JP2008256732A - Preserving method and manufacturing method of photochromic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means for obtaining a photochromic lens having excellent photoresponsive and optical characteristics. <P>SOLUTION: In the preserving method preserves the photochromic lens, the photochromic lens including a photochromic film of ≥800 nm ultramicro-indentation hardness on the extreme surface and in which the extreme surface of the photochromic film exists on the extreme surface is preserved under an atmosphere of a reduced oxygen concentration and/or humidity. The method for manufacturing the photochromic lens uses the method. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photochromic lens storage method and manufacturing method.

  In recent years, plastic photochromic lenses using organic photochromic dyes are commercially available for eyeglasses. They develop colors in bright outdoors and have the same anti-glare effect as high-density color lenses, and recover high transmittance when moving indoors. A photochromic lens is required to respond quickly when predetermined light is incident and develop a color at a high density, and to discolor quickly when placed in an environment without the light.

As a photochromic lens, a lens provided with a coating (photochromic film) containing a photochromic dye on a lens substrate is widely used. On the photochromic film, various coatings such as a hard coat and an antireflection film are usually further applied. Therefore, various production methods for obtaining a photochromic lens having excellent photoresponsiveness (reaction speed and color density) and excellent adhesion to a lens substrate or a hard coat layer have been studied (for example, Patent Documents 1 to 3). reference). However, the photoresponsiveness of the conventional photochromic lens is not always sufficient, and further improvement of the photoresponsiveness has been demanded.
International Publication WO03 / 011967 JP 2005-308767 A Japanese Patent Laid-Open No. 10-231331

Conventionally, it has been considered that the reaction rate and color density of the photochromic dye in the photochromic film depend on the characteristics unique to the photochromic dye resulting from the molecular structure. However, as a result of repeated studies by the applicant of the present application, if the photochromic film is not completely cured but has flexibility (fluidity), the dye moves easily in the film, and the reaction speed and color density of the color change are large. I got new knowledge that it would improve.
Therefore, based on the above findings, the applicant of the present application has previously filed a patent application for a photochromic film having an ultra-fine indentation hardness of at least 800 nm and having an appropriate flexibility (Japanese Patent Application No. 2007-020484). ).

  Although the above photochromic film exhibits excellent photoresponsiveness, as a result of repeated studies by the present inventors, a lens such as a hard coat or an antireflection film is formed on the surface of the photochromic film. It has been found that there is a new problem that optical defects (eg haze, coloration, etc.) may occur.

  Therefore, an object of the present invention is to provide a means for obtaining a photochromic lens having excellent photoresponsiveness and optical characteristics.

As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
For example, as described in Patent Documents 1 and 2, the raw material liquid of the photochromic film further includes an interface for improving the durability of the photochromic compound, improving the color development speed, improving the fading speed, and improving the moldability. Additives such as activators, antioxidants, radical scavengers, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and plasticizers are added as necessary. Is done. On the other hand, the above-described photochromic film developed by the applicant of the present application is usually formed without performing a curing process until the photochromic film is completely cured in order to impart flexibility to the outermost surface. Therefore, an unpolymerized portion is included on the outermost surface of the photochromic film. When such a photochromic film is stored in the atmosphere for a long time, the additive added to the raw material liquid of the photochromic film oozes out to the outer surface side (side in contact with air) (in the present invention, it is added That the component derived from the additive or additive comes out on the photochromic film surface side is expressed as “bleed out”), and the component that has exuded reacts with the component in the coating liquid, such as fogging and coloring It is thought to be the cause of the defect. Further, the present inventors have further studied based on the above findings and newly found that the surface of the photochromic lens after the formation of the photochromic film is brought into contact with oxygen or moisture in the air, which causes the above-mentioned bleeding. .
The present invention has been completed based on the above findings.

That is, the means for achieving the above object is as follows.
[1] A photochromic lens including a photochromic film having an ultra-fine indentation hardness of 800 nm or more on the outermost surface and a lens substrate, wherein the outermost surface of the photochromic film is positioned on the outermost surface of the photochromic lens, A method for storing a photochromic lens, wherein the photochromic lens is stored in an atmosphere having a reduced oxygen concentration and / or humidity.
[2] The photochromic lens storage method according to [1], wherein the atmosphere is a vacuum atmosphere.
[3] The photochromic lens storage method according to [1], wherein the atmosphere is an inert gas atmosphere.
[4] The photochromic lens storage method according to [1], wherein the atmosphere is a sealed atmosphere containing an oxygen scavenger.
[5] The photochromic lens storage method according to [4], wherein the sealed atmosphere further includes a desiccant.
[6] The method for storing a photochromic lens according to [1], wherein the atmosphere is a sealed atmosphere containing a desiccant.
[7] A photochromic lens including a photochromic film having an ultra-fine indentation hardness of 800 nm or more on the outermost surface and a lens substrate, wherein the outermost surface of the photochromic film is positioned on the outermost surface of the photochromic lens, A photochromic lens manufacturing method including a film forming step of forming a coating film on the outermost surface,
The said manufacturing method which preserve | saves the photochromic lens before the said film-forming process by the method in any one of [1]-[6].
[8] The method for producing a photochromic lens according to [7], wherein the photochromic film includes a hindered amine light stabilizer.

  According to the present invention, it is possible to provide a photochromic lens having both excellent light response and optical characteristics.

[How to save photochromic lenses]
The present invention is a photochromic lens including a photochromic film having an ultra-fine indentation hardness of 800 nm or more on the outermost surface and a lens substrate, and the outermost surface of the photochromic film is located on the outermost surface of the photochromic lens. It relates to the storage method. In the storage method of the present invention, the photochromic lens is stored in an atmosphere with a reduced oxygen concentration and / or humidity. In the present invention, the “photochromic film” means a film containing at least a photochromic dye and capable of causing a change in transmittance upon irradiation and blocking of light having a predetermined wavelength.
Below, the preservation | save method of this invention is demonstrated in detail.

  In the storage method of the present invention, the photochromic lens to be stored is a photochromic lens including a photochromic film having an ultra-fine indentation hardness of 800 nm or more on the outermost surface and a lens substrate, and the outermost surface of the photochromic film is It is a photochromic lens located on the outermost surface of the photochromic lens. By providing a moderate flexibility with an ultra-fine indentation hardness of 800 nm or more, the photochromic dye can easily move in the photochromic film, and the photoresponsiveness (reaction speed and color density) can be greatly improved. .

  The ultra-fine indentation hardness of the outermost surface of the photochromic film is preferably 5000 nm or less from the viewpoint of preventing mixing at the interface when the coating film is provided thereon and maintaining adhesion with the coating film. The preferable range is 900 to 4000 nm, and more preferably 1200 nm or more.

  Of course, it is possible to give the entire photochromic film the same flexibility. However, it is preferable that the outermost surface has the above-described appropriate flexibility and the surface facing the lens base material has an appropriate hardness in order to achieve both photoresponsiveness and optical characteristics. This point will be further described below.

FIG. 1 is an explanatory diagram showing an outline of a photochromic lens.
In general, a photochromic lens is a lens having optical surfaces on the front surface (surface on the object side when worn by the wearer as a spectacle lens) and the rear surface (surface on the eyeball side when worn on the wearer as a spectacle lens). A base material, a photochromic film formed on the front surface of the lens base material, and a coating film such as a hard coat formed on the photochromic film are provided. As the coating film, various coatings such as an antireflection film, a water repellent film, an antifouling film, and a mirror coat film can be laminated as necessary.
As mentioned above, if the photochromic film is moderately flexible (fluidity) without being completely cured, the photochromic dye can move easily in the photochromic film, and the reaction speed and color density of the color change can be greatly improved. Can do. However, when the flexibility (fluidity) of the entire photochromic film is increased, for example, when the photochromic film is formed by a casting polymerization method described later, the lens raw material liquid and the uncured portion of the photochromic film are mixed during the casting polymerization. There is a risk that the optical characteristics will deteriorate. Therefore, paying attention to the fact that the photoresponsiveness in the photochromic lens is mainly expressed in the surface layer of the photochromic film on the light incident side, the dye existing in the surface layer on the lens front surface side of the photochromic film is made to move easily, and the lens rear surface The side surface layer portion is preferably cured so as not to be mixed with the lens raw material liquid during the casting polymerization. As a method for obtaining such a photochromic film, an index (for example, hardness or polymerization degree) that can evaluate the degree of curing of the photochromic film is measured on the object side and the eyeball side of the photochromic film, and the curing condition is determined based on the result. It is good to set. From the above viewpoint, it is preferable that the ultra-fine indentation hardness of the surface of the photochromic film facing the lens substrate is at least higher than that of the outermost surface. The preferable range is 500-5000 nm. If the indentation hardness of the surface facing the lens substrate is 500 nm or more, the adhesion between the substrate and the photochromic film can be ensured, and if it is 5000 nm or less, it can occur in the cast polymerization method. Mixing at the interface between the substrate and the photochromic film can be prevented, and good optical properties can be secured. The lower limit is more preferably 600 nm, still more preferably 1000 nm, particularly preferably 2500 nm, and the upper limit is more preferably 3500 nm.

The “ultra fine indentation hardness” in the present invention is a value measured by applying a load of 100 mgf using an ultrafine indentation hardness tester ENT-2100 manufactured by Elionix. The measurement can be performed as follows. FIG. 2 shows a schematic diagram of a method for measuring the ultra fine indentation hardness.
First, the photochromic film on the lens substrate is peeled off from the substrate and fixed on the monitor glass so that the measurement target surface (surface A or surface B) is located on the outermost surface. Next, using a triangular pyramid-shaped diamond indenter (ridge interval 115 degrees) on the surface to be measured, a load of 100 mgf is applied and the surface is pushed vertically, and the displacement (nm) of the film at that time is measured. In the present invention, this displacement amount (nm) is defined as ultra-fine indentation hardness. A smaller value means higher hardness, and a larger value means lower hardness and flexibility.

  In the storage method of the present invention, the photochromic lens having the photochromic film is stored in an atmosphere with a reduced oxygen concentration and / or humidity. Here, the “atmosphere with reduced oxygen concentration” refers to an atmosphere with a lower oxygen concentration than in the atmosphere, and the “atmosphere with reduced humidity” refers to an atmosphere with a lower humidity than in the air. As described above, as a result of the study by the present inventors, optical defects generated when a coating film is formed on a photochromic lens after long-term storage are such that the surface of the photochromic film is in contact with oxygen or moisture in the atmosphere during long-term storage. It has been newly found that the components such as additives that have exuded to the surface due to the reaction with the components in the coating liquid are caused. Therefore, by preserving the photochromic lens before forming the coating film in an atmosphere with reduced oxygen and / or humidity that causes bleeding, the photochromic has excellent optical characteristics with few optical defects. A lens can be obtained.

Examples of the atmosphere include (A) a vacuum atmosphere (preferably a degree of vacuum of 10 ⁻¹ Pa or more), (B) an inert gas (rare gas, nitrogen gas, etc.) atmosphere, (C) a sealed atmosphere containing an oxygen scavenger, D) A sealed atmosphere containing a desiccant, (E) (C) + (D) above can be mentioned.

  In order to form (A), for example, a desiccator can be used. As a case where a desiccator is used, for example, a vacuum desiccator can be used, and a vacuum atmosphere can be formed by driving a connected vacuum pump to form a vacuum.

  In order to form (B), a method of flowing an inert gas such as a rare gas or a nitrogen gas using a gas replacement type desiccator can be used. In this case, since it is preferable that the oxygen concentration and the amount of water in the rare gas are small, it is preferable to use a high-purity rare gas.

  In order to form (C) to (E), a known oxygen scavenger and desiccant can be used. Specifically, an oxygen scavenger and a desiccant can be placed in a desiccator to realize the atmosphere.

  A well-known thing can be used as a desiccant, For example, the desiccant which has a silica gel as a main component can be used. Further, the type and amount of the desiccant may be determined in consideration of the moisture content in the storage atmosphere, the storage period, and the like.

Moreover, a well-known thing can be used as an oxygen scavenger. For example, an oxygen scavenger composition that absorbs oxygen can be used which is packaged with a packaging material having air permeability. In addition, you may use what formed the substance containing an oxygen absorber composition in the sheet form. As the oxygen scavenger composition, for example, a composition that absorbs oxygen using an oxidation reaction of a reducing metal can be used. The oxygen absorber using such an oxygen absorber composition includes a moisture-dependent oxygen absorber that needs to be replenished with water from the atmosphere in deoxidation, and a self-reaction that does not require rehydration from the atmosphere. There is a type oxygen scavenger. An example of a moisture-dependent oxygen scavenger is described in Japanese Patent Publication No. 56-33980. This oxygen scavenger composition has a structure in which metal powder such as iron powder is coated with a metal halide.
Examples of the self-reactive oxygen absorber include those described in JP-B-57-31449. In this oxygen scavenger, a water donor is present in the oxygen scavenger, and water necessary for oxygen scavenging is supplied therefrom.
When a self-reactive oxygen absorber is used, water vapor generated from a moisture donor in the oxygen absorber may evaporate in the sealed packaging material, which may affect the lens. In such a case, a desiccant (such as silica gel) may be enclosed in the packaging material together with a self-reactive oxygen absorber. Further, an oxygen scavenger having both a oxygen scavenging function and a drying function may be used (for example, Pharma Keep (KD, KC type) manufactured by Mitsubishi Gas Chemical Co., Ltd.). Moreover, you may use the deoxidation agent which exhibits a deoxidation function in a dry atmosphere, without requiring a moisture donor. Examples of such an oxygen scavenger include an oxygen scavenger having a oxygen scavenging component made of a crosslinked polymer having a carbon-carbon unsaturated bond (see, for example, JP-A-11-70331), or a transition metal supported on a carrier. An oxygen scavenger mainly based on activated metal (see, for example, JP-A-8-38883), or an oxygen scavenger based on activated magnesium obtained by carrying a magnesium compound on a carrier and then reducing it (See, for example, JP-A-2001-37457), an oxygen scavenger having an oxygen-absorbing composition in which a liquid hydrocarbon oligomer having an unsaturated group as a main component and an oxygen-absorption-promoting substance is supported on a carrier (for example, No. 10-113555). Commercially available products include PharmaKeep (KH type) manufactured by Mitsubishi Gas Chemical Co., Ltd. The type and amount of the oxygen scavenger may be determined in consideration of the amount of oxygen in the storage atmosphere and the storage period.

  In addition, an atmosphere with reduced oxygen and / or humidity can be formed using a gas barrier packaging bag. As the method, for example, a lens is put in a packaging bag in which permeation of oxygen and water vapor is suppressed, and a packaging bag is used by using a nozzle type degassing packaging machine or a chamber type vacuum / gas replacement packaging machine as shown in FIG. It is preferable to use a method in which the inside is evacuated and sealed. Moreover, in this invention, you may implement | achieve the atmosphere of said (B) by enclosing and sealing rare gas in a packaging bag using these packaging machines. In addition, as shown in FIG. 4, an oxygen scavenger and / or a desiccant is put together with the lens and the opening of the packaging bag is sealed to realize the atmospheres (C) to (D). May be. In the present invention, “sealing” means that the storage atmosphere is shielded from the outside air to such an extent that permeation of oxygen and / or water vapor can be suppressed. “Gas barrier property” refers to the property of suppressing the permeation of oxygen and water vapor.

The photochromic lens to be stored in the storage method of the present invention is, for example, a method in which molding of a lens base material and formation of a photochromic film on the lens base material is performed in a molding die using casting polymerization (hereinafter referred to as a note). The mold polymerization method). In this method, first, a photochromic liquid is applied to one surface of a mold for forming one surface of a lens, and a photochromic film is formed on the mold surface by applying a curing treatment to the applied photochromic liquid. Thereafter, a lens substrate is subjected to a polymerization reaction using a mold having a photochromic film formed on the surface. Specifically, a photochromic lens having the above-described photochromic film on a lens substrate can be obtained by a casting polymerization method according to the following steps.
(Photochromic liquid application process)
A photochromic liquid (including a photochromic dye, a curable component, and various additives as necessary) is applied to one surface (molding surface) of the first mold for forming one surface of the lens.
(Photochromic liquid curing process)
A photochromic film is formed on the first mold molding surface by performing a curing process so that the photochromic liquid applied on the first mold molding surface does not completely cure.
(Lens mold forming process)
The first mold and the second mold for forming the other surface of the lens are arranged so that the outermost surface of the photochromic film of the first mold faces the molding surface of the second mold, and the two molds The lens mold is formed with a cavity in which the photochromic film is located.
(Cast polymerization process)
A lens raw material liquid containing a curable component is injected into the cavity, and the curing reaction of the curable component is performed in the cavity.
(Release process)
The lens mold is removed to obtain a molded lens. In the obtained lens, the photochromic film formed on the first mold molding surface by the photochromic liquid curing process is peeled off from the first mold molding surface and formed on the lens substrate.
Below, the detail of each process is demonstrated one by one.

(Photochromic liquid application process)
In this step, a photochromic liquid is applied to one surface (molding surface) of a mold (first mold) for forming one surface of the lens.
As the photochromic liquid, a photochromic liquid containing at least a photochromic dye and a curable component and containing various additives as necessary can be used. Details of each component will be described later.

  Application of the photochromic liquid to the surface of the first mold can be performed by a known method such as a dipping method, a spin coating method, or a spray method. From the viewpoint of the viscosity and surface accuracy of the coating solution, it is preferable to use a spin coating method. The coating amount may be appropriately adjusted according to the desired photochromic film thickness.

  In order to form a meniscus lens, a convex mold having a convex surface on the convex side (eyeball side when used) to form a concave surface of the lens, and a concave side to form a convex surface of the lens (object side when used) A concave mold having a molding surface is used. In the present invention, a photochromic film having a photochromic film on the object side can be obtained by applying a photochromic liquid on the concave mold (mold) to form a photochromic film. In the method of manufacturing a photochromic lens by applying and curing a photochromic solution on the lens, the photochromic solution is applied on the convex surface located on the object side during use, so the viscosity of the photochromic solution is low or the application amount is large In some cases, the applied photochromic liquid may flow down from the convex surface. On the other hand, if the photochromic liquid is applied on the concave surface as described above, there is an advantage that it can be stably held without flowing down from the mold surface.

(Photochromic liquid curing process)
In this step, a photochromic film is formed on the first mold by performing a curing process on the photochromic liquid applied on the first mold.

  The cured state of the photochromic film can be controlled by (1) the composition of the photochromic liquid, (2) curing conditions, and (3) the thickness of the photochromic film. The above (1) to (3) will be sequentially described below.

(1) Photochromic liquid (i) Curable component The curable component that can be used for forming the photochromic film is not particularly limited, and is a (meth) acryloyl group, a (meth) acryloyloxy group, a vinyl group, an allyl group, or a styryl. Known photopolymerizable monomers and oligomers having radically polymerizable groups such as groups, and prepolymers thereof can be used. Among these, a compound having a (meth) acryloyl group or a (meth) acryloyloxy group as a radically polymerizable group is preferable because of easy availability and curability. The (meth) acryloyl represents both acryloyl and methacryloyl.

Prevents mixing at the interface between the photochromic film and the lens substrate, facilitates hardness adjustment, cure properties such as solvent resistance, hardness and heat resistance after film formation, or photochromic characteristics such as color density and fading speed In order to make it good, the radical polymerizable monomer includes a homopolymer having an L scale Rockwell hardness of 60 or more (hereinafter sometimes referred to as a high hardness monomer), and a homopolymer. It is more preferable to use an L scale Rockwell hardness of 40 or less (hereinafter sometimes referred to as a low hardness monomer).
L scale Rockwell hardness means the hardness measured according to JIS-B7726. By performing this measurement on the homopolymer of each monomer, it can be easily determined whether or not the hardness condition is satisfied. 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.
The high-hardness monomer has the effect of improving the solvent resistance, hardness, heat resistance and the like of the cured product after curing. In order to make these effects more effective, a radical polymerizable monomer having a homopolymer L-scale Rockwell hardness of 65 to 130 is preferable.
Such a high-hardness monomer is usually a compound having 2 to 15 and preferably 2 to 6 radical polymerizable groups, and preferred specific examples are represented by the following general formulas (1) to (5). Compounds.

Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is a hydrogen atom, a methyl group or an ethyl group, R ¹⁵ is a 3-6 valent organic group, and f is in the range of 0-3. Integer, f ′ is an integer in the range of O to 3, and g is an integer in the range of 3 to 6.)

(In the formula, R ¹⁶ is a hydrogen atom or a methyl group, B is a trivalent organic group, D is a divalent organic group, and h is an integer in the range of 1 to 10.)

Wherein R ¹⁷ is a hydrogen atom or a methyl group, R ¹⁸ is a hydrogen atom, a methyl group, an ethyl group or a hydroxyl group, E is a divalent organic group containing a cyclic group, i and j Is a positive integer such that the average value of i + j is 0-6.)

(In the formula, R ¹⁹ is a hydrogen atom or a methyl group, and F is an alkylene group having 2 to 9 main chain carbon atoms which may have a side chain.)

(In the formula, R ²⁰ is a hydrogen atom, a methyl group or an ethyl group, and k is an integer in the range of 1 to 6.)

In the general formulas (1) to (4), R ^{13 to} R ¹⁹ are all hydrogen atoms or methyl groups, and therefore the compounds represented by the general formulas (1) to (4) are 2 to 6 ( It is a compound having a (meth) acryloyloxy group.
R ¹⁴ in the general formula (1) is a hydrogen atom, a methyl group or an ethyl group.
R ¹⁵ in the general formula (1) is a trivalent to hexavalent organic group. The organic group is not particularly limited, and includes a bond other than a carbon-carbon bond such as an ester bond, an ether bond, an amide bond, a thioether bond, a sulfonyl bond, or a urethane bond in the main chain. Also good.
In order for the L scale Rockwell hardness of the homopolymer to be 60 or more, R ¹⁵ is preferably an organic group having 1 to 30 carbon atoms, more preferably an ether bond and / or a urethane bond. It is a good organic group having 1 to 15 carbon atoms.
F and f ′ are each independently an integer in the range of 0 to 3. Moreover, in order to make L scale Rockwell hardness 60 or more, it is preferable that the sum total of f and f 'is 0-3.

  Specific examples of the high hardness monomer represented by the general formula (1) include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethanetrimethacrylate, tetramethylolmethanetriacrylate, trimethylolbropantrimethacrylate, Tetramethylolmethane tetramethacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triethylene glycol trimethacrylate, trimethylolpropane triethylene glycol triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate, Pentaerythritol tetramethacrylate, dipen Hexaacrylate, urethane oligomer tetraacrylate, urethane oligomer hexa methacrylate, urethane oligomer hexaacrylate, polyester oligomer hexaacrylate, caprolactone-modified dipentaerythritol hexaacrylate, and ditrimethylolpropane tetraacrylate.

In the general formula (2), B is a trivalent organic group, and D is a divalent organic group. B and D are not particularly limited, and the main chain may contain bonds other than carbon-carbon bonds such as ester bonds, ether bonds, amide bonds, thioether bonds, sulfonyl bonds, and urethane bonds. Good. In order for the L-scale Rockwell hardness of the homopolymer to be 60 or more, B is preferably an organic group derived from a linear or branched hydrocarbon having 3 to 10 carbon atoms, and D is a carbon number. An organic group derived from a linear or branched aliphatic hydrocarbon having 1 to 10 carbon atoms or an aromatic hydrocarbon having 6 to 10 carbon atoms.
Moreover, in order to make L scale Rockwell hardness of a homopolymer 60 or more, h is an integer in the range of 1-10, Preferably it is an integer in the range of 1-6.
Specific examples of the high-hardness monomer represented by the general formula (2) include tetrafunctional polyester oligomers (Daicel UCB, EB80, etc.) having a molecular weight of 2,500 to 3,500, and molecular weights of 6,000 to 8,000. Tetrafunctional polyester oligomer (Daicel UCB, EB450, etc.), 6functional polyester oligomer with molecular weight of 45,000-55,000 (Daicel UCB, EB1830, etc.), tetrafunctional polyester oligomer with molecular weight 10,000 (Daiichi Kogyo) Pharmaceutical companies, GX8488B, etc.).

R ¹⁸ in the general formula (3) is a hydrogen atom, a methyl group, an ethyl group or a hydroxyl group. E in the formula (3) is a divalent organic group containing a cyclic group. The organic group is not particularly limited as long as it contains a cyclic group, and in the main chain, carbon- such as ester bond, ether bond, amide bond, thioether bond, sulfonyl bond, urethane bond, etc. Bonds other than carbon bonds may be included. Examples of the cyclic group contained in E include a benzene ring, a cyclohexane ring, an adamantane ring, and the following cyclic groups.

The cyclic group contained in E is preferably a benzene ring, and E is represented by the following formula:
(G is an oxygen atom, a sulfur atom, —S (O ₂ ) —, —C (O) —, —CH ₂ —, —CH═CH—, —C (CH ₃ ) ₂ — and —C (CH ₃ ) (C ₆ H ₅ ) —, R ²¹ and R ²² are each independently an alkyl group having 1 to 4 carbon atoms or a halogen atom, and l and l ′ are each independently Is an integer in the range of 0 to 4.), and most preferable E is represented by the following formula:
It is group shown by these.

In the general formula (3), i and j are positive integers with an average value of i + j being 0-6. The compound represented by the formula (3) is usually obtained as a mixture of a plurality of compounds having different i and j except when both i and j are 0. Since their isolation is difficult, i and j are expressed as the average value of i + j. The average value of i + j is more preferably 2-6.
Specific examples of the high hardness monomer represented by the general formula (3) include bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, and 2,2-bis (3,5-dibromo-4. -Methacryloyloxyethoxyphenyl) propane and the like.

In the general formula (4), R ¹⁹ is a hydrogen atom or a methyl group, and F is an alkylene group having 2 to 9 main carbon atoms which may have a side chain. Examples of the alkylene group having 2 to 9 carbon atoms in the main chain include an ethylene group, a propylene group, a trimethylene group, a butylene group, a neopentylene group, a hexylene group, and a nonylylene group.
Specific examples of the high hardness monomer represented by the general formula (4) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, 1,9-nonylene glycol dimethacrylate, and neopentylene glycol. Examples include dimethacrylate and neopentylene glycol diacrylate.

R ²⁰ in the general formula (5) is a hydrogen atom, a methyl group or an ethyl group, k is an integer in the range of 2 to 6, and preferably k is 3 or 4.
Specific examples of the high hardness monomer represented by the general formula (5) include diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, and tetrapropylene glycol dimethacrylate.
In addition, even in the compounds represented by the general formulas (1) to (5), depending on the combination of substituents, there are homopolymers having L scale Rockwell hardness of less than 60. Is classified into a low-hardness monomer or a medium-hardness monomer described later.
There are also high-hardness monomers not represented by the general formulas (1) to (5), and typical compounds include bisphenol A diglycidyl methacrylate, ethylene glycol bisglycidyl methacrylate, and glycidyl methacrylate.

The low-hardness monomer has an effect of making the cured body tough and improving the fading speed of the photochromic compound.
As such a low hardness monomer, the following general formula (6):
Wherein R ²³ is a hydrogen atom or a methyl group, R ²⁴ and R ²⁵ are each independently a hydrogen atom, a methyl group or an ethyl group, Z is an oxygen atom or a sulfur atom, and m is R ²³ When R is a hydrogen atom, it is an integer of 1 to 70, and when R ²³ is a methyl group, it is an integer of 7 to 70, and m ′ is an integer in the range of 0 to 70.)

Or the following general formula (7):
(Wherein R ²⁶ is a hydrogen atom or a methyl group, R ²⁷ and R ²⁸ are each independently a hydrogen atom, a methyl group, an ethyl group or a hydroxyl group, and I is a divalent organic compound containing a cyclic group. And i ′ and j ′ are integers having an average value of i ′ + j ′ of 8 to 40.)
Or a bifunctional monomer represented by the following general formula (8):

(Wherein R ²⁹ is a hydrogen atom or a methyl group, R ³⁰ and R ³¹ are each independently a hydrogen atom, a methyl group or an ethyl group, and R ³² is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms) , An alkenyl group, an alkoxyalkyl group or a haloalkyl group, an aryl group having 6 to 25 carbon atoms, or an acyl group other than a (meth) acryloyl group having 2 to 25 carbon atoms, Z is an oxygen atom or a sulfur atom, m ″ Is an integer of 1 to 70 when R ²⁹ is a hydrogen atom, an integer of 4 to 70 when R ²⁹ is a methyl group, and m ″ ′ is an integer in the range of 0 to 70. )

Or the following general formula (9):
Wherein R ³³ is a hydrogen atom or a methyl group, R ³⁴ is an alkyl group having 1 to 20 carbon atoms when R ³³ is a hydrogen atom, and 8 carbon atoms when R ³³ is a methyl group. ˜40 alkyl groups.)
The monofunctional monomer shown by these is illustrated.

In the general formulas (6) to (9), R ²³ , R ²⁶ , R ²⁹ and R ³³ are a hydrogen atom or a methyl group. That is, the low hardness monomer usually has 2 or less (meth) acryloyloxy groups or (meth) acryloylthio groups as a polymerizable group.
In the general formula (6), R ²⁴ and R ²⁵ are each independently a hydrogen atom, a methyl group or an ethyl group, and Z is an oxygen atom or a sulfur atom.
In the general formula (6), when R ²³ is a hydrogen atom, that is, when it has an acryloyloxy group or an acryloylthio group as a polymerizable group, m is an integer of 1 to 70, while R ²³ is methyl. When it is a group, that is, when it has a methacryloyloxy group or a methacryloylthio group as a polymerizable group, m is an integer of 7 to 70. M ′ is an integer in the range of 0 to 70.
Specific examples of the low-hardness monomer represented by the general formula (6) include alkylene glycol di (meth) acrylates such as trialkylene glycol diacrylate, tetraalkylene glycol diacrylate, nonyl alkylene glycol diacrylate, and nonyl alkylene glycol dimethacrylate. Kind.

R ²⁶ in the general formula (7) is a hydrogen atom, a methyl group or an ethyl group.
I is a divalent organic group containing a cyclic group. This I is the same as those exemplified as E which is a cyclic group included in the formula (9). I ′ and j ′ in the formula (7) are integers having an average value of i ′ + j ′ of 8 to 40, preferably 9 to 30. These i ′ and j ′ are also usually expressed as average values for the same reason as i and j in the above-mentioned formula (3).
Specific examples of the low hardness monomer represented by the general formula (7) include 2,2-bis (4-acryloyloxypolyethylene glycol phenyl) propane having an average molecular weight of 776.

In the general formula (8), R ²⁹ is a hydrogen atom or a methyl group, and R ³⁰ and R ³¹ are each independently a hydrogen atom, a methyl group or an ethyl group. R ³² is a hydrogen atom, an alkyl group having 1 to 25 carbon atoms, an alkenyl group, an alkoxyalkyl group or a haloalkyl group, an aryl group having 6 to 25 carbon atoms, or an acyl group other than an acryloyl group having 2 to 25 carbon atoms.
Examples of the alkyl group or alkenyl group having 1 to 25 carbon atoms include a methyl group, an ethyl group, a propyl group, and a nonyl group. These alkyl groups or alkenyl groups may be linear or branched, and may be further substituted with a substituent such as a halogen atom, a hydroxyl group, an aryl group, or an epoxy group.
Examples of the alkoxyalkyl group having 1 to 25 carbon atoms include a methoxybutyl group, an ethoxybutyl group, a butoxybutyl group, and a methoxynonyl group.
Examples of the aryl group having 6 to 25 carbon atoms include a phenyl group, a toluyl group, an anthranyl group, and an octylphenyl group. Examples of the acyl group other than the (meth) acryloyl group include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and an oleyl group.
M ″ in the general formula (8) is an integer in the range of 1 to 70 when R ²⁹ is a hydrogen atom, that is, when it has an acryloyloxy group or an acryloylthio group as a polymerizable group, and R ²⁹ is methyl. In the case of a group, that is, when having a methacryloyloxy group or a methacryloylthio group as a polymerizable group, m ″ is an integer of 4 to 70, and m ′ ″ is an integer of 0 to 70.

  Specific examples of the low hardness monomer represented by the general formula (8) include polyethylene glycol methacrylate having an average molecular weight of 526, polyethylene glycol methacrylate having an average molecular weight of 360, methyl ether polyethylene glycol methacrylate having an average molecular weight of 475, an average molecular weight of 1, 000 methyl ether polyethylene glycol methacrylate, polypropylene glycol methacrylate having an average molecular weight of 375, polypropylene methacrylate having an average molecular weight of 430, polypropylene methacrylate having an average molecular weight of 622, methyl ether polypropylene glycol methacrylate having an average molecular weight of 620, poly having an average molecular weight of 566 Tetramethylene glycol methacrylate, octylphenyl ether polyester having an average molecular weight of 2,034 Examples include lenglycol methacrylate, nonyl ether polyethylene glycol methacrylate having an average molecular weight of 610, methyl ether polyethylene thioglycol methacrylate having an average molecular weight of 640, and polyalkylene glycol (meth) acrylates such as perfluorohebutylethylene glycol methacrylate having an average molecular weight of 498. . The preferable range of the average molecular weight of the low hardness monomer represented by the general formula (8) is 200 to 2500, more preferably 300 to 700. In addition, the average molecular weight in this invention is a mass average molecular weight.

In the general formula (9), R ³³ is a hydrogen atom or a methyl group. When R ³³ is a hydrogen atom, R ³⁴ is an alkyl group having 1 to 20 carbon atoms, and R ³³ is a methyl group. R ³⁴ is an alkyl group having 8 to 40 carbon atoms. These alkyl groups may be linear or branched and may be substituted with a substituent such as a halogen atom, a hydroxyl group, an alkoxyl group, an acyl group, or an epoxy group.
Specific examples of the low hardness monomer represented by the general formula (9) include stearyl methacrylate, lauryl methacrylate, ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate.
Among these low-hardness monomers represented by the formulas (6) to (9), methyl ether polyethylene glycol methacrylate having an average molecular weight of 475, methyl ether polyethylene glycol methacrylate having an average molecular weight of 1,000, trialkylene glycol diacrylate, tetra Alkylene glycol diacrylate, nonyl alkylene glycol diacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate are particularly preferred.
Even in the compounds represented by the above formulas (6) to (9), depending on the combination of the substituents, there are those in which the L-scale Rockwell hardness of the homopolymer is 40 or more. The high hardness monomer or the medium hardness monomer described later.

  Examples of the monomer that is neither a high-hardness monomer nor a low-hardness monomer, that is, a monomer that exhibits an L scale Rockwell hardness of more than 40 and less than 60 (sometimes referred to as a medium hardness monomer), for example, having an average molecular weight of 650 Polytetramethylene glycol dimethacrylate, polytetramethylene glycol dimethacrylate having an average molecular weight of 1,400, bifunctional (meth) acrylates such as bis (2-methacryloyloxyethylthioethyl) sulfide; diallyl phthalate, diallyl isophthalate, Polyallyl compounds such as diallyl tartrate, diallyl epoxy succinate, diallyl fumarate, diallyl chlorendate, diallyl hexaphthalate, allyl diglycol carbonate; 1,2-bis (methacryloylthio) ethane, bis (2 Polyacrylic acid and polyvalent thiomethacrylic acid ester compounds such as acryloylthioethyl) ether and 1,4-bis (methacryloylthiomethyl) benzene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride; methacryl Acrylic acid and methacrylic acid ester compounds such as methyl acid, butyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, biphenyl methacrylate; fumaric acid ester compounds such as diethyl fumarate and diphenyl fumarate; methylthioacrylate Thioacrylic acid and thiomethacrylic acid ester compounds such as benzylthioacrylate and benzylthiomethacrylate; styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methyls Vinyl compounds such as ethylene dimer, bromostyrene, divinylbenzene, vinylpyrrolidone; oleyl methacrylate, nerol methacrylate, geraniol methacrylate, linalool methacrylate, farnesol methacrylate, etc., and the hydrocarbon chain having an unsaturated bond in the molecule has 6 to 6 carbon atoms And a radically polymerizable monofunctional monomer such as 25 (meth) acrylate.

  These medium hardness monomers can also be used, and the high hardness monomer, the low hardness monomer, and the medium hardness monomer can be appropriately mixed and used. In order to improve the balance of the cured product properties such as solvent resistance, hardness, heat resistance, etc. of the cured product of the curable composition, or photochromic properties such as color density and fading speed, The low-hardness monomer is preferably 5 to 70% by mass, and the high-hardness monomer is preferably 5 to 95% by mass. Further, as the high hardness monomer to be blended, it is particularly preferable that a monomer having three or more radical polymerizable groups is blended in at least 5% by mass or more in other radical polymerizable monomers.

(Ii) Photochromic dye As the photochromic dye that can be added to the photochromic liquid, known ones can be used, and examples thereof include photochromic compounds such as fulgimide compounds, spirooxazine compounds, and chromene compounds. In the present invention, These photochromic compounds can be used without particular limitation.
Examples of the fulgimide compound, spirooxazine compound, and chromene compound are described in, for example, JP-A-2-28154, JP-A-62-228830, WO94 / 22850, and WO96 / 14596. Can be preferably used.
Examples of compounds having excellent photochromic properties include, for example, JP 2001-114775 A, JP 2001-031670 A, JP 2001-011067 A, JP 2001-011066 A, JP 2000-347346 A. JP, JP 2000-34476, JP 2000-3044761, JP 2000-327676, JP 2000-327675, JP 2000-256347, JP 2000-229976. JP-A 2000-229975, JP-A 2000-229974, JP-A 2000-229773, JP-A 2000-229972, JP-A 2000-219687, JP-A 2000-219686, Open 2000-19685 JP-A-11-322739, JP-A-11-286484, JP-A-11-279171, JP-A-10-298176, JP-A-09-218301, JP-A-09-124645, The compounds disclosed in JP-A-08-295690, JP-A-08-176139, JP-A-08-157467 and the like can also be suitably used.

  Among these photochromic compounds, chromene-based photochromic compounds are particularly suitable because they have higher photochromic property durability than other photochromic compounds, and the improvement in color density and fading speed of photochromic properties is particularly large compared to other photochromic compounds. Can be used for Further, among these chromene-based photochromic compounds, those having a molecular weight of 540 or more can be suitably used because the improvement in the color density and the fading speed of the photochromic properties according to the present invention is particularly large compared to other chromene-based photochromic compounds. .

Further, as a chromene compound having particularly good various photochromic properties such as the color density, fading speed, and durability, those represented by the following general formula (12) are preferable.

[In the formula, the following general formula (13):
Is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted unsaturated heterocyclic group, and R ⁴³ , R ⁴⁴ and R ⁴⁵ are each independently a hydrogen atom or an alkyl group. , Alkoxyl group, aralkoxy group, amino group, substituted amino group, cyano group, substituted or unsubstituted aryl group, halogen atom, aralkyl group, hydroxyl group, substituted or unsubstituted alkynyl group, nitrogen atom as hetero atom A substituted or unsubstituted heterocyclic group in which the nitrogen atom and the pyran ring or the ring of the group represented by the formula (13) are bonded, or an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic base group. A fused heterocyclic group, o is an integer in the range of 0-6,
R ⁴¹ and R ⁴² each independently represent the following general formula (14),
(In the formula, R ⁴⁶ represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, R ⁴⁷ represents a hydrogen atom, an alkyl group, or a halogen atom; A group represented by the following general formula (15):
Wherein R ⁴⁸ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group, and p ′ is an integer of 1 to 3, a substituted or unsubstituted group An aryl group, a substituted or unsubstituted heteroaryl group, or an alkyl group, or R ⁴¹ and R ⁴² may be combined to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. . ]
In addition, examples of the substituent in the substituted aryl group and the substituted heteroaryl group described in the general formulas (14) and (15) and R ⁴¹ and R ⁴² include the same groups as in R ^{43 to} R ^44. .

Among the chromene compounds represented by the general formula (12), the compounds represented by the following general formulas (16) to (21) are particularly suitable from the viewpoint of photochromic properties such as color density and fading speed and durability. .
Wherein R ⁴⁹ and R ⁵⁰ are the same as R ⁴¹ and R ^{42 in} the general formula (12), respectively, and R ⁵¹ and R ⁵² are the same as R ^{45 in the} formula (12), respectively. q and q ′ are each 1 or 2.)

{In the formula, R ⁵³ and R ⁵⁴ are the same as R ⁴¹ and R ^{42 in} the general formula (12), respectively; R ⁵⁵ and R ⁵⁶ are the same as R ^{45 in the} formula (12); L is the following formula:
(In the above formula, P is an oxygen atom or a sulfur atom, R ⁵⁷ 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. }

(Wherein R ⁵⁸ and R ⁵⁹ are the same as R ⁴¹ and R ^{42 in} the formula (12), respectively, and R ⁶⁰ , R ⁶¹ and R ⁶² are the same as R ^{45 in the} formula (12), respectively. And v is 1 or 2.)

(Wherein R ⁶³ and R ⁶⁴ are the same as R ⁴¹ and R ^{42 in the} formula (12), respectively, R ⁶⁵ and R ⁶⁶ are the same as R ^{45 in the} formula (12), and w And w ′ are each independently 1 or 2.)

(In the formula, R ⁶⁷ and R ⁶⁸ are the same as R ⁴¹ and R ^{42 in} the formula (12), respectively, and R ⁶⁹ , R ⁷⁰ , R ⁷¹ and R ⁷² are R ^{45 in the} formula (12), respectively. And x and x ′ are each independently 1 or 2.)

Wherein R ⁷³ and R ⁷⁴ are the same as R ⁴¹ and R ^{42 in} the formula (12), respectively, and R ⁷⁵ , R ⁷⁶ and R ⁷⁷ are the same as R ^{45 in the} formula (12), respectively. Yes,
Is an aliphatic hydrocarbon ring which may have at least one substituent, and y, y ′ and y ″ are each independently 1 or 2. ]

Among the chromene compounds represented by the general formulas (16) to (21), chromene compounds having the following structures are particularly preferable.

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

  In the present invention, the cured state of the photochromic film can be controlled by the photochromic dye concentration in the photochromic liquid. When a curing reaction is performed by photopolymerization, when light irradiation is performed for polymerization, a photochromic dye develops color in response to the light, so that transmission of light irradiated for polymerization into the film is suppressed. This makes it possible to favorably advance the curing reaction in the vicinity of the surface on which the light irradiated for polymerization is incident, and to suppress the progress of the curing reaction on the other surface. In order to acquire said effect, the density | concentration of the photochromic pigment | dye in a photochromic liquid shall be 0.01-20 mass parts with respect to 100 mass parts (radical polymerizable monomers etc.) of the said polymeric components. Preferably, the content is 0.1 to 10 parts by mass.

(Iii) Polymerization initiator The polymerization initiator added to the photochromic liquid can be appropriately selected from known thermal polymerization initiators and photopolymerization initiators according to the polymerization method.
The photopolymerization initiator is not particularly limited. For example, benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, acetophenone, 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-isopropylthiooxane, bis (2 , 6-Dimethoxybenzoyl-2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine And 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like, such as 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthiooxanthone, bis (2,6-dimethoxybenzoyl) -2,4,4-Trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide are preferred.
These photopolymerization initiators can be used by appropriately mixing a plurality of types. As a compounding quantity with respect to the photochromic liquid whole quantity of a photoinitiator, it is 0.001-5 mass parts normally with respect to 100 mass parts of said polymeric components (radical polymerizable monomer etc.), and 0.1-1 It is preferable that it is a mass part.

When the photochromic film is formed by thermal polymerization, usable thermal polymerization initiators include diacyl peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and acetyl peroxide; Peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate; diisopropylperoxydicarbonate, di-2- Percarbonates such as ethylhexyl peroxydicarbonate and di-sec-butyloxycarbonate; 2,2′-azopisisoptyronitrile, 2,2′-azopis (4-dimethylvaleronitrile), 2,2′-azobi (2-methylbutyronitrile), and azo compounds such as 1,1'-azobis (cyclohexane-1-carbonitrile).
The amount of these thermal polymerization initiators used varies depending on the polymerization conditions, the type of initiator, the type and composition of the polymerizable monomer, but is usually from 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable component. It is preferable to be in the range. The above thermal polymerization initiators may be used alone or in combination.

(Iv) Additives The photochromic liquid contains surfactants, antioxidants, radical scavengers, ultraviolet rays for the purpose of improving the durability of the photochromic dye, improving the color development speed, improving the fading speed and improving the moldability. You may add additives, such as a stabilizer, a ultraviolet absorber, a mold release agent, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance | flavor, a plasticizer. As these additives, known compounds are used without any limitation.

  As the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but a nonionic surfactant is preferably used because of its solubility in a polymerizable monomer. 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 Alkoxy polyoxyethylene alkyl amine fatty acid amides, polyoxyethylene alkylphenyl formaldehyde condensate, a single-chain polyoxyethylene alkyl ethers. In using the surfactant, two or more kinds may be mixed and used. The addition amount of the surfactant is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable component.

  Antioxidants, radical scavengers, UV stabilizers, UV absorbers include hindered amine light stabilizers, hindered phenol antioxidants, phenol radical scavengers, sulfur antioxidants, benzotriazole compounds, benzophenones A system compound etc. can be used conveniently. These antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers may be used in combination of two or more. Furthermore, when using these non-polymerizable compounds, surfactants and antioxidants, radical scavengers, UV stabilizers, and UV absorbers may be used in combination. The addition amount of these antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers is preferably in the range of 0.001 to 20 parts by mass with respect to 100 parts by mass of the polymerizable component.

  Among the stabilizers, a hindered amine light stabilizer is a preferable stabilizer from the viewpoint of preventing deterioration of the photochromic dye during curing or improving the durability of the obtained photochromic film. However, as shown in the examples described later, examples of the exudation component include hindered amine light stabilizers. On the other hand, as described above, according to the storage method of the present invention, it is possible to prevent seepage during long-term storage. Therefore, the preservation method of the present invention is effective when applied to a photochromic lens having a photochromic film containing a hindered amine light stabilizer, which may bleed out during long-term storage.

  As the hindered amine light stabilizer, known compounds can be used without any limitation. Among them, when used for coating, as a compound that expresses the effect of preventing deterioration of the photochromic dye, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Asahi Denka Kogyo Co., Ltd. Examples include ADK STAB LA-52, LA-62, LA-77, and LA-82. The addition amount is, for example, in the range of 0.001 to 20 parts by mass, preferably in the range of 0.1 to 10 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable component. Range.

  Further, in the photochromic liquid, it is preferable to contain a surfactant, a leveling agent, etc. in order to improve uniformity during film formation, and it is particularly preferable to add a silicone-based / fluorine-based leveling agent having leveling properties. preferable. Although it does not specifically limit as the addition amount, It is 0.01-1.0 mass% normally with respect to the photochromic liquid whole quantity, and the range of 0.05-0.5 mass% is preferable.

  In the present invention, it is preferable not to add various components (adhesive agents such as coupling agents or polymerization catalysts for coupling agents) that are usually added to improve the adhesion to the photochromic liquid. Thereby, it becomes easy to take out the molded body with the photochromic film from the lens mold after the casting polymerization (fourth step). Moreover, since the liquid life (pot life) of the coating liquid containing a silane coupling agent or the like decreases due to self-polymerization during liquid storage, it is preferable from the viewpoint of workability that such a component is not included.

In the present invention, the method for preparing the photochromic liquid is not particularly limited, and can be performed by weighing and mixing a predetermined amount of each component. The order of addition of each component is not particularly limited, and all the components may be added simultaneously, or only the monomer component is mixed in advance, and a photochromic dye or other additive may be added and mixed immediately before polymerization. Good.
The photochromic liquid preferably has a viscosity at 25 ° C. of 20 to 500 cp, more preferably 50 to 300 cp, and particularly preferably 60 to 200 cp. By setting it as this viscosity range, application | coating of a photochromic liquid becomes easy and the photochromic film | membrane of desired thickness can be obtained easily.

(2) Curing conditions The photochromic film may be cured by either photopolymerization or thermal polymerization. However, in order to obtain photochromic films having different hardnesses on both sides, light whose partial control of the cured state is easy. It is preferred to use polymerization. When using photopolymerization, by performing light irradiation on the photochromic liquid application surface of the first mold, the vicinity of the light irradiation side surface (photochromic film outermost surface) is cured, and the inside is in an uncured state, A photochromic film having an appropriate flexibility on one surface can be obtained. The cured state can be controlled by adjusting the distance between the light source and the mold surface (photochromic liquid application surface), illuminance, irradiation amount, and irradiation time. In order to increase the curing efficiency, it is preferable to perform light irradiation in an inert atmosphere.

  The light to be irradiated may be selected according to the polymerization initiator contained in the photochromic liquid, but as described above, in order to control the curing reaction by the color development of the photochromic dye, light having a wavelength to which the photochromic dye responds, For example, light having a wavelength of 150 to 380 nm, preferably ultraviolet light (having a wavelength of about 200 to 380 nm) can be used.

As the ultraviolet light source, known light sources such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a carbon arc, a germicidal lamp, and an electrodeless lamp can be used. The distance between the light source and the mold surface, the irradiation amount, and the irradiation time are preferably adjusted in consideration of the composition of the photochromic liquid and the coating amount. Specifically, the irradiation amount can be 1 to 100 J / cm ^2, and preferably ¹ to 75 J / cm ² . For example, the distance between the light source and the mold surface can be 100 to 300 mm, the illuminance can be 100 to 250 mW / cm ² , and the irradiation time can be 10 to 400 seconds. The irradiation time is more preferably 10 to 300 seconds.

As described above, by irradiating the photochromic liquid application surface of the first mold with light, the outermost surface can be cured and a photochromic film containing an uncured curable component inside can be formed. In addition, using a mold made of a light-transmitting material (for example, glass) as the first mold, and adjusting the hardness in the vicinity of the surface facing the mold surface by performing light irradiation through the first mold. You can also. Thereby, the durability of the photochromic film can be ensured. Moreover, the bleeding of an additive can be reduced by performing light irradiation through the first mold. However, since the surface facing the mold surface is normally located on the incident surface side during use, the ease of movement of the photochromic dye on the incident surface side can be ensured when light irradiation is performed through the mold. The degree of light irradiation should be. The light irradiation through the mold is preferably performed at a lower irradiation amount than the light irradiation on the photochromic liquid application surface, for example, an irradiation amount of 0.1 to 30 J / cm ² . In addition, when a hard coat or an antireflection film is provided on the photochromic film as will be described later, the surface of the photochromic film is protected by them, so that durability can be ensured without performing light irradiation through a mold. it can.

(3) Thickness of photochromic film The cured state of the photochromic film can also be adjusted by the thickness of the photochromic film. If the photochromic film is excessively thin, most of the irradiated light passes through the film and polymerization of the entire film proceeds, making it difficult to impart appropriate flexibility to the surface facing the first mold. In addition, since the portion where the dye easily moves in the photochromic film is reduced, it is difficult to improve the reaction speed and color density of the color fading. From the above points, the thickness of the photochromic film is preferably 10 μm or more, and more preferably 20 to 60 μm.

  By controlling the cured state in the photochromic film as described above, a photochromic film containing a cured resin formed by curing the curable component and an uncured curable component can be obtained. It is preferable that the outermost surface of the photochromic film (the surface in contact with the lens raw material liquid at the time of casting polymerization) and the vicinity thereof contain a cured resin as a main component, while the cured resin content in the surface in contact with the mold surface and the vicinity thereof. Is preferably lower than the cured resin content on the outermost surface and in the vicinity thereof. Thus, it is possible to obtain a photochromic lens with appropriate flexibility on the incident surface side. In addition, said "near" is an area | region where hardness falls gradually in the surface layer part from the surface to the inside of a photochromic layer, for example.

  In order to obtain the above effect satisfactorily, the photochromic film and the lens substrate should be cured by different polymerization reactions. When the photochromic film and the lens substrate are cured by the same kind of polymerization reaction, the polymerization reaction of the photochromic film also progresses during the polymerization reaction of the lens substrate. The surface facing the mold) is cured, and the ease of movement of the photochromic dye may be impaired. Specifically, in the present invention, the photochromic film is preferably cured by light irradiation, and the lens substrate is preferably cured by thermal polymerization.

(Lens mold forming process)
In the lens mold forming step, the first mold having the photochromic film formed on the molding surface in the photochromic liquid curing treatment step is disposed so as to face the other surface of the second mold, and an annular shape is formed around the two molds. By placing the gasket, a cavity is formed by the two molds and the gasket. Here, the first mold is arranged so that the outermost surface of the photochromic film faces the second mold surface. As a result, the photochromic film is positioned inside the cavity.

  As the mold and gasket, those usually used for casting polymerization can be used as they are, but as the mold, a glass mold subjected to chemical strengthening treatment is used in order to prevent damage and scratches. It is preferable.

  FIG. 5 shows a schematic diagram of a lens mold configured by arranging the first mold, the second mold, and the gasket as described above. Hereinafter, a 3rd process is demonstrated based on FIG. However, the present invention is not limited to the embodiment shown in FIG.

  In FIG. 5, a lens mold 1 includes a first mold 10 which is a concave mold having a molding surface on the concave surface side to form the front surface (convex surface) of the lens, and a molding surface on the convex surface side to form the rear surface (concave surface) of the lens. The cavity 13 is formed in the inside by the 2nd mold 11 which has a shaping | molding surface in the convex surface side which has these, and the gasket 12. FIG. The gasket 12 functions as an outer peripheral holder of the gasket and plays a role of determining the thickness of the lens.

  The first mold and the second mold have non-transfer surfaces (non-use surfaces 101 and 111) that can be handled by a manufacturing jig and transfer surfaces (use surfaces 102 and 112) for transferring the optical surface of the lens. The use surfaces 102 and 112 are surfaces that transfer the optical surface shape and surface state of the lens. On the use surface 102, a photochromic film is formed in the second step.

  When the photochromic film contains an antioxidant, it is preferable to anneal the first mold on which the photochromic film is formed before forming the cavity. Thereby, it is possible to prevent the antioxidant contained in the photochromic film from eluting into the lens raw material liquid in the cavity. The annealing conditions can be set as appropriate.

  In the present invention, it is preferable to perform a dry etching process using UV ozone or plasma on the outermost surface of the photochromic film formed on the surface of the first mold prior to the cavity formation. By performing the said process, the adhesiveness of a lens base material and a photochromic film | membrane can be improved, without using an adhesive agent. Note that the effect obtained by the photochromic film not containing the adhesive is as described above.

  By applying the UV ozone treatment, on the photochromic film surface, bonds are broken at the molecular level, and highly hydrophilic functional groups (for example, —OH, —CHO, —COOH) are expressed, and substances contained in the lens substrate It is considered that the adhesion between the lens substrate and the photochromic film is improved by binding to the photochromic film component. Further, since impurities contained in the photochromic film are washed by the UV ozone treatment, it is considered that the adhesion with the lens substrate is not inhibited by these impurities, which contributes to the improvement of the adhesion.

FIG. 6 shows an example of UV ozone treatment. The UV ozone treatment can be performed by arranging a mold in which a photochromic film is formed under a UV lamp as shown in FIG. 6 so that the photochromic film is located on the surface. Here, the distance between the UV lamp and the photochromic film surface is preferably 10 to 20 cm when the irradiation energy is about 1 to 10 mW / cm ² . The processing time can be set to, for example, 5 to 600 seconds.

  In the case of plasma processing, the processing conditions are preferably an output of 100 to 300 W and a processing time of 10 to 300 seconds. The introduced gas is not particularly limited, but air, oxygen, nitrogen and the like can be used.

(Cast polymerization process)
The casting polymerization step is a step of injecting a lens raw material solution into the cavity formed in the lens mold forming step to perform polymerization of the lens base material and formation of a photochromic film on the lens base material.
The lens raw material liquid injected into the cavity may contain raw material monomers, oligomers and / or prepolymers of various polymers constituting the lens base material, and a mixture of two or more monomers to form a copolymer. Can also be included. If necessary, a catalyst selected according to the kind of monomer can be added to the lens raw material liquid. The lens raw material liquid may also contain various commonly used additives.

  As the lens substrate, various substrates usually used as a plastic lens can be used. Examples of the lens substrate include a copolymer of methyl methacrylate and one or more other monomers, a copolymer of diethylene glycol bisallyl carbonate and one or more other monomers, a copolymer of polyurethane and polyurea, and polycarbonate. , Polystyrene, polyvinyl chloride, unsaturated polyester, polyethylene terephthalate, polyurethane, polythiourethane, sulfide resin utilizing ene-thiol reaction, vinyl polymer containing sulfur, and the like. Of these, urethane systems are preferred, but not limited thereto. The lens base material is preferably a plastic lens base material, more preferably a plastic lens base material for spectacles.

  In the method of obtaining a lens with a photochromic film by applying a coating solution containing a photochromic dye on a plastic lens and curing the coating solution, when the photochromic film is formed by ultraviolet irradiation, the lens substrate is coated with ultraviolet rays. When the absorbent is included, even if the ultraviolet ray is irradiated from the lens substrate side, most of the irradiated ultraviolet ray is absorbed by the lens substrate. Therefore, in this case, ultraviolet irradiation is performed from the photochromic film side. However, with this method, it is difficult to increase the hardness of the surface of the photochromic film that faces the lens substrate as compared with the other surface. On the other hand, according to the casting polymerization method, the photochromic film can be preliminarily subjected to a desired curing treatment, and therefore has a desired hardness on the base material even if the lens base material contains an ultraviolet absorber. A photochromic film can be formed. Therefore, the cast polymerization method is particularly suitable as a method for obtaining a photochromic lens including an ultraviolet absorber in a lens substrate.

  The injection of the lens raw material liquid into the cavity and the subsequent polymerization reaction can be performed in the same manner as in the usual casting polymerization. In the present invention, the photochromic film is preferably cured by photopolymerization, while the lens substrate is preferably cured by thermal polymerization. As described above, when the curing treatment of the photochromic film and the lens base material is performed by the same kind of polymerization reaction, the polymerization state of the photochromic film and the lens base material is affected because one of the polymerization reactions affects the other. It becomes difficult to control separately. On the other hand, when the photochromic film formed by photopolymerization is formed on the lens substrate in the cavity, if the lens substrate is cured by heating, polymerization of the photochromic film will not proceed by this heating. A photochromic film in a state where a predetermined cured state is maintained can be formed on the lens substrate.

  The heating conditions for curing the lens substrate can be appropriately adjusted according to the type and composition of the curable component in the lens raw material liquid (in the case of a mixture), the type of catalyst, and the like.

(Release process)
After the polymerization is completed, the gasket, the first mold, and the second mold are removed to obtain a photochromic lens in which a photochromic film is formed on the lens substrate. The mold release step can be performed in the same manner as the mold release step in ordinary casting polymerization.

  The photochromic lens obtained by the mold release process is stored by the storage method described above. The storage period can be appropriately set in consideration of productivity and the like, and can be, for example, about 0.5 hours to 6 months. Further, after storage, a coating film such as a hard coat can be formed on the outermost surface of the photochromic film. Details of the film forming process will be described later.

[Method of manufacturing photochromic lens]
Furthermore, the present invention is a photochromic lens including a photochromic film having an ultra-fine indentation hardness of 800 nm or more on the outermost surface and a lens substrate, wherein the outermost surface of the photochromic film is located on the outermost surface of the photochromic lens The present invention relates to a photochromic lens manufacturing method including a film forming step of forming a coating layer on the outermost surface. In the photochromic lens manufacturing method of the present invention, the photochromic lens before the film forming step is stored by the storage method of the present invention described above. This makes it possible to form a coating on the outermost surface of the photochromic film that has been prevented or prevented from exuding after long-term storage, and the optical properties deteriorate due to the reaction of the exuding component with the coating component resulting in fogging or coloring. Can be prevented. Further, the photochromic film can exhibit excellent photoresponsiveness because the outermost surface has appropriate flexibility. Therefore, according to the method for producing a photochromic lens of the present invention, a photochromic lens having both excellent photoresponsiveness and optical characteristics can be obtained.

The details of each process up to the formation of the photochromic film and the storage process in the method for producing a photochromic lens of the present invention are as described above.
Hereinafter, the film forming process will be described.

(Film formation process)
In the film forming step, a coating is formed on the outermost surface of the photochromic film of the photochromic lens that has been stored in the atmosphere in which the oxygen concentration and / or humidity has decreased in the storage step. Examples of the coating include a hard coat layer and an antireflection film. Moreover, after forming a hard-coat layer, it is also possible to provide various coatings, such as an antireflection film, on it.

The material for the hard coat layer is not particularly limited, and a coating composition comprising a known organosilicon compound and metal oxide colloidal particles can be used.
Examples of the organosilicon compound include an organosilicon compound represented by the following general formula (III) or a hydrolyzate thereof.
(R ⁹¹ ) _{a ′} (R ⁹³ ) _{b ′} Si (OR ⁹² ) _{4- (a ′ + b ′)} (III)
(In the formula, R ⁹¹ is an organic group having a glycidoxy group, an epoxy group, a vinyl group, a methacryloxy group, an acryloxy group, a mercapto group, an amino group, a phenyl group, etc., and R ⁹² is an alkyl having 1 to 4 carbon atoms. Group, an acyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ⁹³ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms, and a ′ and b ′ are each 0 or 1 is shown.)

Examples of the alkyl group having 1 to 4 carbon atoms of R ⁹² include a linear or branched methyl group, ethyl group, propyl group, and butyl group.
Examples of the acyl group having 1 to 4 carbon atoms of R ⁹² include an acetyl group, a propionyl group, an oleyl group, and a benzoyl group.
Examples of the aryl group having 6 to 10 carbon atoms of R ⁹² include a phenyl group, a xylyl group, and a tolyl group.
Examples of the alkyl group having 1 to 4 carbon atoms of R ⁹³ include a linear or branched methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group.
Examples of the aryl group having 6 to 10 carbon atoms of R ⁹³ include a phenyl group, a xylyl group, and a tolyl group.

  Specific examples of the compound represented by the general formula (III) include methyl silicate, ethyl silicate, n-propyl silicate, i-propyl silicate, n-butyl silicate, sec-butyl silicate, t-butyl silicate tetraacetoxy. Silane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyl Triphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane , Β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxy Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxy Silane, α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxy Silane, γ-glycidoxybuty Triethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3, 4-epoxycyclohexyl) ethyltributoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) Propyltriethoxy Silane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltriethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α -Glycidoxyethylmethyldimethoxysilane, α-glycidoxyethylmethyldiethoxysilane, β-glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane , Α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyl Ethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycid Xylpropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, ethyl Trimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetate Sisilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltriacetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, β-cyanoethyltriethoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, N- (β-aminoethyl) γ-aminopropyltrimethoxysilane, N -(Β-aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) γ-aminopropyltriethoxysilane, N- (β-aminoethyl) γ-amino Propylmethyldiethoxysilane, dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, dimethyldiacetoxysilane, γ -Methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane and the like.

Examples of the metal oxide colloidal particles include tungsten oxide (WO ₃ ), zinc oxide (ZnO), silicon oxide (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), zirconium oxide ( ZrO ₂ ), tin oxide (SnO ₂ ), beryllium oxide (BeO), antimony oxide (Sb ₂ O ₅ ) and the like can be mentioned, and these can be used alone or in combination of two or more.

The material and formation method of the antireflection film are not particularly limited, and a single layer or a multilayer film made of a known inorganic oxide can be used.
Examples of the inorganic oxide include silicon dioxide (SiO ₂ ), zirconium oxide (ZrO ₂ ), aluminum oxide (Al ₂ O ₃ ), niobium oxide (Nb ₂ O ₅ ), yttrium oxide (Y ₂ O ₃ ), and the like. Be mentioned

  In the photochromic lens obtained by the production method of the present invention, the thickness of the lens substrate, and the hard coat and antireflection film provided as necessary is not particularly limited, but the thickness of the lens substrate is, for example, 1 to 30 mm. The thickness of the hard coat can be, for example, 0.5 to 10 μm, and the thickness of the antireflection film can be, for example, 0.1 to 5 μm. The thickness of the photochromic film is as described above.

  In the following, the present invention will be further explained by examples. However, this invention is not limited to the aspect shown in the Example.

[Example 1] (UV single-sided irradiation, oxygen scavenger + desiccant enclosed)
1. Preparation of photochromic liquid 20 parts by mass of trimethylolpropane trimethacrylate, 35 parts by mass of BPE oligomer (2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane), 10 parts by mass of EB6A (polyester oligomer hexaacrylate) in a plastic container , 100 parts by mass of a radical polymerizable monomer consisting of 10 parts by mass of polyethylene glycol diacrylate having an average molecular weight of 532 and 10 parts by mass of glycidyl methacrylate, 3 parts by mass of chromene 1 as a photochromic dye, and hindered amine light as an antioxidant Sanol LS765 (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate), methyl (1,2,2,6,6-pentamethyl-4-piperi) manufactured by Sankyo Lifetech Co., Ltd. (Silyl) sebacate) 5 parts by mass, CGI-184 (1-hydroxycyclohexyl phenyl ketone) as an ultraviolet polymerization initiator 0.4 parts by mass, CGI 403 (bis (2,6-dimethoxybenzoyl-2,4,4-trimethyl) (Pentylphosphine oxide) was added in an amount of 0.1 part by mass, and the solution was degassed for 2 minutes with a rotation and revolution type stirring and deaerator (AR-250, manufactured by Sinky Corporation) to obtain a photochromic liquid. The viscosity of the obtained liquid was 200 mpa / s.

2. Formation of photochromic film A photochromic film was formed on the mold by the following process using the photochromic solution obtained in the above.
(1) About 2 g of photochromic liquid was dropped on the concave surface side of a cleanly cleaned glass mold, and coating was performed at 600 rpm for 20 seconds by a spin coating method.
(2) Thereafter, the photochromic liquid was cured by irradiating ultraviolet rays from the concave side of the mold with a UV lamp manufactured by Toshiba Lilac in a nitrogen atmosphere. The ultraviolet irradiation was performed at an irradiation distance of 330 mm and an irradiation time of 165 seconds.
(3) The film thickness of the photochromic film formed on the mold was 30 microns.
(4) Next, the glass mold with the photochromic film was subjected to heat treatment (annealing) at 110 ° C. for 100 minutes, and then subjected to 180 seconds of UV ozone treatment (manufactured by Eyegraphic).

3. Casting Polymerization A photochromic lens was formed by the following process using a mold in which the formation of the photochromic film was completed.
(1) The mold on which the photochromic film was formed was pressed into a cylindrical gasket so as to be a lens convex surface, and a mold without a photochromic film was pressed into a predetermined amount on the surface to be a lens concave surface and assembled to form a cavity.
(2) Next, a lens raw material containing a thermosetting urethane monomer was injected into the cavity formed in (1), and the monomer was cured by heat polymerization using a predetermined polymerization program.
(3) The mold was released from the cured lens after polymerization. At this time, the photochromic film formed on the mold was transferred to the lens.
(4) The lens to which the photochromic film was transferred was washed after cutting the outer periphery, and annealed with a predetermined program.
Through the above steps, a meniscus photochromic lens having a photochromic film on the convex surface was obtained.

4). Preservation process in oxygen / moisture-reduced atmosphere The obtained photochromic lens is sandwiched so as to cover both optical surfaces of the lens with a lens protective sheet, and an oxygen scavenger and desiccant are placed outside the lens protective sheet on the concave side of the lens In this state, it was inserted from the opening into a lens packaging bag in which permeation of oxygen and moisture was suppressed. And the opening part of the lens packaging bag was adhere | attached by thermocompression bonding in air | atmosphere, and the packaging bag was sealed.
A Japanese paper sheet was used as the lens protection sheet.
The lens packaging bag was formed into a bag shape using a gas barrier film having an oxygen permeability of approximately 0 ml / m ² · atm · 24 h and a water vapor permeability of approximately 0 g / m ² · 24 h. As the gas barrier film, when formed as a lens packaging bag, the first layer located on the innermost side is low density polyethylene (30 μm), the second layer is polyethylene (20 μm), the third layer is aluminum foil (7 μm), A composite film composed of polyethylene (13 μm) for the fourth layer and polyethylene terephthalate (12 μm) for the fifth layer was used. The volume excluding the lens in the sealed packaging bag was about 30 to 40 ml.
As the oxygen scavenger, an oxygen scavenger having an oxygen absorption amount of about 20 ml (manufacturer: Mitsubishi Gas Chemical Co., Ltd., trade name: Ageless, model number: Z-20PK) was used.
Moreover, as a desiccant, a product in which silica gel (manufacturer: manufactured by Asahi Glass S-Tech Co., Ltd., components: silicon dioxide 98% or more, cobalt chloride 0.09%) was packaged in a Japanese paper bag was used. Since the oxygen scavenger is a self-reactive type, water vapor evaporates from the moisture donor in the oxygen scavenger into the packaging bag, but the silica gel is in excess of the required amount calculated from the amount of water evaporated and the volume in the packaging bag. Was enclosed in a packaging bag.

[Example 2] (UV single-sided irradiation, vacuum)
1. Preparation of photochromic solution Same as Example 1.
2. Formation of Photochromic Film Same as Example 1.
3. Cast polymerization The same as in Example 1.
4). Storage Step in Oxygen / Moisture Reduced Atmosphere The obtained photochromic lens was stored in a vacuum desiccator at a pressure of 10 ⁻¹ Pa with a rotary pump.

[Example 3] (UV single-sided irradiation, nitrogen substitution)
1. Preparation of photochromic liquid As in Example 1.
2. Formation of Photochromic Film Same as Example 1.
3. Cast polymerization The same as in Example 1.
4). Storage Step in Oxygen / Moisture-Reduced Atmosphere The obtained photochromic lens was placed in a gas replacement desiccator that was replaced with nitrogen gas, and stored while flowing nitrogen gas. Nitrogen gas having a purity of 99.999 vol% or more, oxygen of 1 vol ppm or less, and moisture (dew point of −70 ° C. or less) was used. Further, the oxygen concentration in the desiccator was 0.06% or less.

[Example 4] (UV single-sided irradiation, encapsulating desiccant)
1. Preparation of photochromic solution Same as Example 1.
2. Formation of Photochromic Film Same as Example 1.
3. Cast polymerization The same as in Example 1.
4). Storage step in an oxygen / moisture-reduced atmosphere Same as Example 1 except that only the desiccant was enclosed in the lens packaging bag without adding the oxygen scavenger.

[Example 5] (UV single-sided irradiation, deoxidation material enclosed)
1. Preparation of photochromic solution Same as Example 1.
2. Formation of Photochromic Film Same as Example 1.
3. Cast polymerization The same as in Example 1.
4). Storage step in oxygen / moisture-reduced atmosphere Same as Example 1 except that only the oxygen scavenger was enclosed in the lens packaging bag without the desiccant.

[Example 6] (Double-sided UV irradiation, deoxidized material + desiccant)
1. Preparation of photochromic solution Same as Example 1.
2. Formation of Photochromic Film Example 1-2. (1) to (2) were the same. Thereafter, the photochromic liquid was cured by irradiating ultraviolet rays from the convex side of the mold with a UV lamp manufactured by Toshiba Lilac in a nitrogen atmosphere. The ultraviolet irradiation was performed at an irradiation distance of 330 mm and an irradiation time of 40 seconds. The thickness of the photochromic film formed on the mold was measured and found to be 30 microns.
Next, the glass mold with the photochromic film was subjected to heat treatment (annealing) at 110 ° C. for 100 minutes, followed by 180 seconds of UV ozone treatment (manufactured by Eyegraphic).
3. Cast polymerization The same as in Example 1.
4). Storage step in oxygen / moisture-reduced atmosphere Same as Example 1.

[Example 7] (Double-sided UV irradiation, vacuum)
The formation of the photochromic film was performed in the same manner as in Example 6.2. As in Example 2, except that UV irradiation was performed from both sides.

[Example 8] (Double-sided UV irradiation, nitrogen substitution)
The formation of the photochromic film was performed in the same manner as in Example 6.2. As in Example 3, except that UV irradiation was performed from both sides.

[Example 9] (Double-sided UV irradiation, encapsulating desiccant)
The formation of the photochromic film was performed in the same manner as in Example 6.2. As in Example 4, except that UV irradiation was performed from both sides.

[Example 10] (Double-sided UV irradiation, oxygen scavenger enclosed)
The formation of the photochromic film was performed in the same manner as in Example 6.2. As in Example 5, except that UV irradiation was performed from both sides.

[Comparative Example 1] (single-sided UV irradiation, storage in air)
Example 1 ~ 3. The photochromic lens formed by the above process was stored in a dark place in the air. The temperature during storage was in the range of 20 ° C to 25 ° C, and the relative humidity was in the range of 30 to 50%.

[Comparative Example 2] (Double-sided UV irradiation, storage in air)
Example 6-1. ~ 3. The photochromic lens formed by the above process was stored in a dark place in the air. The temperature during storage was in the range of 20 ° C to 25 ° C, and the relative humidity was in the range of 30 to 50%.

[Example 11] (Hardcoat layer and antireflection layer formation)
The lenses 4 to 6 after the start of storage in Examples 1 to 10 were subjected to the following treatments 4 to 6 to form a hard coat layer and an antireflection film.

4). Preparation of Hard Coating Solution Under a 5 ° C. atmosphere, 45 parts by mass of modified stannic oxide-zirconium oxide-tungsten oxide-silicon oxide complex methanol sol, 15 parts by mass of γ-glycidoxypropyltrimethoxysilane and 3 parts by mass of tetraethoxysilane And the mixture was stirred for 1 hour. Thereafter, 4.5 parts by mass of 0.001 mol / L hydrochloric acid was added and stirred for 50 hours. Thereafter, 25 parts by mass of propylene glycol monomethyl ether (PGM), 9 parts by mass of diacetone alcohol (DAA) and 1.8 parts by mass of aluminum trisacetylacetonate (AL-AA) as component (C), perchloric acid 0.05 parts by mass of aluminum was sequentially added and stirred for 150 hours. A solution obtained by filtering the obtained solution through a 0.5 μm filter was used as a coating composition.

5. Formation of Hard Coat Layer UV ozone treatment for 30 seconds was performed on the photochromic film surface of the photochromic lens formed in Example 1. Then, after immersing for 5 minutes in an aqueous solution of sodium hydroxide at 10 ° C. at 60 ° C., sufficiently washing / drying with pure water, Using the hard coating composition prepared in (1), coating was carried out by a dipping method (pickup speed 20 cm / min), and a hard coat layer was formed by heating and curing at 110 ° C. for 60 minutes.

6). 4. Formation of antireflection film The plastic lens on which the hard coat layer was formed was put into a vapor deposition apparatus, heated to 85 ° C. while being evacuated, evacuated to 2.7 mPa (2 × 10 ⁻⁵ torr), and then the evaporation raw material was formed by an electron beam heating method. An underlayer having a thickness of 0.6λ made of SiO _{2 is} deposited, and a mixed layer made of Ta ₂ O ₅ , ZrO ₂ , Y ₂ O ₃ (nd = 2.05, nλ = 0. 075λ) and a SiO ₂ layer (nd = 1.46, nλ = 0.56λ), a first refractive layer, a mixed layer made of Ta ₂ O ₅ , ZrO ₂ , Y ₂ O ₃ (nd = 2.05, A second low-refractive index layer (nd = 1.46, nλ = 0.25λ) composed of nλ = 0.075λ) and a SiO ₂ layer was formed, and an antireflection film was applied.

[Evaluation of photochromic lens]
(1) Appearance inspection In Examples 1 to 10 and Comparative Examples 1 and 2, after 2 days, 5 days, 10 days, 20 days, and 30 days after the start of storage, the lens surface was subjected to an optical microscope (OPTIPHOT2 manufactured by Nikon Corporation). Used for visual inspection. In the appearance inspection, the number of spots where bleeding occurred in the differential interference mode 200 times and the observation area 425 μm × 325 μm was visually counted. The results of Examples 1 to 5 and Comparative Example 1 are shown in Table 1, and the results of Examples 6 to 10 and Comparative Example 2 are shown in Table 2. In these tables, the case where the number of exudation locations is 0 to 50 is indicated by the symbol ◯, the case where the number is 51 to 100 is indicated by the symbol Δ, and the case where it is 101 or more is indicated by the symbol ×. FIG. 7 shows a photograph of the differential interference mode 200 times of the optical microscope.

As a result of the above-described appearance evaluation, in Examples 1 to 10, the additive oozes out less even when stored for a longer time than in the comparative example. In particular, when stored in an atmosphere in which both oxygen and moisture in the air are reduced using an oxygen scavenger and a desiccant (Examples 1 and 6), and when stored in a vacuum atmosphere (Example 2, 7) No oozing was observed even after 30 days. In addition, when stored in a nitrogen-substituted atmosphere (Examples 3 and 8), exudation occurred when the storage period was long. This was because oxygen contained in nitrogen gas was present in the desiccator. Is considered to be the cause. Moreover, when it preserve | saved in the atmosphere which reduced oxygen in the air using an oxygen absorber (Examples 5 and 10), the time until oozing out was quicker than other examples. This is presumably because the oxygen scavenger used was self-reactive and the water released from the scavenger was affected. In the case of double-sided UV irradiation (Examples 6 to 10), it was difficult for the same oxygen / moisture reducing means to ooze out compared to the case of single-sided UV irradiation (Examples 1 to 5).
In Example 11, optical defects such as fogging and coloring were not observed after coating in any lens, and the optical characteristics were good.

In Example 11, the lens obtained by forming the hard coat layer and the antireflection layer in this order on the lens of Example 1 was evaluated for photochromic properties by the following method according to JIS T7333.
For the photochromic film on the obtained photochromic lens, for 15 minutes (900 seconds) through an aeromass filter using a xenon lamp, against the photochromic film surface (the surface opposite to the surface facing the lens substrate) The photochromic film was colored by light irradiation. At this time, the transmittance at 550 nm was measured with a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. The light irradiation was performed so that the irradiance and the tolerance of the irradiance had values shown in Table 3 below as defined in JIS T7333. It shows that photochromic property is excellent, so that this figure is small. Similarly, the light fading speed was irradiated with light for 15 minutes (900 seconds), and the transmittance (550 nm) from the time when the irradiation was stopped was measured. The faster the rate at which the transmittance returns with time, the better the photochromic properties. FIG. 8 shows the light transmittance (550 nm) of the photochromic lens after irradiation (0 to 900 seconds), irradiation end (900 seconds), and irradiation end (900 seconds). As can be seen from FIG. 8, the lens obtained by forming the coating on the lens of Example 1 had a high reaction speed and color density for color development and excellent photoresponsiveness.

[Analysis of exuded components]
For the lenses 10 days after the start of storage in Comparative Examples 1 and 2 and the lenses 30 days after the start of storage in Examples 3, 4 and 5, the substances that ooze out on the photochromic film surface were collected using a microneedle. Then, the collected substance was placed on a diamond cell, and the spectrum was measured by a transmission method using a Fourier transform type micro-infrared spectrophotometer (μ-IR8000 manufactured by Shimadzu Corporation). As a result, it agreed with the spectrum of LS765, which is a hindered amine light stabilizer. From this result, it is considered that LS765 is contained in the exuding substances in the comparative examples and examples.

  According to the present invention, a photochromic lens having excellent photoresponsiveness and optical characteristics can be obtained. In particular, the photochromic lens obtained by the present invention is suitable as a spectacle lens.

It is explanatory drawing which shows the outline of a photochromic lens. It is the schematic of the measuring method of super micro indentation hardness. It is the schematic of a chamber type vacuum and gas replacement packaging machine. An example of a lens storage method will be described. It is the schematic of a lens casting_mold | template. An example of UV ozone treatment is shown. It is an optical microscope photograph which shows the result of the external appearance inspection of the photochromic lens in storage. The light transmittance (550 nm) of the photochromic lens after completion | finish of irradiation of the photochromic lens of Example 11 which formed the hard-coat layer on the lens of Example 1 at the time of light irradiation end is shown.

Claims (8)

A photochromic lens including a photochromic film having an ultra-fine indentation hardness of 800 nm or more on the outermost surface and a lens base material, wherein the outermost surface of the photochromic film is positioned on the outermost surface of the photochromic lens, oxygen concentration and A method for storing a photochromic lens that is stored in an atmosphere with reduced humidity. The method for storing a photochromic lens according to claim 1, wherein the atmosphere is a vacuum atmosphere. The method for storing a photochromic lens according to claim 1, wherein the atmosphere is an inert gas atmosphere. The method for preserving a photochromic lens according to claim 1, wherein the atmosphere is a sealed atmosphere containing an oxygen scavenger. The method for preserving a photochromic lens according to claim 4, wherein the sealed atmosphere further contains a desiccant. The method for storing a photochromic lens according to claim 1, wherein the atmosphere is a sealed atmosphere containing a desiccant. The outermost surface of a photochromic lens including a photochromic film having an ultra-fine indentation hardness of 800 nm or more and a lens base material, wherein the outermost surface of the photochromic film is located on the outermost surface of the photochromic lens A method for producing a photochromic lens including a film forming step of forming a coating film thereon,
The said manufacturing method which preserve | saves the photochromic lens before the said film-forming process by the method of any one of Claims 1-6. The method for producing a photochromic lens according to claim 7, wherein the photochromic film includes a hindered amine light stabilizer.