as a hard segment and polyether or polyester as a soft segment. The mass ratio of the hard segment to the soft segment is usually the former / the latter = about 30/70 to 10/90.

  Further, the same metal oxide inorganic fine particles as those of the urethane primer are used for adjusting the refractive index.

  (3) In this embodiment, a single-layer or multilayer optical inorganic vapor deposition film 13 is formed on the hard coat film 17 to reduce or increase the reflectance. That is, an antireflection film or a mirror film is formed.

The optical inorganic vapor-deposited film 13, must be provided with a outermost layer is formed by SiO ₂ (SiO ₂ outermost layer). In the present invention, since heat treatment (55 ° C. or higher, preferably 75 ° C. or higher) is essential when manufacturing the optical element, it is desirable that the optical inorganic vapor deposition film has a heat resistant specification. It is further desirable that at least one layer inside the outermost SiO ₂ layer has high heat resistance substantially consisting of a sintered mixture (specific vapor deposition film material) having the following composition.

  Specifically, the sintered mixture may be one described in Japanese Patent Application Laid-Open No. 2002-226967 as a vapor deposition material for producing a high refractive index optical layer (edited from the summary and cited).

“Vapor deposition material is titanium oxide (TiO _x ; x = 1.5 to 1.8) 10 to 65% by mass,
Lanthanum oxide (La ₂ O ₃₎ 33~74 wt%, 2 to 7 wt% titanium (Ti). "

  More specifically, “a mixture of 37.9% by mass of titanium oxide, 58.9% by mass of lanthanum oxide and 3.2% by mass of titanium is homogeneously mixed, granulated to a particle size of about 1 to 4 mm, and subjected to reduced pressure. A mixture obtained by calcining at 1500 ° C. for 6 hours (“Example 1”) or “a mixture of 34% by mass of titanium oxide, 63% by mass of lanthanum oxide, and 3.0% by mass of titanium” What was granulated to 4 mm and baked at about 1500 ° C. for 6 hours under reduced pressure (the “Example 2”) can be preferably used.

  More specifically, “Substance H4” and “Substance H5” (both are trademarks) marketed by Merck & Co., Inc. can be mentioned.

  In addition, the substrate temperature in the vapor deposition of Examples 1 and 2 in the above publication is 280 to 310 ° C., and a plastic substrate (organic glass) is not assumed. However, as described later, the organic glass substrate of the present invention is also a substrate. It can be used if the temperature is lowered.

  And a vapor deposition layer ("specific vapor deposition film") made of the specific vapor deposition film material, and one or more general-purpose inorganics of ceramics or metals such as the metal oxide / metal halide other than the specific vapor deposition film material A general-purpose optical inorganic vapor deposition layer made of a vapor deposition material is combined to form an antireflection film (AR film: reflection lowering film) or a mirror film (reflection mirror: reflection increase film).

  In designing the antireflection film, the optical film thickness is usually selected to be an integral multiple of λ / 4 (for example, λ: 500 nm), the required refractive index is calculated from the non-reflective conditions, and the material having the refractive index is calculated. (See Kose et al. “Optical Engineering Handbook” Asakura Shoten, 1996.2, p170).

  The mirror film is designed to be a transparent high refractive index, low refractive index λ / 4 repeating multilayer film (see p. 171).

  Here, as the vapor deposition film material other than the specific vapor deposition film material, the following exemplified a) inorganic oxide, b) inorganic halide, c) simple metal, and a mixture of the same kind or different kinds of combination (of the simple metal) In some cases, an alloy is included).

a) Titanium, tantalum, zirconium, niobium, antimony, yttrium, indium, tin, lanthanum, cerium, magnesium, aluminum, silicon,
b) Magnesium, lanthanum, aluminum, lithium,
c) Silicon, germanium, chromium, aluminum, gold, silver, copper, nickel, platinum.

  Optical inorganic vapor deposition film (antireflection film or mirror film) usually uses a dry plating method (PVD method) such as vacuum deposition method (including ion assist method), sputtering method, ion plating method, arc discharge method, etc. To form.

Then, one layer or a plurality of layers of the antireflection film or the mirror film may be deposited (film formation) by ion assist. When forming a particular deposition film on the organic glass, an evaporation material put into a vacuum vessel which is heated to less than 120 ° C., while timely fed a gas containing at least O ₂ 5.0 × 10 ^-1 ~5. It is preferable to heat the film while adjusting the pressure to 0 × 10 ⁻³ Pa, and to form a film while performing ion assist using an ion gun.

  When forming a specific vapor deposition film on organic glass, as heating temperature in a vacuum vessel, it is normal temperature -120 degreeC, Preferably, it is desirable to set it as 60-90 degreeC. Under normal temperature, the density of the formed film is low and sufficient film durability cannot be obtained. When the temperature exceeds 120 ° C., the substrate on which the film is formed may be deteriorated or deformed.

  As ion assist conditions, the gas introduction amount is usually 1 to 100 sccm (preferably 5 to 50 sccm) and the acceleration voltage 100 to 1200 V (preferably 200 to 1000 V). Here, “sccm” is an abbreviation of “standard cc / m”, and represents one at 0 ° C. and 101.3 kPa (1 atm).

The gas introduced into the ion gun is preferably O ₂ , Ar, or a mixed gas thereof.

  Prior to the ion assist, it is desirable to perform surface treatment of the hard coat film. Specific examples include (a) plasma treatment in an oxygen or argon atmosphere, (c) chemical treatment with acid / alkali, (b) ion irradiation treatment with oxygen or argon gas (ion cleaning) with an ion gun, and the like. it can. Among these, it is desirable to combine ion cleaning with ion assist.

  Note that ion cleaning and ion assist are described in detail in JP-A-10-123301 and JP-A-11-174205, respectively. Some of the descriptions in these publications are summarized below.

  ・ Ion cleaning: When depositing an optical inorganic vapor deposition film, it is desirable to perform a surface treatment of the hard coat film as a pre-treatment in order to increase the adhesion of the optical inorganic vapor deposition film. Examples include plasma treatment with oxygen or argon, chemical treatment with acid or alkali, and oxygen ion or argon ion irradiation treatment with an ion gun.

  Of the above, it is desirable to obtain a good surface by irradiating oxygen ions or argon ions with an ion gun. "

  ・ Ion assist method “At least the high refractive index layer is deposited using the ion beam assist method. For other films, the ion beam assist method may be used, or other physical deposition. The law may be used. "

  The other constituent layers of the antireflection film or mirror film other than the specific vapor deposition film may be the same ion assist as that of the specific vapor deposition film or other vacuum vapor deposition such as an electron beam. Usually, it is desirable to use an electron beam because the same vacuum chamber can be used.

The refractive index (n) of each vapor deposition material is shown below.
Specific vapor deposition film: 2.0-2.2
SiO ₂ : 1.43 to 1.47
TiO _2: 2.2~2.4
ZrO ₂ : 1.90 to 2.1
Ta ₂ O ₅ : 2.0 to 2.3

In the present embodiment, on the optically inorganic deposited film of the outermost layer formed of SiO ₂ with a heat-resistant (SiO ₂ outermost layer), to form the antifogging function film. The antifogging functional film is formed of a coating composition having a (meth) acrylic polymer having an alkoxysilyl group (—Si (OR) ₃ ) as a coating film forming element.

Then, it is desirable that the surface of the outermost SiO ₂ layer of the optical inorganic vapor deposition film is subjected to an activation treatment to generate and increase OH groups. It can be expected that the adhesion of the antifogging functional film to the optical inorganic vapor-deposited film (SiO ₂ outermost layer) is increased and the adhesion and wear resistance of the antifogging functional film are improved (see test examples described later).

  Examples of the activation treatment include plasma treatment, ultraviolet ozone cleaning, piranha cleaning, RCA cleaning, supercritical cleaning, and the like, and one or more of these treatments are appropriately selected. Of these, plasma treatment (especially oxygen plasma treatment) is desirable because it easily generates OH groups.

As the (meth) acrylic polymer having an alkoxysilyl group (—Si (OR) ₃ ), those having the following constitution described in Patent Document 10 can be suitably used.

  The paragraphs 0019 to 0023 and paragraphs 0040 to 0074 of the cited document 10 are cited with appropriate editing correction.

<Begin citation>
The (meth) acrylic polymer used in this embodiment is
Formula (I):

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrophilic group)
Having a repeating unit represented by formula (II) at least at one end:

(In the formula, R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and among R ³ , R ⁴ and R ⁵ , At least one group of C 1-4 is an alkoxy group, and R ⁶ is an alkylene group of 1-12 carbon atoms)
It is formed by the (meth) acrylic-type polymer which has the alkoxy silyl group represented by these.

And
In the repeating unit represented by the formula (I), R ¹ is a hydrogen atom or a methyl group.

R ² is a hydrophilic group. Examples of R ² include a hydrogen atom and an alkyl group having 1 to 4 carbon atoms having at least one hydroxyl group, and a polyethylene glycol group having 1 to 20 carbon atoms having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end. , A polypropylene glycol group having 1 to 10 carbon atoms having a hydrogen atom or an alkyl group having 1 to 4 carbon atoms at one end, Formula (III):

(Wherein R ⁷ and R ⁸ are each independently an alkylene group having 1 to 4 carbon atoms, and R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)
A group represented by formula (IV):

Wherein R ¹¹ is an alkylene group having 1 to 4 carbon atoms, R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹⁴ is an organic group, and X ⁻ is an anion. Show)
Although the group etc. which are represented by these are mentioned, this invention is not limited only to this illustration. Among these groups, the group represented by the formula (III) is preferable from the viewpoint of increasing the coating film strength.

In the formula (III), R ⁷ and R ⁸ are each independently an alkylene group having 1 to 4 carbon atoms. R ⁷ is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group. R ⁸ is preferably a methylene group or an ethylene group. R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the formula (IV), R ¹¹ is an alkylene group having 1 to 4 carbon atoms. R ¹¹ is preferably a methylene group, an ethylene group, an n-propylene group or an isopropylene group, more preferably a methylene group or an ethylene group. R ¹² and R ¹³ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹⁴ is an organic group. Specific examples of the organic group include an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a carboxyalkyl group having 2 to 6 carbon atoms. However, the present invention is limited only to such examples. Is not to be done. X ⁻ is an anion. X ^- is a suitable example of an alkyl chloride ion having 1 to 4 carbon atoms, a monovalent dialkyl sulfate ion carbon atoms in the alkyl group is 1-4, 6 to 8 carbon atoms aryl chloride ions, carbon atoms in the alkyl group Alkyl sulfate halide ions, halogen ions, acetate ions, borate ions, citrate ions, tartrate ions, hydrogen sulfate ions, bisulfite ions, sulfate ions, phosphate ions and the like having 1 to 4 numbers are included. Is not limited to such examples. Examples of the halogen atom in the halide include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the halogen atom in the halogen ion include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among X ⁻ , alkyl chloride ions having 1 to 4 carbon atoms, monovalent dialkyl sulfate ions having 1 to 4 carbon atoms in the alkyl group, and aryl chloride ions having 6 to 8 carbon atoms are preferable.

  From the viewpoint of imparting hydrophilicity to the substrate surface, the lower limit of the number of repeating units represented by formula (I) is preferably 1 or more, more preferably 10 or more, and the repeating units represented by formula (I). The upper limit of the number is preferably 1000 or less, more preferably 500 or less.

In the alkoxysilyl group represented by the formula (II), R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms (alkoxyl group). And at least one of R ³ , R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms. The reason why at least one of R ³ , R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms is that the antifogging coating is chemically bonded to the outermost SiO ₂ layer of the optical inorganic vapor-deposited film (dehydration condensation). (Si—O—Si bond). Thus, R ^3, it is preferable that at least one of the radicals R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms, R ^3, R ⁴ and at least two groups having a carbon number of R ⁵ more preferably 1 to 4 alkoxy group, more preferably any of R ^3, R ⁴ and R ⁵ is an alkoxy group having 1 to 4 carbon atoms. Among the alkyl groups having 1 to 4 carbon atoms, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. Among the alkoxy groups having 1 to 4 carbon atoms, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

In the alkoxysilyl group represented by the formula (II), R ⁶ is an alkylene group having 1 to 12 carbon atoms. Among R ⁶ , an alkylene group having 1 to 6 carbon atoms is preferable, and an alkylene group having 2 to 6 carbon atoms is more preferable.

  The alkoxysilyl group represented by the formula (II) is present at least at one end of the (meth) acrylic polymer, but the (meth) acrylic polymer is used from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer. It is preferable that it exists only in the one terminal. In the case where the alkoxysilyl group represented by the formula (II) is present only at one end of the (meth) acrylic polymer, from the viewpoint of sufficiently expressing the properties of the (meth) acrylic polymer at the other end, For example, it is preferable that a group such as a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or a residue of a polymerization initiator is present.

   A (meth) acrylic polymer having a repeating unit represented by the formula (I) and having an alkoxysilyl group represented by the formula (II) at least at one end is, for example, the formula (V):

(Wherein R ¹ and R ² are the same as above)
A (meth) acrylic monomer represented by formula (VI):

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above)
It can prepare by polymerizing in presence of the alkoxysilyl group containing compound represented by these.

  Examples of the (meth) acrylic monomer represented by the formula (V) include a methyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate, a dimethyl sulfate salt of N, N-dimethylaminoethyl (meth) acrylate, Diethyl sulfate of N, N-dimethylaminoethyl (meth) acrylate, benzyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate, methyl chloride salt of N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate dimethyl sulfate, N, N-dimethylaminopropyl (meth) acrylate diethyl sulfate, N, N-dimethylaminopropyl (meth) acrylate benzyl chloride salt, N, N- Diethylaminoethyl (meth) acrylate Methyl chloride salt, dimethyl sulfate salt of N, N-diethylaminoethyl (meth) acrylate, diethyl sulfate salt of N, N-diethylaminoethyl (meth) acrylate, benzyl chloride salt of N, N-diethylaminoethyl (meth) acrylate, N , N-diethylaminopropyl (meth) acrylate methyl chloride salt, N, N-diethylaminopropyl (meth) acrylate dimethyl sulfate, N, N-diethylaminopropyl (meth) acrylate diethyl sulfate, N, N-diethylaminopropyl (Meth) acrylate, N- (meth) acryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N- (meth) acryloylaminoethyl-N, N-dimethylammonium-α-N-methyl Carboxymethyl betaine, methoxy triethylene glycol (meth) acrylate, 2,2,2 although such trifluoroethyl methacrylate, present invention is not limited only to those exemplified. These (meth) acrylic monomers may be used alone or in combination of two or more. Among these (meth) acrylic monomers, the methyl chloride salt of N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminoethyl (meth) acrylate can be easily obtained at low cost. Of these, diethyl sulfate is preferred. N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine is, for example, disclosed in JP-A-9-95474, JP-A-9-95586, and JP-A-11-222470. Can be easily prepared with high purity.

  Examples of the alkoxysilyl group-containing compound represented by the formula (VI) include 1-thiopropyl-3-trimethoxysilane, 1-thiopropyl-3-triethoxysilane, 1-thiopropyl-3-triisopropoxysilane, Examples include thiopropyl-3-methyldimethoxysilane, 1-thiopropyl-3-methyldiethoxysilane, 1-thiopropyl-3-methyldipropoxysilane, and the like, but the present invention is not limited to such examples. These alkoxysilyl group-containing compounds may be used alone or in combination of two or more.

  The amount of the alkoxysilyl group-containing compound represented by the formula (VI) is not particularly limited, but usually it is preferably about 0.01 to 10 parts by mass per 100 parts by mass of the total amount of monomers to be subjected to polymerization.

  Note that the (meth) acrylic monomer represented by the formula (V) may be used in combination with another polymerizable monomer as long as the object of the present invention is not inhibited.

  Examples of other polymerizable monomers include styrene, α-hydroxystyrene, p-hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. Isobutyl, tert-butyl (meth) acrylate, neopentyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic Stearyl acid, cetyl (meth) acrylate, ethyl carbitol (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methoxyethyl (meth) acrylate , Methoxybutyl (meth) acrylate, N-methyl (meth) acrylamide, N-ethyl (meth) acrylate Luamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, N-octyl (meth) acrylamide, N, N-dimethyl (Meth) acrylamide, N, N-diethyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone (meth) acrylamide, styrene, methyl itaconate, ethyl itaconate, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, N -Vinylcaprolactam etc. are mentioned, However, this invention is not limited only to this illustration. These other polymerizable monomers may be used alone or in combination of two or more.

  When the (meth) acrylic monomer represented by the formula (V) is polymerized in the presence of the alkoxysilyl group-containing compound represented by the formula (VI), it is preferable to use a polymerization initiator.

  Examples of the polymerization initiator include azoisobutyronitrile, methyl azoisobutyrate, azobisdimethylvaleronitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, benzophenone derivatives, phosphine oxide derivatives, benzoketone derivatives, phenylthioether derivatives, azides Derivatives, diazo derivatives, disulfide derivatives and the like can be mentioned, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  Although the quantity of a polymerization initiator is not specifically limited, Usually, it is about 0.01-5 mass parts per 100 mass parts of monomer whole quantity with which the polymerization containing the (meth) acrylic-type monomer represented by Formula (V) is represented. It is preferable.

  Examples of the method for polymerizing the (meth) acrylic monomer represented by the formula (V) include a solution polymerization method, but the present invention is not limited to such examples. When the (meth) acrylic monomer represented by the formula (V) is polymerized by a solution polymerization method, for example, the (meth) acrylic monomer represented by the formula (V) is dissolved in a solvent, Polymerization can be performed by adding a polymerization initiator while stirring.

  Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene. Examples include compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl acetate and ethyl acetate. However, the present invention is limited only to such examples. is not. These solvents may be used alone or in combination of two or more.

  The amount of the solvent is usually such that the monomer concentration of the solution obtained by dissolving the monomer mixture for polymerization containing the (meth) acrylic monomer represented by the formula (V) in the solvent is about 10 to 80% by mass. It is preferable to prepare it.

  The polymerization conditions such as polymerization temperature and polymerization time when polymerizing the (meth) acrylic monomer represented by the formula (V) depend on the type of monomer and the amount used, the type of polymerization initiator and the amount used. It is preferable to adjust appropriately.

  The atmosphere when the (meth) acrylic monomer represented by the formula (V) is polymerized is preferably an inert gas. Examples of the inert gas include nitrogen gas and argon gas, but the present invention is not limited to such examples.

  The completion of the polymerization reaction and the presence or absence of unreacted monomers in the reaction system can be confirmed by, for example, a general analysis method such as gas chromatography.

  A (meth) acrylic polymer having an alkoxysilyl group can be obtained by polymerizing the (meth) acrylic monomer represented by the formula (V) and other monomers used as necessary as described above.

  The viscosity average molecular weight of the (meth) acrylic polymer having an alkoxysilyl group is preferably 100 or more, more preferably 500 or more, and (meth) having an alkoxysilyl group from the viewpoint of sufficiently expressing the surface modification effect. From the viewpoint of increasing the solubility of the acrylic polymer, it is preferably 100,000 or less, more preferably 50,000 or less. The viscosity average molecular weight of the (meth) acrylic polymer having an alkoxysilyl group can be measured by, for example, gel permeation chromatography.

The (meth) acrylic polymer having an alkoxysilyl group can be used after being dissolved in a solvent. Examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethylene glycol, and propylene glycol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene. Examples include compounds, aliphatic hydrocarbon compounds such as n-hexane, alicyclic hydrocarbon compounds such as cyclohexane, and acetic acid esters such as methyl acetate and ethyl acetate. However, the present invention is limited only to such examples. is not. These solvents may be used alone or in combination of two or more.
<End of citation>

The antifogging functional film is a (meth) acrylic polymer (hereinafter referred to as “specific acrylic polymer”) having the above alkoxysilyl group on the SiO ₂ outermost layer in the inorganic vapor deposition film 13 formed on the substrate 11 or a solution thereof. (Hereinafter referred to as “specific acrylic paint”).

  The specific acrylic polymer is the “LAMBIC” (trademark) series marketed by Osaka Organic Chemical Industry Co., Ltd., and “LAMBIC-400EP”, “LAMBIC-500EP”, “LAMBIC-770W”, etc. are preferably used. it can. Of these, relatively high molecular weight “LAMBIC-770W” is particularly desirable. This is because “LAMBIC-770W” particularly exhibits excellent anti-fogging durability and scratch resistance. The measured value of 10% viscosity (20 ° C.) of “LAMBIC-770W” was “8.3 mPa · s”.

A specific acrylic polymer or a specific acrylic paint having an alkoxysilyl group is applied onto the optical inorganic vapor deposition film having the outermost SiO ₂ layer. The coating concentration in that case shall be 0.001-4 mass% (desirably 0.01-2 mass%). The paint temperature is 10 to 40 ° C (desirably 20 to 30 ° C).

  The application method is not particularly limited. Examples thereof include a flow coating method, a spray coating method, a dipping method, a brush coating method, and a roll coating method.

  The coating amount of the (meth) acrylic polymer having an alkoxysilyl group or a solution (paint) thereof is preferably as thin as possible within a range where the antifogging property and durability after the required rubbing test can be exhibited. . Specifically, for example, when the paint viscosity is 1 to 2 mPa · s, it is the coating amount when dip coating is performed at a lifting speed of 50 to 500 mm / min (desirably 100 to 200 mm / min).

In the present invention, after applying the anti-fogging functional paint on the SiO ₂ outermost layer of the optical inorganic vapor-deposited film, it is necessary to heat-treat the substrate at a specific temperature, and further, the surface of the SiO ₂ outermost layer is coated. It is desirable to activate. As shown in Examples described later, an antifogging functional film excellent in durability (particularly in a rubbing test) cannot be formed on an optical inorganic vapor deposition film unless heat treatment is performed.

That is, the heat treatment promotes hydrolysis of the alkoxysilyl group to increase the number of OH groups of the specific acrylic polymer that forms the anti-fogging functional film, and generates the OH group on the outermost SiO ₂ layer and the hydrolysis. This is probably because the dehydration condensation with the OH group to be promoted promotes the formation of a strong bond (Si—O) by the dehydration condensation. In addition, it is considered that the activation treatment increases the number of OH groups in the outermost SiO ₂ layer and further increases the bond due to dehydration condensation.

  In the case of organic glass, the conditions for the heat treatment are appropriately selected within the range of usually 55 to 120 ° C. × 5 to 60 min, desirably 75 to 120 ° C. × 10 to 30 min. In the case of inorganic glass, it is appropriately selected within the range of 55 to 200 ° C. × 5 to 60 min, desirably 75 to 200 ° C. × 5 to 60 min.

  As shown in the examples below, if the temperature is too low or the processing time is short, it is difficult to maintain the antifogging property / appearance after the rubbing test, and if the temperature is too high or the processing time is too long, the organic glass In the case of a base material, the base material may be thermally deteriorated, and in the case of an inorganic glass base material, an appearance defect after a rubbing test tends to occur.

As described above, the specific inorganic paint is applied on the optical inorganic vapor deposition film having the outermost SiO ₂ layer formed on the surface of the base material, and heat-treated at a specific temperature, thereby performing the optical inorganic vapor deposition. The present inventors have found that an antifogging functional film excellent in durability (particularly in a rubbing test) can be formed on the film.

The anti-fogging functional film of the present invention imparts hydrophilicity to the base material because an anti-fogging functional film having a specific acrylic polymer as a coating film forming element is formed on the optical inorganic vapor deposition film having the outermost SiO ₂ layer. It is possible to prevent the water from being washed away when water adheres as in the case of using a conventional surfactant. Furthermore, it has been found that the specific acrylic polymer that forms the antifogging functional film in the present invention can provide a sufficient antifogging function even if the film thickness is thin. For this reason, it is not necessary to make the anti-fogging functional film thick as in the case of using a conventional hydrophilic graft polymer. For this reason, it is possible to prevent the low-reflectivity of the antireflection film from being impaired due to the thick surface layer, and to make the heat treatment temperature relatively high, so that the antifogging after the rubbing test can be prevented. Excellent in properties and appearance.

  Hereinafter, Examples and Comparative Examples performed for confirming the effects of the present invention will be described in detail. FIG. 1 is a model cross-sectional view showing an optical basic configuration of an example / comparative example, and FIG. 2 is a schematic manufacturing process diagram.

  (1) The drug and optical substrate are as follows.

<Primer metal oxide fine particles>
TPEE "Pesresin A-160P" (manufactured by Takamatsu Yushi Co., Ltd., polyester-polyether type water-dispersed emulsion (aqueous), solid content concentration 27%)
-Titania-based metal oxide fine particles A "Optlake 1130F-2 (A-8)" (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 30%, dispersion solvent methyl alcohol)
-Titania-based metal oxide fine particle B "Optlake 1120Z (S-7, G)" (manufactured by Catalyst Kasei Kogyo Co., Ltd., solid content concentration 20%, dispersion solvent methyl alcohol)

<Antireflection film (optical inorganic vapor deposition film) material>
Lanthanum titanate “Substance H4” (hereinafter referred to as “specific vapor deposition film material”)

<Organic glass substrate>
Refractive index 1.60: “MR-20” (Mitsui Chemicals, Inc.)

<Inorganic glass substrate>
-Refractive index 1.52: Commercial quartz glass plate

  Each of the above substrates was pre-treated by being immersed in a 10% NaOH aqueous solution at 40 ° C. for 3 minutes, then washed with water and dried.

(2) The primer composition was prepared as follows.
To 100 parts of commercially available TPEE “Pesresin A-160P”, 57 parts of titania-based metal oxide fine particles “Optlake 1120Z (S-7.G)”, 350 parts of methyl alcohol as a diluent, and silicone-based surfactant “L- A primer composition was prepared by mixing 1 part of 7001 "and stirring until uniform.

(3) The hard coat (HD) composition was prepared as follows.
150 parts of γ-glycidoxypropyltrimethoxysilane and 25 parts of tetraethoxysilane are added with 150 parts of methyl alcohol, and 40 parts of 0.01N hydrochloric acid are added dropwise with stirring to perform hydrolysis overnight to prepare a hydrolyzate. did.

  The hydrolyzate was mixed with 170 parts of titania-based metal oxide fine particles “Optlake 1130F-2 (A-8)”, 1 part of a silicone surfactant (L-7001) and 1.0 part of acetylacetone aluminum as a catalyst. The mixture was stirred for a whole day and night to prepare a hard coat composition.

  (4) Anti-fogging functional film coating was prepared by diluting LAMBIC770W, a 10% aqueous solution of a specific acrylic polymer marketed by Osaka Organic Chemical Co., Ltd. mPa · s) was prepared.

(5) Sample preparation for each test example For each organic glass substrate sample, each substrate was washed with an alkali, and then a primer coat composition was applied and cured under conditions of 100 ° C. × 20 min, and then a hard coat composition. Was applied and cured under conditions of 110 ° C. × 2 h to form primer coat films / hard coat films (HD films) 19 and 17.

Furthermore, while heating the vacuum chamber in the vacuum deposition apparatus to 60 ° C., exhausting to a pressure of 1.33 × 10 ⁻³ Pa or less, performing oxygen ion cleaning, and performing ion assist on the HD film, An antireflection film (AR1, AR2, AR4) having the structure shown in Table 1 was formed by vacuum deposition.

  For the inorganic glass substrate, an alkali-cleaned substrate is formed with an antireflection film (AR3 / AR5 / AR6) having the structure shown in Table 1 in the same manner as the organic glass substrate described above. The sample which each processed and formed each anti-fogging functional film was prepared.

  The ion cleaning was performed at an acceleration voltage of 200 V and an ion assist acceleration voltage of 600 V.

  The plasma treatment was performed at an output of 500 W and a time of 80 seconds.

  Then, after the coating material for the antifogging function film is dip-coated on the surface of each sample under the condition of the pulling speed (150 mm / min), the heating temperature is changed for each group and the heat treatment is performed for 15 min to perform the antifogging function film 15. Each test piece was prepared by forming a film. The heating temperature at this time is 3 points in the range of 60 to 80 ° C. in the case of the organic glass substrate (Tables 2 and 3), and 6 points in the range of 60 to 180 ° C. in the case of the inorganic glass (Tables 4 and 5). It was.

  Further, an anti-fogging treatment film is formed on an object to be processed having a hard film of an organic glass substrate or an object to be processed having an antireflection film (AR2) on the hard film in the same manner as in the example. Specimens that were not heat-treated were prepared as Control Examples 1 and 2, respectively.

  In addition, after preparing each test piece, the surface impurities were removed with pure water, and the surface was dried by air blow.

  (6) The physical properties / evaluation tests of the following items were performed on the test pieces of each reference example and example group prepared as described above. The number of samples was n = 5 for each test item. Moreover, the numerical value of the contact angle was an arithmetic average value of intermediate n = 3.

  Further, the contact angle test was not performed after various cleaning treatments or after the rubbing test when the contact angle greatly exceeded the acceptance standard of 10 ° (the superhydrophilic performance was sufficiently exhibited).

<Test items>
As the performance of the anti-fogging function film, two characteristics of “exhalation spray appearance” and “(water) contact angle” were used as judgment criteria. That is, the former is a sensory characteristic, and the latter is a quantitative characteristic, which is substantially in a relative relationship, but as shown in the test results described later, depending on the test conditions, it is not necessarily a correlation. .

1) Initial exhalation appearance Immediately after preparation of each test piece, exhalation was sprayed, and the state of the antifogging functional film was visually observed. The judgment criteria were as follows.

○: There is a water thin film on the entire surface (Note: A water thin film is formed on the entire surface and is not fogged)
Δ: Partially thin water film (Note: The part where the water thin film is not formed is cloudy)
×: No water thin film on the entire surface (Note: No water thin film on the entire surface and fogging occurs)

2) Appearance of exhaled breath after rubbing test For each test piece, the following rubbing test is performed for the number of times indicated (50, 1000, 3000 times). Visual observation was performed. ○, Δ, and × of the breath blowing appearance determination criteria are the same as in 1) above.
-A load of 500 g was applied to the glasses cloth, and it was carried out at a stroke of 1 sec.

3) Initial contact angle About each test piece, the contact angle was measured by the following method immediately after preparation.
-A water drop was dripped at each test piece, and the contact angle with water was measured in the atmosphere at 25 ° C using a contact angle meter (manufactured by Elma Co., Ltd.).

4) Contact angle after cleaning After each test piece was cleaned by the following methods, the surface was dried by air blow and the contact angle was measured by the above method.
・ Water washing: pure water (20 ℃) x immersion 5min
・ Hot water washing: Heated pure water (40 ℃) x Immersion 5min
・ Ultrasonic cleaning: 25Hz x immersion 5min

5) Contact angle after rubbing test For each test piece, the rubbing test was performed the number of times indicated (50, 1000, 3000 times) in the same manner as 2) above, and the contact angle was measured.

<Test results and discussion>
The test results are shown in Table 2 (appearance test) and Table 3 (contact angle) when the transparent substrate is an organic glass, and Table 4 and Table 5 when the transparent substrate is an inorganic glass.

1) Organic glass substrate:
In Reference Example 1-1 at a treatment temperature of 60 ° C., Examples 1-1 and 1-2 were performed in the initial breathing appearance and the breathing appearance after the rubbing test shown in Table 2 and in the contact angle after washing shown in Table 3. It turns out that it is substantially equivalent to -1. Moreover, in the contact angle after a rubbing test, when the frequency | count of rubbing increases (3000 times), it turns out that the reference example 1-1 with a process temperature of 60 degreeC can hardly exhibit an anti-fogging function.

  When the reference example 1-2 and the reference example 1-3 at the processing temperatures of 80 ° C. and 100 ° C. are compared with the examples 1-2, 1-3 and the examples 2-2, 2-3, the number of rubbing is 1000 times. It can be seen that there is a clear significant difference in contact angle at 3000 times.

From the above, even in the outermost SiO ₂ layer, when the processing temperature is low, the inorganic vapor-deposited film and the antifogging functional film are generated by hydrolysis of the OH group on the outermost SiO ₂ layer and the alkoxysilyl group. This is considered to be because it is difficult to stably obtain the state of being bonded through dehydration condensation with the OH group. From the above results, it can be seen that the treatment temperature is preferably 55 ° C. or higher, and more preferably 75 ° C. or higher in order to reliably obtain the effects of the present invention.

  Furthermore, in the case of Example 2 group in the case of a heat-resistant vapor deposition film, it can be seen that if the treatment temperature is increased (Example 2-3), it is easy to ensure the antifogging property stably (Table 2, Table 2). (Refer to spray appearance and contact angle after rubbing test in 3).

In addition, it was confirmed that the comparative example 1 group which is the non-SiO ₂ outermost layer of the inorganic vapor-deposited film can obtain only antifogging property inferior to the reference example 1 group in which the antifogging functional film is directly applied to the HD film. That is, the comparative example 1 group has an initial contact angle of 30 °, and the reference example 1 group has an initial contact angle of 4 ° (see Table 3).

  Further, as is apparent from Comparative Examples 1 and 2, it can be seen that, when the heat treatment is not performed, even if the antifogging functional film is formed, the antifogging property cannot be exhibited at all after the cleaning treatment. That is, it is presumed that the anti-fogging functional film flows out without heat treatment.

2) Inorganic glass substrate:
Reference Example 2 group, in which an anti-fogging functional coating film was directly formed on inorganic glass and heat-treated, was in contact with Examples 3-5 group in which the inorganic vapor deposition film of the outermost SiO ₂ layer was formed, and contact after the same cleaning and rubbing test. The corners are approximately equivalent (see Table 5).

  However, in the appearance after the rubbing test, as shown in Tables 4 and 5, in the case of the reference example 2 group, when the heat treatment temperature of the antifogging functional film is low (60 ° C.), the fogging occurs 1000 times in the rubbing test. In the case (100 ° C.), clouding occurred after 3000 rubbing tests, and it was found that the sensory test was inferior to the groups of Examples 3 to 5, respectively.

  Furthermore, when the heat treatment temperature is increased, as shown in Table 5, the tendency of increasing the contact angle is small even when the number of rubbing is relatively large, as compared with Reference Example 2 applied directly on the inorganic glass. I understand. That is, it can be said that it is excellent in abrasion resistance.

11 Transparent substrate (organic glass substrate)
13 Optical inorganic vapor deposition film (Antireflection film)
15 Anti-fogging functional film 17 Hard coat film 19 Primer coat film

Claims (13)

In an optical element comprising a single-layer or multilayer optical inorganic vapor deposition film on one or both sides of a transparent substrate, and further comprising an antifogging functional film on the upper surface of the optical inorganic vapor deposition film,
The optical inorganic vapor-deposited film has a heat resistant specification and includes an outermost layer formed of silica (SiO ₂ ) (hereinafter referred to as “SiO ₂ outermost layer”).
The antifogging functional film comprises a coating film of a (meth) acrylic polymer having an alkoxysilyl group (—Si (OR) ₃ , where R: an alkyl group having 1 to 4 carbon atoms, the same shall apply hereinafter),
The optical inorganic vapor-deposited film and the antifogging functional film are bonded through dehydration condensation between an OH group on the outermost SiO ₂ layer and an OH group generated by hydrolysis of the alkoxysilyl group.
An optical element characterized by that. The heat-resistant optical inorganic vapor deposition film is characterized in that at least one layer inside the outermost SiO ₂ layer is formed of a vapor deposition film of a sintered mixture of the following composition (hereinafter referred to as “specific vapor deposition film”). The optical element according to claim 1.
Titanium oxide (TiO _x ; x = 1.5 to 1.8) 10 to 65% by mass,
Lanthanum oxide (La ₂ O ₃ ) 33-74% by mass
Titanium (Ti) 2-7% by mass The film structure of the optical inorganic vapor-deposited film is characterized in that a vapor-deposited film selected from one or more of ZrO ₂ , a TiO ₂ mixture and ITO is interposed inside the outermost SiO ₂ layer. 2. The optical element according to 2.   The said transparent base material is formed with organic glass, and the said optical inorganic vapor deposition film is formed through the hard-coat film | membrane on the said transparent base material, The Claim 1, 2, or 3 characterized by the above-mentioned. Optical element.   The optical element according to claim 4, wherein a primer coat film is interposed between the transparent substrate and the hard coat film.   5. The hard coat film according to claim 4, wherein the hard coat film is formed of a hard coat composition obtained by adding a catalyst and metal oxide fine particles (including composite fine particles) to a hydrolyzate of organoalkoxysilane. Optical element. A method for producing an optical element comprising a single-layer or multilayer optical inorganic vapor-deposited film on one or both sides of a transparent substrate, and further comprising an antifogging functional film on the upper surface of the optical inorganic vapor-deposited film,
The optical inorganic vapor-deposited film having a heat resistant specification and the SiO ₂ outermost layer is vapor-deposited, and the anti-fogging functional film is coated with a paint having a (meth) acrylic polymer having an alkoxysilyl group as a film-forming element. When forming with a film,
A method for producing an optical element, wherein heat treatment is performed after the coating film is formed.   8. The method of manufacturing an optical element according to claim 7, wherein the transparent substrate is made of organic glass, and the heat treatment is performed under conditions of a temperature of 55 to 120 ° C. × 5 to 60 min.   The method of manufacturing an optical element according to claim 8, wherein the heat treatment is performed under a condition of 75 to 120 ° C. × 10 to 30 minutes.   8. The method of manufacturing an optical element according to claim 7, wherein the transparent substrate is made of inorganic glass, and the heat treatment is performed under conditions of 55 to 200 ° C. × 5 to 60 minutes.   The method of manufacturing an optical element according to claim 10, wherein the heat treatment is performed under a condition of 75 to 200 ° C. × 5 to 60 min. 8. The method of manufacturing an optical element according to claim 7, wherein the surface of the outermost SiO ₂ layer is activated.   13. The method of manufacturing an optical element according to claim 12, wherein the activation process is performed by a plasma process.

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