JP4606215B2 - Photochromic optical article and method for producing the same - Google Patents

Description

  The present invention relates to a photochromic optical article such as a photochromic plastic lens having excellent durability and a method for producing the same.

  Photochromic glasses are lenses that quickly color and function as sunglasses when exposed to light containing ultraviolet rays such as sunlight. Demand for spectacles that function as spectacles, particularly those using photochromic plastic lenses, has increased in recent years.

As a method for producing a plastic lens having photochromic properties, the following three methods are broadly known. (In the following description, a normal lens that does not have photochromic properties is simply referred to as a lens substrate.)
(i) A method of directly obtaining a photochromic lens by dissolving a photochromic compound in a monomer and polymerizing it (mixing method);
(ii) A method (impregnation method) of forming a photochromic layer on the surface of a composition containing a photochromic compound by impregnating a lens substrate;
(iii) A method (coating method) of forming a photochromic layer on the surface of a lens substrate by coating a composition (photochromic coating agent) in which a photochromic compound is dispersed;
Among the above methods, the kneading method has a limitation that it is necessary to use a special monomer composition in order to develop good photochromic properties. In the impregnation method, it is necessary to use a soft base material that easily diffuses the photochromic compound as the lens base material. On the other hand, the coating method has an advantage that, in principle, photochromic properties can be imparted to any lens substrate, and has recently attracted particular attention.

  In the coating method, it was a big technical problem to firmly adhere the photochromic layer to the lens substrate, but a coating agent that can form a photochromic layer having high adhesion to the lens substrate has also been developed. Practical use is becoming a reality. For example, Patent Document 1 discloses such a photochromic coating agent as “a radical polymerizable monomer containing a radical polymerizable monomer having a silanol group or a group that generates a silanol group by hydrolysis, an amine compound, and A curable composition containing a specific amount of a photochromic compound has been proposed.

  In this way, the coating method can be said to be a very excellent method for producing a photochromic lens. However, when a photochromic layer is formed by such a coating method, the photochromic compound in the photochromic layer deteriorates when used for a long time. As a photochromic compound, indenonaphthopi has a good photochromic property. When a orchid compound is used, the deterioration is remarkable. In addition, such a problem is similarly generated in a lens in which a photochromic layer is formed by an impregnation method. The main cause of the deterioration of the photochromic compound is that the photochromic compound is oxidized and deteriorated by contact with oxygen in the atmosphere.

  As a method for preventing such oxidative degradation of the photochromic compound in the photochromic layer, Patent Document 2 discloses that a thin film made of metal oxide particles or metal fine particles is formed on the surface of a photochromic layer having a thickness of about 20 μm. Proposed.

International Publication No. 03/011967 Pamphlet JP-A-6-192651

  However, the thin film as proposed in Patent Document 2 can suppress oxidation degradation to some extent and prevent deterioration of the characteristics of the photochromic layer, but the effect is not yet sufficient and practical. From the aspect, it is required to further improve the photochromic durability. In particular, when a compound having a good photochromic property such as an indenonaphthopyran compound developed in recent years is used, the photochromic property can be obtained simply by providing a thin film such as a metal oxide as in Patent Document 2. The decrease cannot be effectively suppressed, and it has been difficult to maintain the excellent photochromic property for a long period of time.

  Accordingly, an object of the present invention is to form a photochromic layer containing an indenonaphthopyran compound as a photochromic compound on the surface of an optical substrate such as a plastic lens, and the deterioration of the characteristics of the photochromic layer due to oxidative degradation is highly suppressed. An object of the present invention is to provide a photochromic optical article and a method for producing the same, which are extremely excellent in durability.

〔前記式（１）において、
Ｒ ^２６ 、Ｒ ^２７ 、Ｒ ^２８ およびＲ ^３０ は、それぞれ、水酸基、アルキル基、トリフルオロメチル基、アルコキシ基、アルコキシカルボニル基、カルボキシル基、アルコキシメチル基、ヒドロキシメチル基、アラルコキシ基、アミノ基、置換アミノ基、シアノ基、ニトロ基、ハロゲン原子、アラルキル基、置換もしくは非置換のアリール基、置換若しくは非置換のヘテロアリール基、窒素原子をヘテロ原子として有し且つ該窒素原子が上記インデノナフト環に結合している置換もしくは非置換の複素環基、又は前記複素環基に芳香族炭化水素環もしくは芳香族複素環が縮合した縮合複素環基であり；
環Ｑは脂肪族炭化水素環基であり；
ｙ、ｙ’、ｙ”およびｙ”’は、各々、０〜２の整数であり；
Ｒ ^２９ は、ジアルキルアミノ基、窒素原子をヘテロ原子として有し且つ該窒素原子が上記フェニル基に結合している置換もしくは非置換の複素環基である〕
で表されるインデノナフトピラン化合物が使用され、且つ前記フォトクロミック層は、３０〜５０μｍの厚みを有しているとともに、
前記金属酸化物薄膜は、０．０１〜１μｍの厚みを有しており、且つ単層構造を有していることを特徴とするフォトクロミック性光学物品が提供される。 According to the present invention, an optical substrate having a photochromic layer in which a photochromic compound is dispersed in a resin is formed on at least one surface, and a buffer layer having a thickness of 0.1 to 20 μm is formed on the photochromic layer. a photochromic optical article comprising a deposition film of metal oxides,
As the photochromic compound, the following general formula (1):

[In the above formula (1),
R ²⁶ , R ²⁷ , R ²⁸ and R ³⁰ are each a hydroxyl group, alkyl group, trifluoromethyl group, alkoxy group, alkoxycarbonyl group, carboxyl group, alkoxymethyl group, hydroxymethyl group, aralkoxy group, amino group, substituted An amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a nitrogen atom as a heteroatom, and the nitrogen atom is bonded to the indenonaft ring Substituted or unsubstituted heterocyclic group, or a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the heterocyclic group;
Ring Q is an aliphatic hydrocarbon ring group;
y, y ′, y ″ and y ″ ′ are each an integer from 0 to 2;
R ²⁹ is a dialkylamino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom bonded to the phenyl group]
And the photochromic layer has a thickness of 30 to 50 μm, and an indenonaphthopyran compound represented by :
The metal oxide thin film has a thickness of 0.01 to 1 μm and has a single layer structure , and a photochromic optical article is provided.

According to the present invention, the photochromic layer having a thickness of 30 to 50 μm and an indenonaphthopyran compound represented by the general formula (1) dispersed in the resin has a thickness of 0. An optical substrate formed through a buffer layer of 1 to 20 μm is prepared, and a metal oxide thin film having a thickness of 0.01 to 1 μm and having a single layer structure is formed on the photochromic layer by vapor deposition. A method for producing a photochromic optical article is provided.

  In the present invention, the photochromic layer formed of a resin in which an indenonaphthopyran compound is dispersed uses another photochromic compound in which the degree of reduction in photochromic properties due to oxidative degradation greatly depends on the thickness of the photochromic layer. It was made on the basis of a new finding that it has a property that is not seen in some cases, and its thickness is made comparatively thick at 30 to 50 μm, and a metal oxide thin film is formed on the photochromic layer having such a thickness. Thus, it is possible to effectively suppress deterioration in characteristics of the photochromic layer due to oxidative degradation and to maintain the excellent photochromic properties of the indenonaftpyran compound over a long period of time. Thus, it is quite unexpected that the degradation of the characteristics of the photochromic layer is suppressed by making the thickness of the photochromic layer relatively thick only when the indenonaftpyran compound is used. Estimates are as follows.

That is, when the photochromic layer in which the indenonaphthopyran compound is dispersed is thin, it is not possible to completely block oxygen transmitted through the photochromic layer despite the provision of the metal oxide thin film. Although it is a small amount, oxygen diffuses throughout the photochromic layer, and the indenonaphthopyran compound is oxidatively deteriorated throughout the layer, so that the photochromic property is lowered (that is, the photochromic durability is low). For example, as shown in Comparative Example 7 described later, when the thickness of the photochromic layer is about 20 μm, the photochromic durability is considerably low. Such a decrease in photochromic properties is the same when other photochromic compounds are used (Comparative Example 6).

  However, when the thickness of the photochromic layer in which the indenonaphthopyran compound is dispersed is 30 to 50 μm, as shown in Example 1 or the like, the deterioration of the photochromic property is remarkably suppressed, and the photochromic durability is improved. In particular, it can be seen that the yellowing suppression effect is remarkably improved. However, in the photochromic layer in which other photochromic compounds are dispersed, even when the thickness is 40 μm, the improvement in photochromic durability is not sufficient and the yellowing suppression effect is low (Comparative Example 2). Considering this fact, when an indenonaftpyran compound is used, this compound is superior in oxidation resistance (durability against oxidation degradation) compared to other photochromic compounds. By increasing the thickness, a small amount of oxygen that permeated through the thin metal oxide layer is blocked at the upper region of the photochromic layer (the metal oxide thin film side), and diffusion to the inside is suppressed. It is done. That is, the deterioration stops in the upper region, and does not proceed to the inside or the lower region (substrate side) of the photochromic layer. Other photochromic compounds are considered to have low oxidation resistance and a large mechanism for deterioration only by light, so even if the thickness of the photochromic layer is increased, the deterioration proceeds throughout the photochromic layer, resulting in photochromic durability. It is considered that there is no improvement in sex.

  As described above, in the photochromic optical article of the present invention, since the deterioration of the characteristics of the photochromic layer due to oxidative degradation is effectively suppressed, the durability of the photochromic property is remarkably excellent. The topyran compound is not colored yellow in an uncolored state, and the color density in the colored state of the compound does not decrease.

In the present invention, the metal oxide thin layer provided on the photochromic layer is, for example, a single layer and does not have a multilayer structure such as an antireflection film. Is.

Referring to FIG. 1, the photochromic optical article of the present invention has a photochromic substrate denoted by 200 as a whole, and this photochromic substrate 200 has a structure in which a photochromic layer 202 is formed on the surface of an optical substrate 201. Have. On the photochromic layer 202, a metal oxide thin film 300 is provided as a vapor-deposited thin film by a vapor deposition method through a buffer layer 600 . In the example of FIG. 1, the buffer layer 600 is formed of the primer layer 400 and the inorganic fine particle dispersion layer 500, but as described later, only the primer layer 400 can be used as the buffer layer 600, and the inorganic layer is inorganic. Only the fine particle dispersion layer 500 can be used as the buffer layer 600, and the primer layer 400 can also be provided on the inorganic fine particle dispersion layer 500.

Incidentally, the metal oxide thin film 300, as described below, but those that have a single So構 granulation, such thin film 300 is clearly different from the so-called anti-reflection film. That is, as a technique for forming a metal oxide thin film on the surface of a photochromic layer, there is an antireflection treatment performed in a high-grade lens to reduce the surface reflectance of the lens, to suppress flickering and to make it easy to see. The antireflection film formed by this antireflection treatment has a multilayer structure in which five to seven thin layers made of metal oxides having different refractive indexes are laminated in a predetermined order. The physical thin film is not a laminated structure but a single layer , and has substantially no antireflection function for reducing the surface reflectance.

[Optical substrate 201]
The optical substrate 201 is a transparent plate-like body, and has a pair of front and back main surfaces. The plate-like body may be curved, and the thickness thereof is not necessarily constant. For example, when the photochromic optical article of the present invention is used as a photochromic lens, the optical substrate 201 has a lens shape. The optical substrate 201 itself does not have photochromic properties.

  Further, the optical substrate 201 having a transparent plate-like body may be made of any material, for example, plastic or various inorganic materials as long as transparency and appropriate strength can be ensured. Such plastics include various thermosetting or thermoplastic resins such as (meth) acrylic resins; polycarbonate resins; allyl resins obtained by curing diethylene glycol bisallyl carbonate monomers or diallyl phthalate monomers. Thiourethane resin cured with polyisocyanate monomer and polythiol monomer; urethane resin; thioepoxy resin; polyester resin such as polyethylene terephthalate; olefin resin such as polypropylene, polyethylene and polystyrene; epoxy resin; Examples thereof include vinyl resins such as vinyl. Moreover, as an inorganic material, inorganic glass, quartz glass, translucent ceramic, etc. can be illustrated.

Further, the optical substrate 201 may be subjected to surface treatment such as primer treatment, plasma treatment, or corona discharge treatment in order to improve adhesion to the photochromic layer 202. Examples of such surface treatment include chemical treatment by impregnation into a basic aqueous solution or acidic aqueous solution, polishing treatment using an abrasive, plasma treatment using atmospheric pressure plasma, low pressure plasma, and the like. . Such surface treatment is particularly useful when the photochromic layer 202 is formed by a coating method.

[Photochromic layer 202]
The photochromic layer 202 formed on the surface of the optical substrate 201 is made of a resin in which a photochromic compound is dispersed. The presence of the photochromic layer 202 has a reversible change in color due to a predetermined photochromic reaction. In the example of FIG. 1, the photochromic layer 202 is formed only on one surface of the optical substrate 201, but may be formed on the entire surface of the optical substrate 201 having a predetermined shape, depending on the application. It may be formed on the entire surface, or may be partially formed on one surface.

In the present invention, as the photochromic compound dispersed in the photochromic layer 202, it is extremely important to use an indenonaphthopyran compound represented by the following general formula (1) . This compound is a kind of chromene compound and has been recently developed as a photochromic compound that is particularly excellent in photochromic properties such as color development and fading speed. Further, the compound is excellent in durability against oxidative degradation, and by forming the photochromic layer 202 using such an indenonaphthopyran compound, the photochromic durability can be remarkably improved. .

  In the present invention, it is also very important to set the thickness of the photochromic layer 202 in the range of 30 to 50 μm, particularly 30 to 40 μm. As described above, by setting the thickness of the photochromic layer 202 in which the above-mentioned indenonaphthopyran compound is dispersed within the above range, the durability against the oxidative deterioration of the compound is sufficiently exhibited, and metal oxidation described later is performed. Combined with the oxygen barrier function of the physical thin film 300, the photochromic durability is remarkably improved. For example, when a photochromic compound other than an indenonaphthopyran compound is used, the photochromic property is greatly reduced due to oxidative degradation, and the photochromic durability cannot be improved. Even if an indenonaphthopyran compound is used, the photochromic When the thickness of the layer is less than 30 μm, the influence of deterioration due to a slight amount of oxygen that passes through the metal oxide thin film 300 cannot be ignored, and the improvement of the photochromic durability is not brought about. In addition, when the thickness of the photochromic layer is greater than 50 μm, it is not economical and the effect of improving the durability of the photochromic is also reduced. Presumably, defects such as cracks are likely to occur, and a slight amount of oxygen that permeates the metal oxide thin film 300 is diffused throughout the photochromic layer 202 due to physical factors.

The indenonaphthopyran compound described above for use in the present invention, as needed use those represented by the following formula (1).

[In the above formula (1),
R ²⁶ , R ²⁷ , R ²⁸ And R ³⁰ Are a hydroxyl group, an alkyl group, a trifluoromethyl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, an alkoxymethyl group, a hydroxymethyl group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a nitro group, and a halogen atom, respectively. , An aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom bonded to the indenonaphtho ring Or a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the heterocyclic group;
Ring Q is an aliphatic hydrocarbon ring group;
y, y ', y "and y"' are each integers from 0 to 2;
R ²⁹ Is a dialkylamino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom being bonded to the phenyl group]

In the present invention, the indenonaphthopyran compound represented by the above formula (1) can be used alone or in combination of two or more .

The content of indenonaphthopyran compound in photochromic layer 202 is suitably in the range from the point of view of 0.1 to 20 wt% of good color density and durability. In order to improve durability and reduce initial coloring, the content is particularly preferably in the range of 1 to 10% by mass.

In addition to the indenonaphthopyran compound represented by the above formula (1) , the photochromic layer 202 contains other photochromic compounds in order to adjust the color tone of the photochromic lens to an intermediate color such as gray and brown. It may be distributed. Examples of such other photochromic compounds include known photochromic compounds such as fulgimide compounds, spirooxazine compounds, chromene compounds, and indenonaphthopyran compounds other than those represented by the formula (1). Depending on the color tone, it can be used alone or in combination of two or more with the indenonaphthopyran compound represented by the above formula (1) .

  Examples of the fulgimide compound, spirooxazine compound and chromene compound described in JP-A-2-28154, JP-A-62-228830, WO94 / 22850, WO96 / 14596, etc. Can be used. Also, JP 2001-114775, JP 2001-031670, JP 2001-011067, JP 2001-011066, JP 2000-347346, JP 2000-344762, JP 2000-344761. JP, 2000-327676, JP 2000-327675, JP 2000-256347, JP 2000-229976, JP 2000-229975, JP 2000-229974, JP 2000-229973, JP 2000-229972, JP 2000-219687, JP 2000-219686, JP 2000-219685, JP 11-322739, JP 11-286484, JP 11-279171, Special The photochromic compounds described in Kaihei 10-298176, JP 09-218301, JP 09-124645, JP 08-295690, JP 08-176139, JP 08-157467, etc. are also used. be able to.

  In the present invention, among various photochromic compounds used in combination with indenonaphthopyran compounds, the effect of improving the durability of photochromic properties is high, the color density and fading speed are also good, and the indenonaphthopyran compounds are excellent. A chromene compound is preferred because it does not impair the properties. Specific examples of such chromene compounds include WO94 / 22850 pamphlet, WO98 / 45281 pamphlet, US Pat. No. 5,932,725, US Pat. No. 6,525,194, and the like. However, examples of the most suitable chromene compound include chromene compounds shown below.

These other photochromic compounds should generally be used in an amount that does not impair the excellent properties of the indenonaphthopyran compound represented by the general formula (1) described above. The content of is preferably 75% by mass or less of the indenonaphthopyran compound represented by the general formula (1) .

  In the present invention, the above-described photochromic layer 202 can be formed on the surface of the optical substrate 201 by a known impregnation method or coating method.

  In the impregnation method, a coating liquid in which the above-described photochromic compound (indenonaphthopyran compound) is dissolved or dispersed in a predetermined organic solvent together with a resin serving as a binder is prepared, and the optical substrate 201 is immersed in the coating liquid. A photochromic layer 202 is formed by forming a coating liquid film and then drying, and for example, an impregnation method disclosed in US Pat. No. 5,739,243 is suitably employed. On the other hand, in the coating method, a known coating agent made of a curable composition containing a photochromic compound and a polymerizable monomer is used as the surface of the optical substrate 201 described above (the surface treatment described above is performed if necessary). The photochromic layer 202 is formed by applying and polymerizing and curing. In particular, the coating agent is preferably made of a curable composition disclosed in, for example, WO 03/011967 pamphlet. In the present invention, as already described, it is preferable to form the photochromic layer 202 by a coating method in that there are few restrictions on the optical substrate 201.

  When the photochromic layer 202 is formed by a coating method, the content of the photochromic compound in the coating agent (curable composition), particularly the indenonaphthopyran compound, in the photochromic layer 202 formed by curing is in the above-described range. The viscosity (20 ° C.) of the coating agent is 20 to 1000 cP, particularly 50 to 500 cP, so that the thickness of the photochromic layer 202 can be adjusted to the above-described range (30 to 50 μm). It should be in range. Furthermore, as the polymerizable monomer in the coating agent, various radical polymerizable monomers can be used, but at least a part thereof is an epoxy monomer such as glycidyl acrylate or glycidyl methacrylate, γ- It is preferable to use a silyl-based monomer having a silanol group or a group that generates a silanol group by hydrolysis, such as methacryloyloxypropyltrimethoxysilane, in terms of improving adhesion to the optical substrate 201.

Further, in the above coating agent, various polymerization initiators such as radical polymerization initiators such as peroxides and azo compounds and photopolymerization initiators such as benzoin methyl ether are blended, and further, photochromic compound Curing catalysts, surfactants, antioxidants, radical scavengers, UV stabilizers, UV absorbers, to improve durability, improve color development speed, improve fading speed and adhesion, or adjust color tone Additives such as an agent, a release agent, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, and a plasticizer may be added.
As an example of the radically polymerizable monomer, a compounding example that is suitably used from the viewpoint that the durability improving effect of the present invention is particularly noticeable and that the photochromic properties and the adhesion of the photochromic resin layer are good,
For 100 parts by weight of all radical polymerizable monomers,
A) An epoxy monomer or / and a silyl monomer are 0.1 to 30 parts by weight B) A medium or high hardness monomer comprising at least 5 parts by weight of a monomer having three or more radical polymerizable groups 5 to 65 parts by weight,
C) It is particularly preferable that 5 to 90 parts by weight of the low hardness monomer is blended.

  Here, the high, medium and low high monomers of B) and C) can be classified as those having a homopolymer L scale Rockwell hardness of 60 or more, particularly 65 to 130 as a high hardness monomer. A low-hardness monomer has a combined L-scale Rockwell hardness of 40 or less. Furthermore, a monomer having an L scale Rockwell hardness of more than 40 and less than 60 of a single cured product can be defined as a medium hardness monomer. High-hardness monomer has the effect of improving the solvent resistance, hardness, heat resistance, etc. of the cured product after curing, and low-hardness monomer has the effect of making the cured product tough and improving the fading speed of the photochromic compound. Further, by combining a medium hardness monomer as necessary, a photochromic resin excellent in the durability improving effect of the present invention and having excellent photochromic properties and strength is provided.

  Here, L scale Rockwell hardness means hardness measured according to JIS-B7726. It is possible to easily determine whether or not the above-mentioned hardness condition is satisfied by performing the measurement on the homopolymer of each monomer. Specifically, the monomer is polymerized to obtain a cured product having a thickness of 2 mm, and this is easily maintained by measuring the L scale Rockwell hardness using a Rockwell hardness meter after holding it in a room at 25 ° C. for one day. Can be confirmed. The polymer used for the measurement of the L scale Rockwell hardness is obtained by cast polymerization under a condition in which 90% or more of the polymerizable groups of the charged monomer are polymerized. The L scale Rockwell hardness of the cured body polymerized under such conditions is measured as a substantially constant value.

  As the high hardness monomer, low hardness monomer and medium hardness monomer, the high hardness monomer, low hardness monomer and medium hardness monomer used in the photochromic coating agent disclosed in the above-mentioned patent document WO 03/011967, respectively. The same can be used.

  Epoxy monomer or silyl monomer acts as a component for improving adhesion to other components such as a substrate, primer layer or hard coat layer, but for the purpose of further improving adhesion, a curing catalyst comprising an amine compound is used. It is particularly preferred to use it. The amount of the curing catalyst is preferably in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer.

Such a coating agent is an application proposed by the present inventors as a coating agent suitable for producing a photochromic lens by a coating method (WO 03/011967 pamphlet, Japanese Patent Application No. 2002-354291 and Japanese Patent Application No. 2002). -372835).

[Metal oxide thin film 300]
The metal oxide thin film 300 is a deposited thin film formed to block oxygen permeation to the photochromic layer 202, and has a thickness in the range of 0.01 to 1 μm , particularly preferably 0.01 to 0.5 μm. Range . When the film thickness is smaller than this range, the barrier property against oxygen is lowered, and it becomes difficult to improve the photochromic durability. When the film thickness is larger than this range, appearance defects such as cracks are likely to occur in the thin film 300. Become.

Such a metal thin film 300 may be formed of various metal oxides as long as transparency is ensured. For example, the metal oxide thin film 300 is formed of silicon oxide, titanium oxide, zirconium oxide, tin oxide, zinc oxide, cerium oxide, iron oxide, or a composite metal oxide containing these oxide components. Among these, at least one metal oxide selected from the group consisting of silicon oxide, titanium oxide, zirconium oxide, tin oxide and zinc oxide, and titanium oxide / zirconium oxide / tin oxide from the point of not having coloring. From the viewpoint that the composite metal oxide, titanium oxide / zirconium oxide / silicon oxide composite metal oxide, etc. are suitable and the effect of improving the durability by exposure to sunlight is high, silicon oxide, titanium oxide and zinc oxide A thin film made of at least one selected from the group consisting of is particularly suitable, and a thin film made of silicon oxide is most preferred. The thin film 300 is provided as a single layer structure. Therefore, as described above, such a metal oxide thin film 300 is clearly different from an antireflection film having a laminated structure of five or more layers, and can be formed more easily than an antireflection film. It is advantageous.

The metal oxide thin film is formed by a vapor deposition method such as chemical vapor deposition (CVD), physical vapor deposition (PVD), or vacuum vapor deposition. That is, the metal oxide thin film is preferably formed as a vapor-deposited thin film because it can be easily formed at a temperature lower than the heat resistant temperature of the optical substrate.

[Buffer layer 600]
In the present invention, the above-described metal oxide thin film 300 is provided on the photochromic layer 202 via the buffer layer 600 as shown in FIG. That is, the above-described indenonaphthopyran compound is a photochromic compound having excellent photochromic properties, but the metal oxide thin film 300 is directly deposited on the photochromic layer 202 in which such a photochromic compound is dispersed by a vapor deposition method. When formed, a phenomenon that the response speed of the photochromic property is lowered occurs.

Such a phenomenon occurs when the indenonaphthopyran compound is represented by the general formula (1) described above, that is, when the group corresponding to R ²⁹ in the formula (1) contains an amino group ( R ²⁹ in the general formula (1) may be more pronounced der dialkylamino group, a nitrogen atom in the substituted or unsubstituted heterocyclic group and the nitrogen atom has as a hetero atom is bonded to the phenyl group), The tendency for the response speed to decrease is the largest. In these indenonaphthopyrans, the degree of molecular freedom is largely limited by the metal oxide thin film 300 formed densely by vapor deposition, and as a result, the photochromic response speed is greatly reduced. However, by interposing the buffer layer 600 between the photochromic layer 202 and the metal oxide thin film 300, the degree of freedom of the photochromic compound is not limited by the metal oxide thin film 300, and a reduction in response speed is effectively avoided. It becomes possible to do.

  Therefore, the thickness of the buffer layer 600 should be in the range of 0.1 to 20 μm. If this thickness is less than 0.1 μm, a moderate degree of freedom cannot be given to the photochromic compound, and a reduction in response speed due to the metal oxide thin film 300 is unavoidable. On the other hand, if this thickness exceeds 20 μm, cracks will occur. Such a defect is likely to occur, and the effect of suppressing a decrease in response speed does not increase.

  In the present invention, such a buffer layer 600 can be a primer layer or an inorganic fine particle dispersed layer, and the laminated structure of the primer layer and the inorganic fine particle dispersed layer has a buffer layer as long as the total thickness is within the above-described range. For example, as shown in FIG. 1, an inorganic fine particle dispersion layer 500 is formed on the primer layer 400, or a primer layer is further provided on the inorganic fine particle dispersion layer 500. The stacked structure provided with 400 can also function as the buffer layer 600.

  The primer layer 400 functioning as such a buffer layer 600 is formed using a known primer for the purpose of improving adhesion and impact resistance, and includes, for example, an epoxy resin, a urethane resin, and an acrylic resin. It can be formed by using a coating solution containing a primer such as resin, applying by spin coating or dipping, and heating. The thickness of such a primer layer 400 is usually about 1 to 5 μm.

  In addition, the inorganic particle dispersion layer 500 functioning as the buffer layer 600 is obtained by dispersing inorganic particles in a binder resin, and since inorganic particles are dispersed, the adhesion to the metal oxide thin film 300 formed particularly by vapor deposition. It has the characteristic that the property is high. The inorganic particle dispersion layer 500 is coated with a coating agent mainly composed of a colloidal particle of an inorganic compound and a hydrolyzable organosilicon compound as a binder or a hydrolyzate thereof, such as a silicone coating agent. Then, it can be formed by curing.

  Examples of the colloidal particles of the inorganic compound in the coating agent include metal oxides such as silicon oxide, zinc oxide, cerium oxide, zirconium oxide, iron oxide, and titanium oxide, and composite oxides containing these metal oxides. In the coating agent, it is preferably contained in the range of 20 to 70% by mass, particularly 30 to 60% by mass in terms of solid content. When the colloidal particle content is larger than the above range, the adhesion between the inorganic particle dispersion layer 500 and the photochromic layer 202 or the primer layer 400 tends to decrease. In some cases, the inorganic particle dispersion layer is directly formed on the photochromic layer 202. When 500 is formed, the function as a buffer layer is lowered, and the responsiveness reduction preventing function of the photochromic compound may be impaired.

  Moreover, what is generally used as a silane coupling agent is used suitably as a hydrolysable organosilicon compound or its hydrolyzate. Specific examples of such organosilicon compounds include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, vinyltrialkoxysilane, allyltrialkoxysilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, γ-aminopropyltrialkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraacetoxysilane and the like can be exemplified. The binder made of such an organosilicon compound or a hydrolyzate thereof is preferably blended in the coating agent in an amount of 30 to 80% by mass in terms of solid content.

  Moreover, in addition to what was mentioned above, said silicone type coating agent may contain other additives, for example, an acid, a leveling agent, a curing catalyst, and may further contain an organic solvent.

  The acid is used to promote hydrolysis and condensation of the organosilicon compound serving as a binder, and a mineral acid such as hydrochloric acid is preferably used. Such an acid is generally used in an amount of 1 to 10 mmol per 1 mol of the organosilicon compound.

  The organic solvent is used to adjust the viscosity of the coating agent to enhance the coating property, or is used as a dispersion medium (sol) for the colloidal particles described above, and includes methanol, isopropanol, t-butyl alcohol, di-acid. Acetone alcohol, ethylene glycol monoisopropyl ether, and dioxane can be preferably used. The content of the organic solvent in the coating agent is generally 40 to 90% by weight.

  Leveling agents include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, propylene glycol / pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid Examples thereof include esters and polyoxyethylene alkyl ethers. The content of such a leveling agent is about 0.01 to 3% by mass per coating agent.

  Further, the curing catalyst is to accelerate and cure the polycondensation of the hydrolyzed organosilicon compound, and perchloric acids such as perchloric acid, ammonium perchlorate and magnesium perchlorate, Cu (II), Zn (II), Co (II), Ni (II), Be (II), Ce (III), Ta (III), Ti (III), Mn (III), La (III), Cr (III), Acetylacetonate with V (III), Co (III), Fe (III), Al (III), Ce (IV), Zr (IV), V (IV), etc. as the central atom; amino acids such as amine and glycine Lewis acid; organometallic salt; etc. are preferably used. These curing catalysts are added to the coating agent in an amount of 0.1 to 3% by weight per solid content.

  The thickness of the inorganic particle dispersion layer 500 is usually 1 to 5 μm.

  In addition, although it can also form in the inorganic particle dispersion layer 500 mentioned above using the coating agent for forming the hard-coat film | membrane provided in the surface of what is called a plastic lens etc., it is not provided as a hard-coat film | membrane. Therefore, the content of inorganic particles in the coating agent may be smaller than that of the coating agent for hard coat film. Further, when the inorganic particle dispersion layer 500 has the same inorganic particle content as that of the hard coat film, such an inorganic particle dispersion layer 500 may be provided on the surface of the metal oxide thin film 300 as a hard coat film, if necessary. it can.

In the following examples and comparative examples, the following photochromic compounds were used.
Indenonaft Piran (a):

Indenonaft Piran (b):

Chromen (A):

Chromen (B):

Chromen (C):

Moreover, the photochromic characteristic about the photochromic optical article obtained by the Example and the comparative example was performed about the following items.
(1) Maximum absorption wavelength (λmax):
Using a xenon lamp L-2380 (300 mW) manufactured by Hamamatsu Photonics, the sample photochromic optical article was irradiated with light through an aeromass filter (manufactured by Corning) for 120 seconds under the following irradiation conditions to cause color development.

Light irradiation conditions;
Temperature: 20 ± 1 ° C
Beam intensity at the surface
365 nm = 2.4 mW / cm ²
254 nm = 24 μm / cm ²
The maximum absorption wavelength (λmax) at this time was determined with a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.
(2) Color density (Abs.):
In the same manner as described above, the photochromic optical article of the sample was irradiated with light for 120 seconds, the absorbance (ε ₁₂₀ ) at the maximum absorption wavelength (λmax) was measured, and further, the optical article at the wavelength of the optical article not irradiated with light was measured. Absorbance (ε ₀ ) was measured, the difference between the two (ε ₁₂₀ -ε ₀ ) was determined, and this was defined as the color density A. It can be said that the higher this value, the better the photochromic properties.
(3) Durability:
The obtained photochromic optical article was accelerated and deteriorated for 50 hours by a Xenon weather meter X25 (fade meter) manufactured by Suga Test Instruments Co., Ltd. The color density was measured before and after this accelerated deterioration, and the residual rate was determined by the following formula, which was used as an index of color durability.

Residual rate (%) = (A ₅₀ / A ₀ ) × 100
A ₀ : Color density before accelerated deterioration A ₅₀ : Color density after accelerated deterioration The higher the residual ratio, the higher the durability of color development.
(4) Yellowness (Yellow Index; YI):
A 50-hour degradation acceleration test was performed in the same manner as described above, and the change in yellowness (ΔYI) before and after color development of the photochromic optical article before and after degradation acceleration (the photochromic compound was not colored) was determined by the following formula. .

ΔYI = YI ₅₀ −YI ₀
YI ₀ ; yellowness before accelerating deterioration YI ₅₀ ; yellowness after accelerating deterioration Yellowness was measured using a color difference meter (SM-4) manufactured by Suga Test Instruments Co., Ltd. The higher the YI value, the stronger the yellowness, and the larger the ΔYI value, the greater the degree of yellowing before and after deterioration.
(5) Fading speed:
As described above, the sample photochromic optical article was irradiated with light for 120 seconds, and the light absorption at the maximum absorption wavelength (λmax) of the optical article was half the value of the previously measured color density A after the light irradiation was stopped. The time (t _1/2 ; min) until the time of the measurement was measured, and this time (t _1/2 ) was evaluated as the fading speed. The shorter this time (t _1/2 ), the better the photochromic properties.
Example 1
A 2 mm-thick lens base material (refractive index = 1.50) made of a cured bisethylene glycol diallyl carbonate was prepared, and a primer PFR4 (moisture-curable urethane primer) manufactured by Takebayashi Chemical Industry Co., Ltd. was prepared as a primer.

  The above primer and ethyl acetate were mixed at a weight ratio of 9: 1 and sufficiently stirred until uniform in a nitrogen atmosphere to prepare a primer solution. This primer solution is applied to the surface of a lens substrate sufficiently degreased with acetone using a spin coater (MIKASA 1H-DX2) and cured at room temperature for 20 minutes to form a primer layer on the surface of the lens substrate. Formed.

Then the following composition:
2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane; 50 parts by weight Polyethylene glycol diacrylate (average molecular weight 532); 15 parts by weight Trimethylolpropane trimethacrylate; 15 parts by weight Polyester oligomer hexaacrylate (Daicel UCB) EB-1830); 10 parts by weight Glycidyl methacrylate; A mixture of 10 parts by weight of radically polymerizable monomer was prepared. A photochromic polymerizable composition (photochromic coating solution) was prepared according to the following prescription using the mixture of radical polymerizable monomers and the photochromic compound described above.

100 parts by weight indenonaphthopyran (a); 2.35 parts by weight chromene (A); 0.2 parts by weight chromene (B); 1.6 parts by weight polymerization initiator; 5 parts by weight Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (stabilizer); 5 parts by weight γ-methacryloyloxypropyltrimethoxysilane (silane coupling agent); 7 parts by weight As the polymerization initiator, a mixture (weight ratio 3: 1) of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide was used. .

About 2 g of the photochromic coating solution was spin-coated on the surface of the lens substrate (primer layer surface) using the spin coater. The lens substrate coated with this photochromic coating solution is irradiated with light for 3 minutes using a metal halide lamp with an output of 120 mW / cm ² in a nitrogen gas atmosphere to cure the photochromic coating solution. An optical substrate having a photochromic layer on the surface was obtained by performing a heat treatment for 1 hour. The film thickness of the obtained photochromic layer was 40 μm.

  Next, on the photochromic layer, Tokuyama Co., Ltd. hard coat liquid TS-56H (organic silicon sol; silica content 50% by mass in terms of solid content) was applied by dipping and cured at 120 ° C. for 2 hours. An inorganic particle dispersion layer having a thickness of 1.6 μm was formed.

Next, a 0.02 μm-thick silicon oxide thin film was formed on the surface of the inorganic particle dispersion layer by vapor deposition to obtain a photochromic optical article. The photochromic properties of this optical article were evaluated according to the method described above, and the results are shown in Table 1.
Example 2
A photochromic optical article was produced in the same manner as in Example 1 except that a titanium oxide thin film (thickness: 0.02 μm) was formed by vapor deposition instead of the silicon oxide thin film, and the photochromic characteristics were measured. The results are shown in Table 1.
Example 3
Optical base material having a photochromic layer on the surface in the same manner as in Example 1 except that chromene (A) and (B) are not used as the photochromic compound and 1.5 parts by weight of indenonaftpyran (a) is used. Was made. A photochromic optical article was produced in the same manner as in Example 1 except that this photochromic optical substrate was used and the thickness of the silicon oxide thin film was changed to 0.1 μm, and the photochromic characteristics were measured. The results are shown in Table 1.
Comparative Example 1
A photochromic optical article was produced in the same manner as in Example 3 except that a silicon oxide thin film was formed directly on the photochromic layer without forming the inorganic particle dispersion layer, and the photochromic characteristics were measured. The results are shown in Table 1.
Comparative Example 2
A photochromic optical article was produced in the same manner as in Example 3 except that 1.5 parts by weight of indenonaphthopyran (b) was used instead of indenonaphthopyran (a) as a photochromic compound, and the photochromic properties were obtained. It was measured. The results are shown in Table 1.
Comparative Example 3
A photochromic optical article was produced in the same manner as in Comparative Example 2 except that a silicon oxide thin film was formed directly on the photochromic layer without forming the inorganic particle dispersion layer, and the photochromic characteristics were measured. The results are shown in Table 1.
Comparative Example 4
A photochromic optical article was produced in the same manner as in Example 1 except that the silicon oxide thin film was not provided, and the photochromic characteristics were measured. The results are shown in Table 1.
Comparative Example 5
An optical group having a photochromic layer on the surface in the same manner as in Example 1 except that indenonaphthopyran (a) and chromene (B) are not used as the photochromic compound, and 1.5 parts by weight of chromene (A) is used. A material was prepared. A photochromic optical article was produced in the same manner as in Example 1 except that this photochromic optical substrate was used and the thickness of the silicon oxide thin film was changed to 0.1 μm, and the photochromic characteristics were measured. The results are shown in Table 1.
Comparative Example 6
A photochromic optical article was produced in the same manner as in Comparative Example 2 except that the thickness of the photochromic layer was changed to 19 μm, and its photochromic characteristics were measured. The results are shown in Table 1.
Comparative Example 7
A photochromic optical article was produced in the same manner as in Example 1 except that the thickness of the photochromic layer was changed to 19 μm, and the photochromic characteristics were measured. The results are shown in Table 1.
Comparative Example 8
For the optical substrate having a photochromic layer on the surface produced in Example 1, the photochromic properties were measured as they were without forming the inorganic fine particle dispersion layer and the metal oxide thin layer on the photochromic layer, and the results were obtained. It is shown in Table 1.
Comparative Example 9
For the optical substrate having a photochromic layer on the surface produced in Comparative Example 2 , the photochromic characteristics were measured as they were without forming the inorganic fine particle dispersion layer and the metal oxide thin layer on the photochromic layer, and the results were obtained. It is shown in Table 1.
Comparative Example 10
A photochromic optical article was produced in the same manner as in Example 3 except that 1.5 parts by weight of chromene C was used as the photochromic compound, and the photochromic characteristics were measured. The results are shown in Table 1.

FIG. 1 is a diagram showing an example of a cross-sectional structure of the photochromic optical article of the present invention.

Claims (4)

An optical substrate in which a photochromic layer in which a photochromic compound is dispersed in a resin is formed on at least one surface, and a metal oxide formed on the photochromic layer through a buffer layer having a thickness of 0.1 to 20 μm . a photochromic optical article comprising a deposition film,
As the photochromic compound, the following general formula (1):

[In the above formula (1),
R ²⁶ , R ²⁷ , R ²⁸ and R ³⁰ are each a hydroxyl group, alkyl group, trifluoromethyl group, alkoxy group, alkoxycarbonyl group, carboxyl group, alkoxymethyl group, hydroxymethyl group, aralkoxy group, amino group, substituted An amino group, a cyano group, a nitro group, a halogen atom, an aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a nitrogen atom as a heteroatom, and the nitrogen atom is bonded to the indenonaft ring Substituted or unsubstituted heterocyclic group, or a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the heterocyclic group;
Ring Q is an aliphatic hydrocarbon ring group;
y, y ′, y ″ and y ″ ′ are each an integer from 0 to 2;
R ²⁹ is a dialkylamino group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a hetero atom and the nitrogen atom bonded to the phenyl group, and R ³⁰ is R in the formula (1) It is synonymous with the one defined in ¹ )
And the photochromic layer has a thickness of 30 to 50 μm, and an indenonaphthopyran compound represented by :
The metal oxide vapor-deposited thin film has a thickness of 0.01 to 1 μm and has a single-layer structure . The photochromic optical article according to claim 1, wherein the metal oxide is silicon oxide, titanium oxide, zirconium oxide, tin oxide, zinc oxide, cerium oxide, iron oxide, or a composite oxide containing these oxide components. . The photochromic optical article according to claim 1 or 2, wherein the metal oxide is silicon oxide. On at least one surface, a photochromic layer in which the indenonaphthopyran compound represented by the general formula (1) is dispersed in the resin and has a thickness of 30 to 50 μm is interposed through a buffer layer having a thickness of 0.1 to 20 μm. Prepare an optical substrate formed by
A method for producing a photochromic optical article, wherein a metal oxide thin film having a thickness of 0.01 to 1 μm and having a single layer structure is formed on the photochromic layer by vapor deposition.

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