JP2006103298A - Laminate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photochromic product with high photochromic durability by effectively preventing the oxidation degradation of a dispersed photochromic compound, without causing a decrease in color development density, in an optical substrate, at least one side of which is provided with a photochromic surface layer part composed of a resin with the dispersed photochromic compound. <P>SOLUTION: The photochromic surface layer part of the optical substrate is coated with an ultraviolet ray absorbing film with a thickness of 0.1-100 μm, where a ratio of transmitted light ray with a wavelength of 360 nm is 50% or more and where a ratio of transmitted light ray with a wavelength of 320 nm is 10% or less. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a laminate suitable as an optical article having photochromic properties such as a photochromic eyeglass lens.

  Photochromism is a reversible action that quickly changes color when a compound is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp, and returns to its original color when light is turned off and placed in a dark place. It is applied to various uses.

  For example, photochromism is applied also in the field of spectacle lenses, and plastic lenses imparted with photochromic properties by adding various photochromic compounds having the above properties have been obtained. As photochromic compounds, fulgimide compounds, spirooxazine compounds, chromene compounds and the like have been found.

As a manufacturing method of plastic lenses with photochromic properties,
(i) a method of impregnating a surface of a lens having no photochromic property with a photochromic compound (impregnation method);
(ii) A method of directly obtaining a photochromic lens by dissolving a photochromic compound in a monomer and polymerizing it (mixing method);
(iii) A method of providing a photochromic coating layer on the lens surface (coating method);
Has been proposed.

  The photochromic properties of the photochromic plastic lens produced by these methods are closely related to the properties of the resin (or raw material monomer composition) that becomes the matrix of the photochromic compound, and in order to improve the photochromic properties using this property Many studies have been made so far. For example, the glass transition temperature (Tg) of the lens substrate is lowered to make the movement of the photochromic molecule easier to move even in the polymer, or a specific long-chain alkylene glycol dimethacrylate and three or more radicals as a raw material monomer for the matrix resin Photochromic such as color density and fading speed by using a combination of polyfunctional methacrylate having a polymerizable group to expand the free space in the polymer and make the photochromic molecule easier to move. A photochromic lens having relatively good characteristics has been successfully obtained (see Patent Document 1).

  However, in the photochromic plastic lens, there is a problem in durability due to deterioration due to photooxidation of the photochromic compound, although there is a difference depending on the manufacturing method and the type of matrix resin used. For example, in the method shown in Prior Art 1, since the Tg of the lens base material is lowered and the impregnation property of the photochromic compound is improved, the flexibility of the lens base material becomes too high. The transparency increases, and the photochromic compound is easily deteriorated by photooxidation. Therefore, when the photochromic lens obtained by this method is used for a long period of time, the lens base material is yellowed before color development or the color density is lowered. Such deterioration of the photochromic compound can be considerably prevented by devising a monomer system or a photochromic material for obtaining a plastic lens as a base material (see, for example, Patent Document 2), but there is room for further improvement. . In addition, in the photochromic lens produced by the above-described coating method, the thickness of the coating film containing the photochromic compound is as thin as several tens of microns, so that the durability is further reduced as compared with the photochromic lens obtained by the impregnation method or the kneading method. Tend.

  As a method for preventing the deterioration of the photochromic lens and improving its durability, it has been proposed to provide a coating film containing an organic ultraviolet absorber on the surface of the photochromic lens (see Patent Document 3). . Here, it is shown that benzophenone-based and benzotriazole-based ultraviolet absorbers are specifically used as the ultraviolet absorber.

US Pat. No. 5,739,243 International Publication No. 01/05854 Pamphlet US Pat. No. 6,547,390

  However, in the case where a UV-absorbing coating film is provided on the surface of the photochromic lens using the UV absorber specifically shown in Patent Document 3, the UV absorber is effective for excitation of the photochromic compound. It has become clear that there is a problem that the color density of the lens is lowered because it also absorbs ultraviolet rays of a wavelength.

  In Patent Document 3, an organic ultraviolet absorber is added to a silicone coating agent (the most general-purpose coating agent) composed of alkoxysilane / silica gel, and an ultraviolet absorbing coating film is formed using such a coating agent. Forming. However, when such a coating agent is used, there is a problem that the coating film becomes cloudy due to precipitation of the ultraviolet absorber during curing, and the quality of the lens is deteriorated. Even when the degree of white turbidity is small, if it is used for a long time, the ultraviolet absorber will bleed out from the inside of the coating film, and the effect of preventing the oxidative deterioration of the photochromic compound will gradually decrease, and it will be sufficient There is a problem that the durability improvement effect cannot be obtained. In addition, the problem of precipitation of the ultraviolet absorber at the time of curing can be improved by reducing the amount of the ultraviolet absorber added, but when trying to obtain a lens having a practically no problem in terms of optical characteristics. It is necessary to considerably reduce the amount of the ultraviolet absorber. Eventually, it becomes difficult to sufficiently suppress the oxidative deterioration of the photochromic compound, and a satisfactory durability improvement effect cannot be obtained.

  Accordingly, it is an object of the present invention to provide a photochromic product having high photochromic durability and a method for producing the photochromic compound in which oxidation degradation of the photochromic compound is effectively prevented without causing a decrease in color density.

  Another object of the present invention is to effectively prevent white turbidity due to precipitation of the ultraviolet absorber, and to effectively prevent oxidative degradation of the photochromic compound by the ultraviolet absorber without deteriorating the optical properties of the optical substrate such as a lens. It is to provide a photochromic product and a manufacturing method thereof.

  Still another object of the present invention is to effectively suppress the bleeding out of the ultraviolet absorber even when used for a long period of time, to effectively prevent the oxidative deterioration of the photochromic compound by the ultraviolet absorber, and to achieve photochromic durability. It is to provide a highly photochromic product and a manufacturing method thereof.

  In view of the above problems, the present inventors have intensively studied. As a result, an ultraviolet absorbing film having a thickness of 0.1 to 100 μm, a light transmittance of 360 nm of 50% or more and a light transmittance of 320 nm of 10% or less on the photochromic surface layer portion of the optical substrate. By forming, the oxidative degradation can be effectively prevented without causing a decrease in the color density of the photochromic compound, and further, if the ultraviolet absorbing film is produced by a specific method, the turbidity due to precipitation of the ultraviolet absorber The present inventors have found that the bleed-out of the ultraviolet absorber can be effectively suppressed, and have completed the present invention.

  That is, according to the present invention, an optical substrate having a photochromic surface layer portion made of a resin in which a photochromic compound is dispersed on at least one surface, and a thickness formed on the photochromic surface layer portion of the optical substrate is 0.1. A laminate having a light transmittance of 360 nm of 50% or more and a light transmittance of 320 nm of 10% or less (hereinafter referred to as photochromic). Sometimes referred to as a laminate).

In the photochromic laminate of the present invention,
(1) The light transmittance at 560 nm of the ultraviolet absorbing film is 85% or more,
(2) The ultraviolet absorbing film is a coating layer containing an inorganic oxide containing titanium as an ultraviolet absorber,
Is preferred.

  According to the present invention, there is also provided an optical article comprising the photochromic laminate.

  In the photochromic laminate, a silicone coating agent containing colloidal particles of an inorganic compound that selectively absorbs ultraviolet rays having a wavelength of 320 nm as an ultraviolet absorber is applied onto the photochromic surface layer portion of the optical substrate. It can be manufactured by curing to form an ultraviolet absorbing film having a thickness of 0.1 to 100 μm.

  The photochromic laminate is coated with an organic coating agent containing an ultraviolet absorber that selectively absorbs ultraviolet rays having a wavelength of 320 nm on the photochromic surface layer portion of the optical substrate, and then cured to 0 It can also be produced by forming an ultraviolet absorbing film having a thickness of 1 to 100 μm.

  The photochromic laminate is further formed by depositing an ultraviolet absorber that selectively absorbs ultraviolet rays having a wavelength of 320 nm on the photochromic surface layer to form an ultraviolet absorbing film having a thickness of 0.1 to 1 μm. Can also be manufactured.

  In any of the above production methods, the ultraviolet absorbing film can be directly formed on the photochromic surface layer portion, or the photochromic surface layer can be formed through another functional layer as long as it does not impair the effects of the primer layer and the present invention. It can also be formed on the part.

  The light transmission characteristics of the ultraviolet absorbing film formed on the photochromic laminate are as follows: the light transmittance at each wavelength obtained by subtracting the reflection of the quartz glass by forming the ultraviolet absorbing film of the same composition and thickness on the quartz glass. It can be easily confirmed by measuring. In addition, in order to directly measure the light transmission characteristics of the ultraviolet absorbing film formed in the photochromic laminated body using the laminated body, the light absorption at a specific wavelength of the ultraviolet absorbing film is performed using a reflection method. Just measure. For example, a spectrophotometer is attached with a 5 ° specular reflection measuring device, the relative reflectance with aluminum is measured, and the light transmittance of each wavelength is obtained by calculating the absorption of the ultraviolet absorbing film from the relative reflectance. be able to.

  In this specification, the selective absorption of ultraviolet rays having a wavelength of 320 nm means that the absorption intensity of ultraviolet rays having a wavelength of 360 nm is 80% or less, preferably, when the absorption intensity of ultraviolet rays having a wavelength of 320 nm is 100%. It means 60% or less. Such an ultraviolet absorber having a selective absorption ability at a wavelength of 320 nm is often achieved when the absorption maximum wavelength is 300 to 330 nm.

  In the photochromic laminate of the present invention, since the ultraviolet absorbing film formed on the photochromic surface layer portion has a thickness of 0.1 to 100 μm and has a predetermined light transmission property, the optical substrate The photochromic durability is improved without degrading the basic optical characteristics. In other words, since the ultraviolet ray absorbing film has a light transmittance of 320 nm or less of 10% or less, the photochromic compound existing in the photochromic surface layer can be effectively prevented from oxidative deterioration due to ultraviolet rays, and the photochromic durability can be improved. However, since this ultraviolet ray absorbing film has a light transmittance at 360 nm of 50% or more at the same time, the photochromic reaction is not hindered by the ultraviolet ray absorbing film, and for example, a decrease in color density is effectively avoided. ing. Therefore, in the photochromic laminate of the present invention, the color density when the photochromic compound is colored by irradiating with light is the same level as the case without the ultraviolet absorbing film, even though the ultraviolet absorbing film is formed. is there.

  In addition, as described above, the photochromic laminate of the present invention is obtained by applying a silicone coating agent or an organic coating agent containing an ultraviolet absorber that selectively absorbs ultraviolet rays of 320 nm to the photochromic surface layer portion and curing it. Or by depositing the ultraviolet absorber on the photochromic surface layer portion, by forming the ultraviolet absorbing film by such a method, it is caused by white turbidity due to precipitation of the ultraviolet absorber or bleeding out of the ultraviolet absorber. It is possible to effectively prevent the performance of the ultraviolet absorbing film from being deteriorated (decrease in the antioxidant effect). That is, as described above, precipitation or bleed-out of the UV absorber occurs when an organic UV absorber is added to the silicone coating agent. Therefore, according to the present invention, a silicone-based coating agent in which colloidal particles of an inorganic compound such as a titanium-containing inorganic oxide are added as an ultraviolet absorber, or an organic coating agent to which an ultraviolet absorber is added (hydrocarbon polymerization). When a UV absorbing film is formed using a coating agent having a curable monomer as a curable component, white turbidity due to precipitation of the UV absorber does not occur, and excellent light transmittance of visible light is good (For example, the light transmittance at 560 nm is 85% or more), and the bleed-out of the ultraviolet absorber is also effectively suppressed, so that the performance degradation of the ultraviolet absorbing film can be avoided. Of course, when an ultraviolet absorbing film is formed by vapor deposition, precipitation and bleeding out of the ultraviolet absorber can be similarly prevented.

  Further, in the present invention, the ultraviolet absorbing film formed using the silicone-based coating agent is excellent in oxygen barrier properties, so that the oxidative degradation of the photochromic compound due to ultraviolet rays is remarkably high, which is most preferable.

  The photochromic laminate of the present invention can be suitably used as a photochromic optical article such as a photochromic plastic lens.

The photochromic laminate of the present invention is obtained by forming an ultraviolet absorbing film having a specific thickness and a specific light transmittance on a photochromic surface layer part formed on an optical substrate.
[Optical substrate]
The optical substrate means a transparent plate-like body having a pair of front and back main surfaces. The plate-like body may be curved, and the thickness thereof is not necessarily constant. Further, at least one surface of the optical substrate is formed with a photochromic surface layer portion composed of a resin in which a photochromic compound is dispersed, and the presence of the photochromic surface layer portion causes a reversible change in color due to a predetermined photochromic reaction. I have it. Such a photochromic surface layer portion may be formed on the entire surface of a transparent plate state of a predetermined shape, or may be formed on the entire surface of one surface, or on one surface, depending on the application. It may be partially formed. Furthermore, the entire optical substrate may be formed of a resin in which a photochromic compound is dispersed, and may be formed so that a photochromic reaction occurs not only on the surface but also inside.

  As an optical substrate that can be suitably used in the photochromic laminate of the present invention, a photochromic plastic lens produced by an impregnation method, a kneading method or a coating method; a photochromic property similar to a coating method on a transparent substrate such as glass The photochromic optical component which gave is illustrated.

  As the photochromic plastic lens manufactured by the impregnation method, for example, those disclosed in US Pat. No. 5,739,243 (the above-mentioned Patent Document 1) can be suitably used.

  Moreover, as a photochromic plastic lens manufactured by the kneading method, a cured product disclosed in International Publication No. 01/05854 (Patent Document 2) can be suitably used. This cured product includes (A) a polymerizable monomer having an L scale Rockwell hardness of 40 or less, (B) a trifunctional or more polyfunctional polymerizable monomer having an L scale Rockwell hardness of 60 or more, ( C) It is obtained by curing a curable composition comprising a bifunctional polymerizable monomer having an L scale Rockwell hardness of 60 or more and a photochromic compound, and has a hardness of 60 or more. The L scale Rockwell hardness of the polymerizable monomer means the hardness of a polymer obtained by homopolymerizing this monomer.

  As a photochromic plastic lens or photochromic optical component manufactured by the coating method, a photochromic coating layer (photochromic surface layer) is formed using a coating agent made of a curable composition disclosed in WO 03/011967. That is suitable. The curable composition comprises 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 photochromic compound, respectively. A curable composition containing a specific amount and containing no amine compound can also be suitably used as a coating agent.

  As a photochromic compound, well-known photochromic compounds, such as a fulgimide compound, a spirooxazine compound, and a chromene compound which can be used in the curable composition used for manufacture of the optical substrate, can be used without limitation.

  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 the various photochromic compounds shown above, a chromene compound is preferred from the viewpoint of high durability of photochromic properties and good color density and fading speed. These chromene compounds are also preferably used because the effect of maintaining the color density due to the selection of the ultraviolet absorbing film in the present invention is remarkably exhibited.

  Specific examples of such chromene compounds include compounds described in International Publication No. 01/60811 pamphlet, US Pat. No. 6,340,765 and US Pat. No. 6,525,194. The most preferable chromene compounds include the following general formulas: The chromene compound shown by (1) can be illustrated.

  In the general formula (1), the following formula (2):

The group represented by is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted unsaturated heterocyclic group,
R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, alkyl group, alkoxyl group, aralkoxy group, amino group, substituted amino group, cyano group, substituted or unsubstituted aryl group, halogen atom, aralkyl group, A hydroxyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom and the ring of the group represented by the formula (2) bonded to each other; Or a condensed heterocyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic group,
o is an integer from 0 to 6,
R ¹ and R ² are each independently a group represented by the following formula (3) or the following formula (4), a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group It is. R ¹ and R ² may be combined to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.

(Wherein R ⁶ is a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R ⁷ is a hydrogen atom, an alkyl group, or a halogen atom, and p is 1 to 3. (It is an integer.)

(In the formula, R ⁸ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and p ′ is an integer of 1 to 3).
The above formula (3), the formula (4) or above R ^1, and as the substituent group of the substituted aryl group or a substituted heteroaryl groups in R ^2, include the R ³ to R ⁴ as defined in group Can do.

  Of the chromene compounds represented by the above formula (1), the compounds represented by the following formulas (5) to (10) are particularly preferred from the viewpoint of photochromic properties such as color density and fading speed and durability.

In equation (5),
R ⁹ and R ¹⁰ are respectively synonymous with R ¹ and R ² in the formula (1),
R ¹¹ and R ¹² have the same meaning as R ⁵ in the formula (1),
q and q ′ are each an integer of 1 to 2.

In equation (6),
R ¹³ and R ¹⁴ have the same meanings as R ¹¹ and R ¹² in the formula (1),
R ¹⁵ and R ¹⁶ have the same meaning as R ⁵ in the formula (1),
L is the following formula:

(In the above formula, P is an oxygen atom or a sulfur atom, R ¹⁷ is an alkylene group having 1 to 6 carbon atoms, and s, s ′ and s ″ are all integers of 1 to 4). ), And
r and r ′ are each independently 1 or 2.

In equation (7),
R ¹⁸ and R ¹⁹ have the same meanings as R ¹ and R ² in the formula (1),
R ²⁰ , R ²¹ and R ²² have the same meaning as R ⁵ in the formula (1),
v is 1 or 2.

In equation (8),
R ²³ and R ²⁴ have the same meanings as R ¹ and R ² in the formula (1),
R ²⁵ and R ²⁶ have the same meaning as R ⁵ in the formula (1),
w and w ′ are each independently 1 or 2.

In equation (9),
R ²⁷ and R ²⁸ have the same meanings as R ¹ and R ² in the formula (1),
R ²⁹ , R ³⁰ , R ³¹ and R ³² have the same meaning as R ⁵ in the formula (1),
x and x ′ are each independently 1 or 2.

In equation (10),
R ³³ and R ³⁴ have the same meanings as R ¹ and R ² in the formula (1),
R ³⁵ , R ³⁶ and R ³⁷ have the same meaning as R ⁵ in formula (1),
Ring Q is an aliphatic hydrocarbon ring,
y, y ′, and y ″ are each independently 1 or 2.

  In the present invention, among the chromene compounds represented by the above formulas (5) to (10), a chromene compound having the following structure is particularly preferably used.

  The above-described photochromic compounds can be used by appropriately mixing a plurality of types in order to develop an appropriate color tone.

  The optical substrate used in the present invention has a photochromic surface layer portion formed of the resin composition in which the above-described photochromic compound is dispersed. The concentration of the photochromic compound in the resin composition is such that a good color density can be obtained. From the viewpoint, it is preferably in the range of 0.002 to 20% by weight.

  Moreover, the optical substrate manufactured by the kneading method has the entire optical substrate formed of the above resin composition (that is, the inside has the same composition as the photochromic surface layer portion). In the case of a kneaded optical substrate, when the photochromic plastic lens has a thickness of 2 mm or more, the resin composition is preferably used from the viewpoint that a good color density is realized with low initial coloring (referred to coloring in a non-irradiated state). The content of the photochromic compound in the product is particularly preferably in the range of 0.01 to 1% by weight. Moreover, in the optical substrate in which the photochromic surface layer portion is formed by the coating method or the impregnation method, particularly when the thickness of the photochromic surface layer portion is 10 to 100 μm, the content of the photochromic compound in the photochromic surface layer portion from the same viewpoint as described above Is preferably in the range of 0.1 to 15% by weight, and when the thickness of the photochromic surface layer part is 10 to 40 μm, the content of the photochromic compound in the surface layer part is 0.1 to 5% by weight. It is particularly preferred.

  In the photochromic laminate of the present invention, the photochromic surface layer part is preferably formed by a coating method or an impregnation method. The cause of oxidative degradation of the photochromic compound is oxygen and harmful ultraviolet rays. In particular, the thinner the portion where the photochromic compound is dispersed, the greater the diffusion of oxygen and the more likely it is subject to oxidative degradation. That is, the optical substrate on which the photochromic surface layer portion is formed by a coating method or the like has the property that the photochromic compound is more likely to be oxidized and deteriorated than the optical substrate by the kneading method. In the present invention, in order to prevent such oxidative degradation of the photochromic compound by providing an ultraviolet absorbing film having specific light transmission characteristics described later, when the present invention is applied to an optical substrate by a coating method or the like, The advantage of the present invention that the photochromic durability is improved by preventing the oxidative deterioration of the compound is extremely great.

  In addition, the resin in which the photochromic compound is dispersed (hereinafter referred to as a photochromic resin composition) prevents the yellowing and improves the moldability, further improves the durability of the photochromic compound when the photochromic compound is added, and the color development speed. Various additives known per se may be included for improving the color fading and fading speed.

  Surfactant can be illustrated as such an additive. As the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but it is preferable to use a nonionic surfactant because of its solubility in a radically polymerizable monomer that forms a resin component as a matrix. . Specific examples of nonionic surfactants that can be suitably used 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 ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol / phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil / cured Castor oil, polyoxyethylene lanolin, lanolin alcohol, beeswax derivative, poly Surfactant with a hydrophobic group consisting of a polyoxyethylene alkylphenyl formaldehyde condensate, a polyoxyethylene alkylphenyl formaldehyde condensate, a single chain polyoxyethylene alkyl ether silicone chain (polyalkylsiloxane unit), a perfluoroalkyl group-containing ester system Examples include oligomers, perfluoroalkyl group-containing alkylene oxide adducts, and fluorine aliphatic polymer esters. The above-mentioned surfactants may be used alone or in combination of two or more. The content of the surfactant in the photochromic resin composition is generally preferably in the range of 0.001 to 20% by weight.

  In addition, the above additives include various antioxidants such as hindered phenol antioxidants and sulfur antioxidants, various radical scavengers such as phenol radical scavengers, and various light such as hindered amine light stabilizers. Stabilizers and ultraviolet absorbers such as benzotriazole compounds and benzophenone compounds can be used alone or in combination of two or more. This type of additive may also be generally contained in the photochromic resin composition in an amount of 0.001 to 20% by weight, respectively. Among these additives, a hindered amine light stabilizer is particularly preferable in that it has a high effect of preventing deterioration of the photochromic compound. For example, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Hindered amines such as Adeka Stub LA-52, LA-57, LA-62, LA-63, LA-67, LA-77 and LA-82 manufactured by Asahi Denka Kogyo Co., Ltd. are preferably used. The addition amount of such a hindered amine light stabilizer is most preferably in the range of 0.1 to 10% by weight, particularly 1 to 10 parts by weight.

In addition to the various additives described above, a photochromic resin composition may include a release agent, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, and a plasticizer as long as the photochromic properties are not impaired. It may be added inside.
[Ultraviolet absorbing film]
In the photochromic laminate of the present invention, the ultraviolet absorbing film formed on the photochromic surface layer portion of the optical substrate described above must have a thickness of 0.1 to 100 μm. When the thickness of the film is less than 0.1 μm, sufficient durability-improving curing cannot be obtained, and when it exceeds 100 μm, it is difficult to obtain a film having a uniform thickness. The optical characteristics will deteriorate. Further, as will be described later, the ultraviolet absorbing film is formed by a coating method or a vapor deposition method. In particular, an ultraviolet absorbing film formed by the coating method has a thickness in terms of film durability, optical characteristics, and the like. Is preferably in the range of 0.5 to 30 μm, and in the ultraviolet absorbing film formed by vapor deposition, the thickness is preferably in the range of 0.1 to 1 μm.

  Further, such an ultraviolet absorbing film has a light transmittance at 360 nm of 50% or more, preferably 55% or more, and most preferably 60% or more. At the same time, a light transmittance at 320 nm is 10% or less, preferably 5%. It is also important that it is below%, most preferably below 3%. That is, the oxidative degradation of the photochromic compound is strongly caused by light having a short wavelength of about 320 nm, while the excitation of the photochromic compound proceeds well by light having a wavelength of about 360 nm. By providing the ultraviolet absorbing film, it is possible to effectively prevent oxidative deterioration of the photochromic compound and improve the durability of the photochromic without causing a decrease in the color density. For example, when the light transmittance at 360 nm of the ultraviolet absorbing film is lower than the above range, the color density of the photochromic compound is lowered, and when the light transmittance at 320 nm is higher than the above range, the photochromic compound It is not possible to effectively suppress the oxidative degradation of. Sufficient photochromic durability cannot be improved. That is, in the present invention, since the ultraviolet absorbing film has the light transmission characteristics as described above, it is possible to achieve both improvement in durability and color density of the photochromic compound.

Further, it is preferable that the ultraviolet absorbing film is free of opaque foreign matters (for example, deposits of ultraviolet absorbing agent) that can be visually confirmed and is excellent in transparency. Accordingly, although the preferred range varies depending on the refractive index of the film because of reflection at the film interface, in general, the light transmittance at 560 nm of this ultraviolet absorbing film is preferably 85% or more, more preferably 90% or more. It is desirable to be.
[Formation of UV absorbing film]
The above-described photochromic laminate uses an ultraviolet absorber that selectively absorbs ultraviolet rays having a wavelength of 320 nm, and has predetermined light characteristics within the above-described film thickness range, depending on the amount of the ultraviolet absorber used. It is manufactured by selecting an appropriate film thickness and forming an ultraviolet absorbing film on the photochromic surface layer portion of the optical substrate. As a method for forming an ultraviolet absorbing film employed in such a production method, in particular, a film having no precipitation of an ultraviolet absorber and having a light transmittance of 560 nm of 85% or more is obtained. The method (a) by the coating method using a silicone-based coating agent containing an ultraviolet absorber, and the use of an organic coating agent containing an ultraviolet absorber in that a film that does not easily bleed out is obtained. A method (b) by a coating method and a method (c) by vapor deposition of an ultraviolet absorber are preferably employed.
Method by coating (a):
In this method, a silicone-based coating agent containing an ultraviolet absorber is applied to the photochromic surface layer portion, and the coating film is cured to form an ultraviolet absorbing film.

  As the ultraviolet absorber, colloidal particles of an inorganic compound that selectively absorbs ultraviolet rays having a wavelength of 320 nm are used. Examples of such inorganic compounds include metal oxides such as zinc oxide, cerium oxide, zirconium oxide, iron oxide, and titanium oxide, and composite oxides containing these metal oxides. Among these, zinc oxide, titanium oxide, cerium oxide, and composite oxides containing these metal oxides are preferred, and composite metal oxides containing titanium oxide are most preferred from the point of no coloring. Specifically, titanium oxide / zirconium oxide / tin oxide composite metal oxide and titanium oxide / zirconium oxide / silicon oxide composite metal oxide are most preferable. In the composite metal oxide, the content of the metal oxide that selectively absorbs a wavelength of 320 nm as exemplified above is preferably 30% by weight or more, more preferably 50% by weight or more, It is preferable that the content of titanium oxide is not less than these amounts. Such colloidal particles of metal oxide or composite oxide can be prepared by a so-called sol-gel method, and sols containing such colloidal particles are also preferably used because they can be obtained industrially or as reagents. Is done.

  The colloidal particles of the inorganic compound may contain a small amount of other inorganic compound components as long as they can selectively absorb ultraviolet rays having a wavelength of 320 nm.

  The content of the ultraviolet absorber in the silicone-based coating agent is appropriately determined so that the light transmittance of 360 nm and the light transmittance of 320 nm of the obtained ultraviolet absorbing film are within the above-described ranges. The ultraviolet absorbing film preferably contains 15 to 90% by weight, more preferably 15 to 70% by weight. Furthermore, when using an ultraviolet absorber as a metal oxide, its content is most preferably 15 to 50% by weight. When using it as a composite oxide containing these metal oxides, its content is Most preferably, it is 25 to 70% by weight.

  The thickness of the ultraviolet absorbing film is set in the above-described range (0.1 to 100 μm). In such a range, it is preferable to adjust the film thickness according to the amount of the ultraviolet absorbing agent, for example, the ultraviolet absorbing agent. When the amount is small, it is preferable to increase the film thickness, and when it is large, it is preferable to decrease the film thickness. This is because if the film thickness is larger than necessary compared to the amount of the UV absorber in the film, cracks or the like may occur in the UV absorber film. For example, when the amount (concentration) of the ultraviolet absorber in the ultraviolet absorbing film is 15 to 70% by weight, the film thickness is preferably in the range of 0.5 to 30 μm, more preferably in the range of 1 to 10 μm. is there.

  Moreover, the silicone type coating agent used in the method (a) contains a hydrolyzable organosilicon compound or a hydrolyzate thereof as a curing component. As the hydrolyzable organosilicon compound or its hydrolyzate, those generally used as silane coupling agents are preferably used. 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 curing component comprising such an organosilicon compound or a hydrolyzate thereof is used in such an amount that the content in the ultraviolet absorbing film (cured film) is 10 to 25% by weight.

  The silicone-based coating agent may contain other additives (for example, an acid, a leveling agent, a curing catalyst, etc.) and an organic solvent in addition to the ultraviolet absorber described above.

  The acid is used to promote hydrolysis and condensation of the organosilicon compound that is a curing component, 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.

Moreover, as a curing catalyst, 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), V (III), Co (III), Fe (III), Acetylacetonate having Al (III), Ce (IV), Zr (IV), V (IV) or the like as a central atom; amino acids such as amines and glycines; Lewis acids; organometallic salts; . These curing catalysts are added to the coating agent in an amount of 0.1 to 3% by weight per solid content.

The silicone-based coating agent described above may contain colloidal particles of an inorganic oxide such as colloidal silica as a reinforcing agent or the like within a range that does not impair the light transmission characteristics of the obtained ultraviolet absorbing film.
Method (b) by coating:
In this method, the above-described ultraviolet absorbing film is formed by coating with an organic coating agent containing an ultraviolet absorber.

  The ultraviolet absorber blended in the organic coating agent also selectively absorbs ultraviolet rays having a wavelength of 320 nm, and may be used, for example, in the method (a) as long as it has such light transmission characteristics. Inorganic ultraviolet absorbers such as inorganic compounds (particularly inorganic oxides) can be used, and organic ultraviolet absorbers can also be used. However, it is preferable to use an organic ultraviolet absorbent in terms of preventing white turbidity due to precipitation of the ultraviolet absorbent during film formation. Examples of such organic ultraviolet absorbers include ultraviolet rays having a wavelength of 320 nm among compounds belonging to benzophenone, benzotriazole, salicylic acid ester, cyanoacrylate, hydroxybenzoate, benzoxazinone, triazine, and the like. Those satisfying the condition of selective absorption and capable of forming the film having the above-mentioned light transmission characteristics are used alone or in combination of two or more kinds, but particularly large in the short wavelength ultraviolet region of 320 nm. Cyanoacrylate-based, salicylic acid ester-based and hydroxybenzoate-based ones are preferred in that they have absorption and are difficult to reduce the color density of the photochromic compound. Many benzotriazole-based and benzophenone-based organic ultraviolet absorbers do not satisfy the above-mentioned requirements, and generally cannot be used alone.

  In the present invention, representative examples of organic ultraviolet absorbers that can be particularly preferably used include ethyl-2-cyano-3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl acrylate, and 2′-ethylhexyl. -Cyanoacrylate UV absorbers such as 2-cyano-3,3-diphenyl acrylate; Salicylic acid ester UV absorbers such as phenyl saltylate and pt-butylphenyl salicylate; 2,4-di-t-butyl Examples thereof include hydroxybenzoate ultraviolet absorbers such as phenyl-3 ′, 5′-di-t-butyl-4′-hydroxybenzoate.

  The content of these ultraviolet absorbers is also adjusted so that the light transmission characteristics (ultraviolet absorption characteristics) of the cured film satisfy the above-mentioned conditions, as in the method (a) described above. It is set in the range of 0.1 to 10% by weight, preferably 0.1 to 5% by weight per solid content of the coating agent. When the concentration of the agent is 0.1 to 5% by weight, the film thickness of the ultraviolet absorbing film to be formed is preferably in the range of 0.5 to 30 μm.

  In addition, the organic coating agent blended with the ultraviolet absorber as described above is a hydrocarbon-based polymerizable monomer that gives a transparent cured product (a polymerizable monomer whose main skeleton is formed of hydrocarbons) And may contain an oxygen atom, a nitrogen atom, a sulfur atom or the like as a curing component if it is partially.

Such hydrocarbon-based polymerizable monomer components include monofunctional or polyfunctional (meth) acrylate compounds, monofunctional or polyfunctional vinyl compounds, monofunctional or polyfunctional epoxy compounds, polyfunctional urethanes (polyisocyanates). A known polymerizable monomer (monomer) known to give a transparent cured product such as a compound, a monofunctional or polyfunctional hydroxy compound, and a mixture of these monomers can be used without particular limitation. Specific examples of monomers that can be suitably used include the following monomers.
(1) Monofunctional or polyfunctional (meth) acrylate compound, vinyl compound trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane triacrylate, trimethylolpropane triethylene glycol triacrylate, penta Erythritol tetramethacrylate, dipentaerythritol hexaacrylate, urethane oligomer tetraacrylate, urethane oligomer hexamethacrylate, urethane oligomer hexaacrylate, polyester oligomer hexaacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene Glycol dimethacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxy-ethoxyphenyl) propane, glycidyl methacrylate,
2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane having an average molecular weight of 776, methyl ether polyethylene glycol methacrylate having an average molecular weight of 475, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, diallyl phthalate, diethylene glycol bisallyl carbonate etc.
(2) Monofunctional or polyfunctional epoxy monomer 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, trimethylolpropane diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, Pentaerythritol triglycidyl ether, bisphenol A diglycidyl ether, bis-2,2-hydroxycyclohexylpropane diglycidyl ether, and the like.
(3) polyfunctional urethane (polyisocyanate) compound tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, triphenylmethane triisocyanate, tris (isocyanate phenyl) thiophosphate, Aromatic isocyanate compounds such as tetramethylxylene diisocyanate; trimethylhexamethylene diisocyanate, hexamethylene diesocyanate, isophorone diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, lysine diisocyanate, lysine ester triisocyanate, 1,6 , 11-Undecane triisocyanate, 1,8-diisocyanate Various aliphatic isocyanate compounds such as -4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, etc., and compounds having active hydrogen at various charging ratios that leave isocyanate groups A polyisocyanate compound or a polyisocyanate oligomer compound bonded by the method described above.
(4) Monofunctional or polyfunctional hydroxy compound ethylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, dipropylene glycol, diethylene glycol Alkylene glycols such as; polypropylene glycol, polyethylene glycol, polyalkylene glycols such as polytetramethylene glycol; poly (diethylene adipate), poly (tetramethylene adipate), poly (hexamethylene adipate), poly (neopentylene adipate) Poly (alkylene adipates) such as; polycaprolactones such as poly-ε-caprolactone, polycaprolactone diol, polycaprolactone tolyl; poly (1,4- Tandiene) glycol, polybutadiene glycols such as poly (1,2-butanediene) glycol; poly (alkylene carbonates) such as poly (hexamethylene carbonate); polyester polyols; 1,2,4-butanetriol, 1,2 Polyols containing 3 or more hydroxy groups such as 1,6-hexanetriol; silicone polyols and the like.

  Moreover, it is preferable that the organic coating agent described above contains a curing catalyst. As the curing catalyst, a radical polymerization initiator, a photopolymerization initiator, or the like is appropriately used depending on the reactivity of the polymerizable monomer to be used.

  Examples of radical polymerization initiators include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; t-butylperoxy-2-ethylhexanoate, t -Peroxy esters such as butyl peroxydicarbonate, cumyl peroxyneodecanate, t-butyl peroxybenzoate; diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyloxycarbonate, etc. 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1 ′ -Azobis Cyclohexane-1-carbonitrile) and the like can be exemplified azo compounds such as. The amount of such radical polymerization initiator used varies depending on the type, polymerization conditions, and the type and composition of the polymerizable monomer component to be used and cannot be generally limited. It is suitable to use in the range of 0.01 to 10 parts by weight per part.

  As photopolymerization initiators, benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, aethofenone 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl Methyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthiooxane, acylphosphine oxide, diacylphosphine oxide, etc. It can be illustrated. Such a photopolymerization initiator is generally used in the range of 0.001 to 5 parts by weight per 100 parts by weight of all radical polymerizable monomers.

  Moreover, as a curing catalyst other than the above, various epoxy resin curing agents, various organosilicon resin curing agents, and the like can be used. Specific examples of such curing agents include various organic acids and acid anhydrides thereof; nitrogen-containing organic compounds such as tertiary amine compounds; various metal complex compounds or metal alkoxides such as organic tin compounds and organic zinc compounds; And various salts such as alkali metal organic carboxylates and carbonates. In this case, the addition amount is preferably 0.1 to 5 parts by weight, particularly 0.5 to 2 parts by weight per 100 parts by weight of the total weight of the polymerizable monomers.

  Furthermore, the organic coating agent may contain an organic solvent for dilution as necessary, or may contain a stabilizer other than the ultraviolet absorber. The organic solvent is not particularly limited as long as it can dissolve the monomer component and various additives, and for example, toluene, xylene, ethyl acetate and the like can be used. Stabilizers other than ultraviolet absorbers include hindered amine light stabilizers, hindered phenolic antioxidants, sulfur-containing secondary antioxidants, phosphorus-containing secondary antioxidants, nickel-based singlet oxygen quenching. An agent etc. can be mentioned.

  In the method (a) and (b) of forming the ultraviolet absorbing film by coating as described above, the method for applying the coating agent to a predetermined portion of the optical substrate is not particularly limited, and it may be applied by spin coating, dipping, spin dipping or the like. it can. The thickness of the finally obtained ultraviolet absorbing film can be controlled by adjusting the rotational speed in spin coating, the viscosity of the coating agent, and the like.

  Prior to the application of these coating agents, it is preferable to pretreat the surface of the optical substrate in order to improve the adhesion between the ultraviolet absorbing film and the optical substrate. Examples of the pretreatment include chemical treatment using a basic aqueous solution or acidic aqueous solution, polishing treatment using an abrasive, plasma treatment using atmospheric pressure plasma and low pressure plasma, corona discharge treatment, or UV ozone treatment. it can. Moreover, it is also preferable from an adhesive viewpoint to form a primer layer by pre-processing and to form an ultraviolet absorption film on a primer layer. After forming the primer layer as necessary, various primer typified by urethane primer, preferably moisture-curing urethane primer is applied to the photochromic surface layer of the optical substrate. And then cured. The thickness of such a primer layer is usually about 2 to 10 μm.

Moreover, the coating layer applied to a predetermined part on the surface of the optical substrate is cured in accordance with the type of the coating agent to form a target ultraviolet absorbing film. For example, when a silicone coating agent is used (the method (a)), the coating layer is cured by heat condensation to form an ultraviolet absorbing film. When an organic coating agent is used (the method (b)), the coating layer is cured by thermal polymerization and / or photopolymerization to form an ultraviolet absorbing film. At this time, in the case of thermal polymerization, it is generally sufficient to heat at a temperature of 40 to 200 ° C. for 5 minutes to 30 hours, and in the case of photopolymerization, a metal halide lamp, high-pressure mercury in an inert atmosphere such as nitrogen. A lamp, a xenon lamp, an electrodeless discharge light source D or a V bulb may be used as a light source, and light irradiation may be performed at a light intensity of 10 to 200 mW / cm ² for 1 second to 30 minutes.

In addition, when using these coating agents, rather than directly applying the coating agent to the optical substrate, using these coating agents to separately produce an ultraviolet absorbing film, the resulting film using an adhesive or the like, It can also be adhered to a predetermined site on the surface of the optical substrate.
Method by vapor deposition (c):
In this method, the aforementioned ultraviolet absorbing film is formed by depositing an ultraviolet absorber.

  The ultraviolet absorber used in this method is an inorganic oxide that selectively absorbs ultraviolet rays having a wavelength of 320 nm exemplified in the method (a), such as zinc oxide, cerium oxide, zirconium oxide, iron oxide, and titanium oxide. Metal oxides and composite oxides containing these metal oxides. By forming such an inorganic oxide serving as an ultraviolet absorber into a film by vapor deposition using a vacuum vapor deposition technique such as CVD, PVD or sputtering, an ultraviolet absorbing film is formed.

  In such a method, by setting the thickness of the ultraviolet absorbing film (deposited film) formed by vapor deposition in the range of 0.1 to 1 μm, the light transmission characteristics described above can be satisfied. In addition, when forming an ultraviolet absorption film by vapor deposition, in order to improve the adhesion of the ultraviolet absorption film (deposition film), a silicone-based coating film is previously formed as a primer layer on the surface of the substrate. preferable. The thickness of the primer layer is also about 2 to 10 μm.

  In the present invention, among the methods (a) to (c) for forming the ultraviolet absorbing film, the method (a) is obtained by the fact that the resulting ultraviolet absorbing film (cured film) is hard and dense. It is advantageous in that it has a high barrier property and acts synergistically with the effect of blocking harmful ultraviolet rays around 320 nm, the effect of preventing the photochromic photochromic compound from being oxidized and deteriorated, and the effect of improving the photochromic durability is extremely high.

  The ultraviolet absorbing film is usually provided as a single layer structure, but has a thickness of 0.1 to 1 μm, preferably 0.5 to 30 μm (μm in the case of an ultraviolet absorbing film formed by vapor deposition). If it is in the range, it may be provided as a multi-layer structure of a small number of layers. A single layer structure is most preferable from the viewpoint of 0.1 to 1 because it is easy to form a film and does not require labor and cost, and appearance defects such as cracks are less likely to occur. Is preferable. Note that such an ultraviolet absorbing film that is a thin layer but is a small number of layers is an antireflection film that is applied in the antireflection treatment of the lens, that is, a metal oxide having a different refractive index is alternately deposited by a vapor deposition method or the like. It is clearly different from the layer-layered film.

The photochromic laminate of the present invention can be used as it is as a photochromic optical article, but when the ultraviolet absorbing film is not formed by the method (a), the ultraviolet absorbing film is made of a hard coat material. It is preferable to coat. By coating with a hard coat film, the scratch resistance of the surface can be improved. As the hard coat film, known ones can be used without any limitation, and a hard coat liquid mainly composed of a silane coupling agent or an oxide sol such as silicon, zirconium, antimony or aluminum, or an organic polymer is mainly used. It can be formed using a hard coat liquid as a component. Furthermore, antireflection treatment or antistatic treatment by vapor deposition of a thin film made of a metal oxide such as SiO ₂ or coating of a thin film of organic polymer on the surface of the photochromic laminate of the present invention or the surface coated with a hard coat material. It is also possible to perform processing and secondary processing.

In such a photochromic laminate of the present invention, it can be used without limitation to the application of irradiating light containing ultraviolet rays to express its photochromic properties, but for example, irradiating sunlight or mercury lamps containing a lot of harmful light of 320 nm. It is preferably used in applications.
Examples Hereinafter, the excellent effects of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The following photochromic compounds were used for production of optical substrates in Examples and Comparative Examples.
Photochromic compound A:
A compound having a structure represented by the following formula.

Photochromic compound B:
A compound having a structure represented by the following formula.

Photochromic compound C:
A compound represented by the following formula.

(Manufacture of optical substrate having photochromic surface layer)
A plastic lens (refractive index = 1.50) obtained by polymerizing diethylene glycol bisallyl carbonate was prepared as a lens substrate.

  Moisture-curing primer (Primer PFR4 manufactured by Takebayashi Chemical Co., Ltd.) and ethyl acetate were prepared so as to have a weight ratio of 9: 1, and thoroughly stirred until uniform in a nitrogen atmosphere to prepare a primer coating solution. . After sufficiently degreasing the surface of the lens substrate with acetone, the primer coat solution is spin-coated on the lens substrate surface using a spin coater (Mikasa spin coater 1H-DX2) and cured at room temperature for 20 minutes. Thus, a lens substrate having a primer layer on the surface of the lens substrate was produced.

In addition, the following formulation:
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 10 parts by weight allows radical polymerization A mixture of monomers was prepared. Next, 2.35 parts by weight of photochromic compound A, 0.2 parts by weight of photochromic compound B, and 1.6 parts by weight of photochromic compound C were added to 100 parts by weight of this radical polymerizable monomer mixture and mixed sufficiently. Later, further
Polymerization initiator 0.5 part by weight Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate
(Stabilizer) 5 parts by weight γ-methacryloyloxypropyltrimethoxysilane
(Silane Coupling Agent) A photochromic polymerizable composition (photochromic coating solution) was prepared by adding 7 parts by weight and mixing well. As the polymerization initiator, a mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide (weight ratio: 3 to 1) is used. It was.

Next, about 2 g of the above-mentioned photochromic coating solution is spin-coated on the surface of the lens substrate using the above-mentioned spin coater, and 3 minutes in a nitrogen gas atmosphere using a metal halide lamp having a light intensity of 405 nm and 120 mW / cm ^2. An optical substrate having a photochromic coating layer (photochromic surface layer portion) is obtained by curing the coating film of the photochromic coating solution on the surface of the lens substrate by irradiating light, and further performing a heat treatment in a thermostat at 110 ° C. for 1 hour. Lens substrate) was obtained. The film thickness of the obtained photochromic coat layer was 40 μm.
Example 1
On the photochromic coating layer of the optical substrate produced above, an ultraviolet absorbing film was formed as follows to obtain a photochromic laminate.

First, the following prescription:
γ-glycidoxypropyltrialkoxysilane (GTS) 9.15 g
t-Butyl alcohol (TBA) 5.6 g
Diacetone alcohol (DAA) 2.8 g
Leveling agent ("L7001" manufactured by Nihon Unicar Co., Ltd.) 0.025g
Accordingly, after mixing the components, 2.09 g of 0.05N aqueous hydrochloric acid solution was added dropwise with stirring, and the mixture was stirred for 4 hours.

In the above mixture,
Aluminum acetylacetonate (Al (AcAc) ₃ ) 0.094 g
Isopropyl alcohol (IPA) 2.8 g
Ethylene glycol isopropyl ether (EGiPE) 2.8g
And stirred for 30 minutes. In this liquid, as an ultraviolet absorber,
Methanol-dispersed titanium oxide / zirconium oxide / silicon oxide composite metal oxide fine particle sol (weight ratio: 65/5/30, solid content concentration 30% by weight) 25.07 g
And stirring at room temperature overnight to prepare a solution containing fine oxide particles (ultraviolet absorber), and then filtering the solution through a 0.5 micron filter, and a silicone-based coating agent containing the ultraviolet absorber Was prepared. The composition of this silicone coating agent is shown in Table 1.

  4 g of the silicone-based coating agent thus prepared was applied on the photochromic coating layer of the previously prepared optical substrate using the same spin coater as described above. The spin coating conditions were 650 rpm and 15 seconds.

  After spin coating, preliminary drying was performed at 70 ° C. for 15 minutes, followed by main curing at 120 ° C. for 1 hour to obtain a photochromic laminate having an ultraviolet absorbing film having a thickness of 2 μm.

The ultraviolet absorption characteristics and photochromic characteristics of this photochromic laminate were evaluated by the following methods.
Evaluation of UV absorption characteristics:
The silicone coating agent containing the ultraviolet absorber used above was spin-coated and cured on quartz glass under exactly the same conditions as described above to produce a cured film (ultraviolet absorbing film) having the same film thickness. By measuring the light transmittance of 320 nm, 360 nm and 560 nm of the cured film, the ultraviolet absorption characteristics of the ultraviolet absorption film in the photochromic laminate were evaluated. The light transmittance at 560 nm was 90%, and there was no turbidity visually and it was transparent. The light transmittance at 360 nm was 74%, and the light transmittance at 320 nm was 1%. The results are shown in Table 2.
Evaluation of photochromic properties:
The photochromic properties of the obtained photochromic laminate were evaluated by measuring the color density, durability, and yellowness by the following methods. The results are shown in Table 3.
(1) Color density A ₀ (Abs.);
Using the xenon lamp L-2480 (300W) SHL-100 manufactured by Hamamatsu Photonics, the obtained photochromic laminate was irradiated with light at 20 ° C. ± 1 ° C. for 120 seconds through an aeromass filter (manufactured by Corning). Color was developed.

The beam intensity on the surface of the laminate was 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² . The absorbance at the maximum absorption wavelength at this time was determined with a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd., and the color density was calculated by the following method.

The difference {A ₀ = ε () between the absorbance {ε (120)} at 590 nm after light irradiation for 120 seconds and the absorbance {ε (0)} at the wavelength of the cured body in the state without light irradiation. 120) −ε (0)} was determined as the color density. It can be said that the higher this value, the better the photochromic properties.
(2) Durability;
The durability of color development by light irradiation was evaluated by the following deterioration acceleration test.

That is, the obtained photochromic laminate was accelerated and deteriorated for 50 hours by a Xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. The color density before and after this accelerated deterioration was measured (A ₀ : color density before test, A ₅₀ : color density after test), and the value of {(A ₅₀ / A ₀ ) × 100} was the residual rate (%) And used as an index of color durability. The higher the remaining rate, the higher the durability of coloring.
(3) Yellowness (YI);
The yellow color before color development of the photochromic laminate was measured before and after the above-described deterioration acceleration test using a color difference meter (SM-4) manufactured by Suga Test Instruments Co., Ltd. The yellowness after the test was indicated as “YI50”. Moreover, the yellowing degree ((DELTA) YI = YI50-YI0) before and behind a deterioration test was also calculated | required. The higher the YI value, the stronger the yellow color, and the larger the ΔYI value, the greater the yellowing degree before and after the deterioration test.
Examples 2 and 3
A photochromic laminate was produced in the same manner as in Example 1 except that the composition of the silicone coating agent used for forming the UV absorbing film was changed as shown in Table 1, and the UV absorbing properties and photochromic properties were evaluated. The results are shown in Tables 2 and 3.
Example 4
A photochromic laminate was produced in the same manner as in Example 1 except that the ultraviolet absorbing film was changed as follows.

  As a coating solution for forming an ultraviolet absorbing film, a hard coating solution (product name: 160-74NT) manufactured by SCL International was prepared. This coating solution is a hard coating solution containing titanium oxide, the solid concentration is about 33% by weight, and the refractive index of the hard coating film is 1.60 as a catalog value. 4 g of this coating solution was applied on the photochromic coating layer of the optical substrate prepared previously using the same spin coater as described above. The spin coating conditions were 600 rpm and 10 seconds. After spin coating, after preliminary drying at 70 ° C. for 15 minutes, main curing was performed at 120 ° C. for 1 hour to obtain a photochromic laminate. The thickness of the ultraviolet absorbing film obtained at this time was 4.8 μm.

The ultraviolet absorption characteristics and photochromic characteristics of this photochromic laminate were evaluated in the same manner as in Example 1, and the results are shown in Tables 2 and 3.
Example 5
A photochromic laminate was produced in the same manner as in Example 1 except that the ultraviolet absorbing film was formed using an organic coating agent as follows.

90 parts by weight of 2-hydroxyethyl methacrylate and 10 parts by weight of urethane oligomer hexaacrylate were mixed to prepare a mixture of radical polymerizable monomers. Then the following prescription:
100 parts by weight of the above-mentioned radical polymerizable monomer mixture Ethyl-2-cyano-3,3-diphenyl 1 acrylate (cyanoacrylate organic ultraviolet absorber) 1.5 parts by weight Photopolymerization initiator The components were mixed thoroughly to prepare an organic coating agent. As a photopolymerization initiator, a mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide (weight ratio: 3: 1) was used. .

About 2 g of the above organic coating agent was spin-coated on the surface of the photochromic coating layer of the optical substrate using the above-described spin coater under exactly the same conditions as in Example 1. Then, using a metal halide lamp, the optical substrate was irradiated with light for 1 minute in a nitrogen atmosphere at a light intensity of 405 nm of 120 mW / cm ² to cure the coating film of the organic coating agent. By performing the heat treatment for a time, a photochromic laminate having an organic ultraviolet absorbing film on the surface of the photochromic coat layer was obtained. The film thickness of the obtained organic ultraviolet absorbing film was 10 μm.

  The ultraviolet absorption characteristics and photochromic characteristics of this photochromic laminate were evaluated in the same manner as in Example 1, and the results are shown in Tables 2 and 3.

Example 6
A photochromic laminate was produced in the same manner as in Example 1 except that the ultraviolet absorbing film was formed by vapor deposition of a metal oxide as follows.

  First, a general-purpose silicone coating agent (alkoxysilane / silica sol system; TS-56H manufactured by Tokuyama Co., Ltd.) was applied to the surface of the previously produced optical substrate by dipping, cured at 120 ° C. for 2 hours, and primer layer Formed. The primer layer had a thickness of 1.6 μm. The coating agent does not contain an ultraviolet absorber, and this primer layer does not contain an ultraviolet absorber.

  Next, a thin film of titanium oxide (ultraviolet absorption film) was formed on the primer layer by vapor deposition to obtain a photochromic laminate having an ultraviolet absorption film (deposition film) on the surface of the photochromic coating layer. The thickness of this deposited film was 0.2 μm.

  The ultraviolet absorption characteristics and photochromic characteristics of this photochromic laminate were evaluated in the same manner as in Example 1, and the results are shown in Tables 2 and 3.

Comparative Example 1
The UV absorber sol added to the silicone-based coating agent is changed to a methanol-dispersed titanium oxide / zirconium oxide / silicon oxide composite metal oxide fine particle sol (weight ratio: 20/5/75, solid content concentration: 30% by weight) A photochromic laminate was produced in the same manner as in Example 1 except that the composition of the silicone coating agent was changed as shown in Table 1.

  The ultraviolet absorption characteristics and photochromic characteristics of this photochromic laminate were evaluated in the same manner as in Example 1, and the results are shown in Tables 2 and 3.

Comparative Example 2: Blank Test The photochromic characteristics of the previously prepared optical substrate were evaluated without any lamination on the surface of the photochromic coating layer, and the results are shown in Table 3. The ultraviolet absorption characteristics of the optical substrate are shown in Table 2 with the light transmittance at each wavelength being 100%.

Comparative Example 3
For the optical substrate (substrate before the deposition film is formed) on which the primer layer prepared in Example 6 was formed, the ultraviolet absorption characteristics and the photochromic characteristics were evaluated in the same manner as in Example 1, and the result Are shown in Table 2 and Table 3. The ultraviolet absorption characteristic is a characteristic of the primer layer.

(Comparative Example 4)
Oxide fine particles (ultraviolet absorber) exactly as in Example 1 except that the same amount of methanol-dispersed silicon oxide metal oxide fine particle sol (solid content concentration 30 wt%) was used instead of the composite metal oxide fine particle sol. Solution) was prepared.

  Next, 1.8 parts by weight of 2- (5-chloro-2′-hydroxy-3′-t-butyl-5′-methylphenyl) -benzotriazole was further mixed with 100 parts by weight of this solution as an organic ultraviolet absorber. Then, the solution was stirred until the organic ultraviolet absorber was dissolved, and this solution was filtered with a 0.5 micron filter to prepare a silicone coating agent containing the organic ultraviolet absorber.

  Using this silicone-based coating agent, a photochromic laminate having an ultraviolet absorbing film having a thickness of 2 μm was prepared in exactly the same manner as in Example 1. The ultraviolet absorption characteristics and photochromic properties of this photochromic laminate were the same as in Example 1. The results are shown in Tables 2 and 3.

Claims (7)

From an optical substrate having a photochromic surface layer portion made of a resin in which a photochromic compound is dispersed on at least one surface, and an ultraviolet absorbing film having a thickness of 0.1 to 100 μm formed on the photochromic surface layer portion of the optical substrate The ultraviolet absorbing film has a light transmittance of 360% or more and a light transmittance of 320 nm of 10% or less. The laminate according to claim 1, wherein the ultraviolet absorption film has a light transmittance of 560 nm of 85% or more. The laminate according to claim 1 or 2, wherein the ultraviolet absorbing film is a coating layer containing an inorganic oxide containing titanium as an ultraviolet absorber. The optical article which consists of a laminated body as described in any one of Claims 1-3. Prepare an optical substrate having a photochromic surface layer portion composed of a resin in which a photochromic compound is dispersed on at least one surface;
A silicone-based coating agent containing colloidal particles of an inorganic compound that selectively absorbs ultraviolet rays having a wavelength of 320 nm as an ultraviolet absorber is applied directly or via a primer layer on the photochromic surface layer portion of the optical substrate. The method for producing a laminate according to claim 1, wherein an ultraviolet absorbing film having a thickness of 0.1 to 100 μm is formed by curing. Prepare an optical substrate having a photochromic surface layer portion composed of a resin in which a photochromic compound is dispersed on at least one surface;
An organic coating agent containing an ultraviolet absorber that selectively absorbs ultraviolet rays having a wavelength of 320 nm is applied directly or via a primer layer on the photochromic surface layer portion of the optical substrate, and this is cured. The method for producing a laminate according to claim 1, wherein an ultraviolet absorbing film having a thickness of 1 to 100 μm is formed. Prepare an optical substrate having a photochromic surface layer portion composed of a resin in which a photochromic compound is dispersed on at least one surface;
An ultraviolet absorber that selectively absorbs ultraviolet rays having a wavelength of 320 nm is deposited on the photochromic surface layer portion directly or through a primer layer to form an ultraviolet absorbing film having a thickness of 0.1 to 1 μm. The manufacturing method of the laminated body of Claim 1.