JP4921998B2 - Manufacturing method of photochromic lens - Google Patents

Description

  The present invention relates to a method for producing a photochromic lens having a photochromic film excellent in photoresponsiveness and optical characteristics.

  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.

As a photochromic lens, a lens provided with a coating (photochromic film) containing a photochromic dye on a lens substrate is widely used. In general, as a method for producing a photochromic lens having the above-described configuration, after applying a photochromic liquid on a lens base material, the curable component contained in the photochromic liquid is irradiated by irradiating the application surface with light such as ultraviolet rays. A curing method is used (for example, see Patent Document 1).
JP 2005-246268 A

  The photochromic film is required to respond quickly when predetermined light is incident and develop a color with a high concentration, and to discolor quickly when placed in an environment without the light. Conventionally, it has been considered that the reaction rate and color density of the photochromic film depend on the characteristics unique to the photochromic dye resulting from the molecular structure. Therefore, it has been studied to improve the responsiveness (reaction rate and color density) of the photochromic film by using a photochromic dye having a specific molecular structure.

  However, the responsiveness (reaction speed and color density) of the conventional photochromic film is not always satisfactory, and further improvement of the photoresponsiveness has been demanded.

  Under such circumstances, the present invention has been made for the purpose of providing a photochromic lens having a photochromic film having excellent photoresponsiveness.

The inventors of the present invention have made extensive studies in order to achieve the above object.
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, the present inventors have obtained the following new knowledge regarding the photoresponsiveness of the photochromic film.
(1) If flexibility (fluidity) is provided without completely curing the photochromic film, the dye can move easily in the film, and the reaction speed and color density of color development are greatly improved.
(2) Since the photoresponsiveness in the photochromic lens is manifested mainly in the object-side (incident surface side) surface layer portion on which light is incident, at least the dye existing in the object-side surface layer portion of the photochromic film should be in a state where it can move easily. High photoresponsiveness can be obtained.
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 method for producing a photochromic lens having a photochromic film on a lens substrate,
Apply a photochromic liquid containing a photochromic dye and a photocurable component on one side of the lens substrate,
By curing at least a part of the previous SL-curable component irradiated with light with respect to the photochromic liquid, to form a photochromic film outermost surface has a hardness indentation ultrafine above 800 nm,
Irradiation of light to the photochromic liquid is performed through the lens base material without performing the photochromic liquid application surface of the lens base material, or light irradiation to the photochromic liquid is performed on the photochromic liquid application surface of the lens base material. The method for producing a photochromic lens according to claim 1, wherein the photochromic lens is formed through a lens base material, wherein the light irradiation through the lens base material is performed at a higher dose than the light irradiation on the photochromic liquid application surface.
[2 ] The method for producing a photochromic lens according to [1 ], wherein the wavelength of the irradiated light is in a range of 150 to 380 nm.
[ 3 ] The method for producing a photochromic lens according to [1 ] or [2], wherein the lens substrate does not contain an ultraviolet absorber.

  According to the present invention, a photochromic lens having excellent photoresponsiveness and optical characteristics can be provided.

The manufacturing method of the photochromic lens of this invention obtains the photochromic lens which has a photochromic film | membrane on a lens base material by performing the following processes.
(Step I) A photochromic liquid containing a photochromic dye and a photocurable component is applied on one surface of the lens substrate.
(Step II) The photochromic liquid is irradiated with light through at least a lens substrate, and at least a part of the curable component is cured, so that the outermost surface has an indentation hardness of 800 nm or more. A photochromic film is formed.

In the present invention, the photochromic film coated on the lens base material is irradiated with light through at least the lens base material to form a photochromic film having an ultra-fine indentation hardness having an outermost surface of 800 nm or more. .
In a conventional photochromic lens manufacturing method, a coating liquid is applied onto a lens substrate, and then light such as ultraviolet rays is applied to the application surface to cure a curable component contained in the coating liquid. As described above, light irradiation was performed from the coated surface side. In the conventional method, it is necessary to irradiate high energy light to cure the photochromic liquid, and light irradiation is performed from the lens substrate side. This is because the lens substrate is damaged and the optical characteristics are lowered.
On the other hand, as described above, as a result of the study by the present inventors, if the photochromic film has an appropriate flexibility (fluidity), the dye can move easily in the film, and the reaction speed and color development of the color change. It was found that the concentration was greatly improved. Furthermore, since the photoresponsiveness in the photochromic film is manifested mainly in the object-side surface layer portion where light enters, at least if the dye existing in the object-side surface layer portion of the photochromic film is in a state where it can move easily, high photoresponsiveness is achieved. It was also found that it can be obtained.
A photochromic lens having a photochromic film on a lens substrate is usually used in a state where the photochromic film is disposed on the object side (incident surface side) as shown in FIG. Therefore, in the present invention, the photochromic liquid is introduced into the photochromic liquid through at least the lens substrate so that the outermost surface of the photochromic film disposed on the object side (incident surface side) in use has an ultra fine indentation hardness of 800 nm or more. Irradiate the light. If the outermost surface of the light has such an energy that can provide a moderately flexible photochromic film having the above-mentioned ultra-fine indentation hardness, it may damage the lens substrate even if it is irradiated through the lens substrate. Absent. Moreover, if the ultra-fine indentation hardness of one surface of the photochromic film is 800 nm or more, the photochromic dye can move easily in the vicinity of the surface. Responsiveness can be obtained. Thus, according to the present invention, it is possible to obtain a photochromic lens in which the lens substrate exhibits excellent optical characteristics without being damaged by light irradiation, and the photochromic film exhibits high photoresponsiveness.

  The higher the micro-indentation hardness on the outermost surface of the photochromic film, that is, the higher the flexibility (fluidity) in the vicinity of the outermost surface, the more easily the photochromic dye moves, which is preferable in terms of photochromic performance. However, if the outermost surface is excessively flexible, it may be difficult to maintain the surface shape, or when a coating film is provided on the photochromic film, mixing may occur at the interface, or adhesion may be reduced. From the above viewpoint, the ultra-fine indentation hardness of the outermost surface of the photochromic film is preferably 5000 nm or less, more preferably 4000 nm or less, and even more preferably 3500 nm or less. Further, the ultra-fine indentation hardness of the outermost surface of the photochromic film is preferably 900 nm or more, more preferably 1200 nm or more, and still more preferably 2000 nm or more. The light irradiation may be performed so that the outermost surface of the photochromic film has the flexibility having the ultra-fine indentation hardness in the above range, and the entire photochromic film has the same flexibility. Alternatively, the hardness of one surface may be higher than the hardness of the other surface.

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. A method for controlling the ultra-fine indentation hardness of each surface of the photochromic film in the present invention will be described later.

  The hardness (flexibility) of the surface layer portion of the measurement target surface can be evaluated by the ultra-fine indentation hardness. Similarly, as an index of the hardness of the surface layer part, indentation hardness, Martens hardness, and composite Young's modulus are also known.

The indentation hardness is a value obtained from a displacement-load curve from indenter load to unloading and is defined in ISO 14577. The indentation depth h (nm) corresponding to the indentation load P (mgf) over the entire process from the start of load to unloading using the ultrafine indentation hardness tester ENT-2100 manufactured by Elionix Co., Ltd. ) Is measured continuously to create a Ph curve. The indentation hardness H can be obtained from the created Ph curve by the following formula (1).
H (mgf / μm ² ) = Pmax / A (1)
[Pmax: Maximum load (mgf), A: Indenter projected area (μm ² )]

The composite Young's modulus E ^* (mgf / μm ² ) can be obtained from the Ph curve according to the following formula (2).
[P: load (mgf), Pmax: maximum load (mgf), A: indenter projection area (μm ² ), h: indentation depth (nm)]

  Martens hardness is also defined in ISO 14577. Martens hardness is defined as the value obtained by dividing the load F by the surface area As penetrated by the indenter when the indenter is pushed down to a predetermined pushing amount h with the load F applied, and includes both components of plasticity and elastic deformation. It is. This is the hardness measured with the test load applied, and can be determined from the value of the load-indentation depth curve when the load is increased. The measurement can be performed using the above-mentioned Elionix ultra-fine indentation hardness tester ENT-2100.

When the hardness (flexibility) of the outermost surface of the photochromic film is expressed by indentation hardness, it is preferably 0.5 or more, more preferably 1.2 to 10, and when expressed by a composite Young's modulus, preferably 1.0 or more. More preferably, it is 3-150, and when expressed by Martens hardness, it is preferably 0.1 or more, more preferably 0.2-5.
Next, the detail of the manufacturing method of this invention is demonstrated.

(Process I)
In this step, a photochromic liquid containing a photochromic dye and a photocurable component is applied to one surface of the lens substrate.
The photochromic liquid contains at least a photochromic dye and a curable component, and can optionally contain a polymerization initiator and various additives. Details of each component will be described later.

  Application of the photochromic liquid to the surface of the lens substrate 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. Also, by applying the photochromic liquid using the coating apparatus described in Japanese Patent Application Laid-Open No. 2005-246268, the film thickness of the photochromic liquid collected from the outer peripheral edge of the coated surface to the outer peripheral surface (called the edge surface) is made uniform. can do. The coating amount may be appropriately adjusted according to the desired photochromic film thickness. In addition, before applying the photochromic liquid onto the lens substrate, the lens base is subjected to chemical treatment with acid, alkali, various organic solvents, physical treatment with plasma, ultraviolet light, ozone, etc., and detergent treatment with various detergents. The adhesion between the material and the photochromic film can be improved.

(Step II)
In this step, the photochromic liquid applied on the lens base material is irradiated with light through at least the lens base material, and at least a part of the curable component contained in the photochromic liquid is cured. A photochromic film is formed on the material. The cured state of the photochromic film (ultra fine indentation hardness of each surface) can be controlled by (1) the composition of the photochromic liquid, (2) the curing conditions, and (3) the thickness of the photochromic film. The above (1) to (3) will be sequentially described below.

(1) Photochromic liquid The photochromic liquid can be formed from a curable component, a photochromic dye, a polymerization initiator, and an additive that is optionally added. Below, each component is demonstrated.

(I) Curable component The curable component that can be used for photochromic film formation is not particularly limited, and radical polymerization such as (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, styryl group, etc. Known photopolymerizable monomers and oligomers having a functional group, 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.

To make the photochromic film easy to adjust the hardness, hardened body properties such as solvent resistance and hardness after film formation, heat resistance, etc., or photochromic properties such as color density and fading speed, radical polymerizable monomer As the body, a homopolymer having an L scale Rockwell hardness of 60 or more (hereinafter sometimes referred to as a high-hardness monomer) and a homopolymer having an L scale Rockwell hardness of 40 or less ( Hereinafter, it is more preferable to use in combination with 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, average molecular weight 375 polypropylene glycol methacrylate, average molecular weight 430 polypropylene methacrylate, average molecular weight 622 polypropylene methacrylate, average molecular weight 620 methyl ether polypropylene glycol methacrylate, average molecular weight 566 poly 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.

In addition to the above components, the curable component contained in the photochromic liquid includes a radical polymerizable monomer having at least one epoxy group and at least one radical polymerizable group in the molecule (hereinafter simply referred to as an epoxy monomer). It is preferable that it is further blended. Depending on the structure of this epoxy monomer, there are some which show L scale lock hardness of a single cured product of 60 or more, and others which show 40 or less. When classified according to the hardness of the homopolymer, it is classified into one of a high hardness monomer, a low hardness monomer, and a medium hardness monomer according to the hardness. By using this epoxy monomer as a curable component, the durability of the photochromic dye can be further improved, and the adhesion of the photochromic film can be further improved. A known compound can be used as such an epoxy monomer, but a compound having a (meth) acryloyloxy group as a radical polymerizable group is preferred.
Specific examples of the epoxy monomer include a monomer represented by the following general formula (10).

{Wherein R ³⁵ and R ³⁸ are each independently a hydrogen atom or a methyl group, and R ³⁶ and R ³⁷ are each independently an alkylene group having 1 to 4 carbon atoms, or 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 ) any group selected from (C ₆ H ₅ ) —, wherein R ³⁹ and R ⁴⁰ are each independently an alkyl group having 1 to 4 carbon atoms or a halogen atom, and l ″ and l ″. 'Is each independently an integer of 0 to 4). }

Examples of the alkylene group having 1 to 4 carbon atoms represented by R ³⁶ and R ³⁷ include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a butylene difference. These alkylene groups may be substituted with a hydroxyl group, a halogen atom or the like.
Also, R ³⁶ and / or R ³⁷ are represented by the following formula:
In the group represented by the formula, G ′ represents 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 )-are any groups selected, and R ³⁹ and R ⁴⁰ are each independently a methyl group, an ethyl group, a propyl group, a butyl group or the like. An alkyl group having 1 to 4 carbon atoms or a halogen atom such as a chlorine atom or a bromine atom, and l ″ and l ′ ″ are each independently an integer of 0 to 4;
As the group represented by the above formula, the following formula:
The group represented by is most preferable.

Specific examples of the epoxy monomer represented by the general formula (10) include glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2 -Oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3-glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate, average molecular weight 540 And glycidyloxypolyethylene glycol methacrylate. Among these, glycidyl acrylate, glycidyl methacrylate and glycidyloxypolyethylene glycol methacrylate having an average molecular weight of 40 are particularly preferable.
When using these epoxy-type monomers, the mixture ratio is 0.01-30 mass% normally in a sclerosing | hardenable component, and it is suitable that it is 0.1-20 mass%.

(Ii) Photochromic dye As the photochromic dye that can be added to the photochromic liquid, known ones can be used, and examples 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, WO96 / 14596, and the like. 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, 2000-34476, 2000-344761, 2000-327676, 2000-327675, 2000-256347, 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. Thereby, the curing reaction proceeds well on the surface on which the light irradiated for polymerization is incident, high hardness can be obtained, and the progress of the curing reaction on the other surface can be suppressed. 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 (radically polymerizable monomers etc.) of the said sclerosing | hardenable component. 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 photopolymerization initiators.
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 (radically polymerizable monomers etc.) of the said sclerosing | hardenable component, 0.1-1 It is preferable that it is a mass part.

(Iv) Various additives The adhesiveness of a photochromic film | membrane and a lens base material can be improved by mix | blending the organosilicon compound which has an epoxy group in one terminal to the said photochromic liquid.
Examples of the organosilicon compound include a compound having a silanol group, or a compound having a group that generates a silanol group by hydrolysis, for example, an organosilicon compound represented by the following general formula (I) or a hydrolyzate thereof: Is mentioned.
(R ⁸¹ ) _a (R ⁸³ ) _b Si (OR ⁸² ) _{4- (a + b)} (I)
(In the formula, R ⁸¹ is an organic group having an epoxy group, R ⁸² is an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms, and R ⁸³ is 1 carbon atom. -6 alkyl group or C6-C10 aryl group, a is 1 and b is 0 or 1.)

Examples of the organic group having an epoxy group of R ⁸¹ include, for example, an epoxy group, a glycidoxy group (α-glycidoxy group, β-glycidoxy group, γ-glycidoxy group, δ-glycidoxy group, etc.), 3,4-epoxycyclohexyl group. Etc.
Examples of the alkyl group having 1 to 4 carbon atoms of R ⁸² 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 ⁸² 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 ⁸² include a phenyl group, a xylyl group, and a tolyl group.
Examples of the alkyl group having 1 to 4 carbon atoms of R ⁸³ 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 ⁸³ include a phenyl group, a xylyl group, and a tolyl group.

Specific examples of the compound represented by the general formula (I) include glycidoxymethyltriethoxysilane, α-glycidoxyethyltriethoxysilane, β-glycidoxyethyltrimethoxysilane, β-glycidoxy Ethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β-glycidoxypropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltriphenoxysilane, α-glycidoxy Butyltrimethoxysilane, α-glycidoxybutyltriethoxysila , Β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane , Δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltrimethoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 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) propyltriethoxysilane, 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-Glycidoxypropi Methyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ- Glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane , Γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, etc., γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycid Xipropyltripro Kishishiran, .gamma.-glycidoxypropyl tributoxysilane silane, .gamma.-glycidoxypropylmethyldiethoxysilane, .gamma.-glycidoxypropyl ethyl dimethoxysilane, .gamma.-glycidoxypropyl ethyl diethoxysilane is preferred.
The compounding amount of the organosilicon compound with respect to the total amount of the photochromic liquid is usually 0.1 to 1 part by mass and preferably 1.0 to 10 parts by mass with respect to 100 parts by mass of the curable component.

By blending the photochromic liquid with an organosilicon compound having a radical polymerizable functional group at one end, the film strength of the photochromic film can be improved.
The organosilicon compound is a compound having a silanol group or a compound having a group that generates a silanol group by hydrolysis. For example, an organosilicon compound represented by the following general formula (II) or a hydrolyzate thereof is Can be mentioned.
(R ⁸⁴ ) _c (R ⁸⁶ ) _d Si (OR ⁸⁵ ) _{4- (c + d)} (II)
(In the formula, R ⁸⁴ is an organic group having a radical polymerizable functional group, R ⁸⁵ is an alkyl group having 1 to 4 carbon atoms, an acyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, R ⁸⁶ is (C 1-6 alkyl group or C 6-10 aryl group, c represents 1, d represents 0 or 1)

Examples of the organic group having a radically polymerizable functional group of R ⁸⁴ include (meth) acryloyl group, (meth) acryloyloxy group, vinyl group, allyl group, styryl group, and the like. (Meth) acryloyl group or (meth) acryloyloxy group is preferable from the viewpoint of good quality.
Examples of the alkyl group having 1 to 4 carbon atoms of R ⁸⁵ 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 ⁸⁵ 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 ⁸⁵ include a phenyl group and a xylyl group tolyl group.
Examples of the alkyl group having 1 to 4 carbon atoms of R ⁸⁶ 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 ⁸⁶ include a phenyl group and a xylyl group tolyl group.

Specific examples of the compound represented by the general formula (II) include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, (3-acryloxypropyl) ) Dimethylmethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, (3-acryloxypropyl) trimethoxysilane, (methacryloxymethyl) dimethylethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltrimethoxysilane, Methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane and the like are preferable.
The compounding amount of the organosilicon compound with respect to the total amount of the photochromic liquid is usually 0.1 to 15 parts by mass and preferably 1.0 to 10 parts by mass with respect to 100 parts by mass of the curable component.

An amine compound can also be mix | blended with the said photochromic liquid. By blending the amine compound, the adhesion between the photochromic film and the lens substrate can be greatly improved.
Any known amine compound can be used as the amine compound as long as it is a basic compound that functions as a condensation or addition catalyst for the curable component.

Examples of the amine compound that does not exhibit a function required as the amine compound include the following groups:
(In the above groups, R ⁰¹ is a hydrogen atom or an alkyl group, and R ⁰² , R ⁰³ , R ⁰⁴ and R ⁰⁵ are the same or different alkyl groups, respectively)
The hindered amine compound which has only the amino group represented by these as an amino group is mentioned.

Specific examples of amine compounds that can be used to improve adhesion include non-polymerizable low molecular weight systems such as triethanolamine, N-methyldiethanolamine, triisopropanolamine, 4,4-dimethylaminobenzophenone, diazapicyclooctane, etc. Amine compounds having polymerizable groups such as amine compounds, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, n- (hydroxyethyl) -N-methylaminopropyltrimethoxysilane, dimethoxyphenyl- Examples include amine compounds having a silyl group, such as 2-piperidinoethoxysilane, N, N-diethylaminomethyltrimethylsilane, and (N, N-diethyl-3-aminopropyl) trimethoxysilane.
Among these amino compounds, from the viewpoint of improving adhesion, those having a hydroxyl group, those having a (meth) acryloyloxy group as a radical polymerizable group, or amine compounds having a group capable of generating a silanol group by hydrolysis are included. preferable.

For example, the following general formula (11):
{Wherein R ⁰⁶ is a hydrogen atom or a linear alkyl group having 1 to 4 carbon atoms, R ⁰⁷ is a hydroxyl group, a (meth) acryloyloxy group or a group capable of generating a silanol group by hydrolysis, R ⁰⁸ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a (meth) acryloyloxy group, or a group capable of generating a silanol group by hydrolysis, A ′ is an alkylene group having 2 to 6 carbon atoms, A '' ^Means that when R ⁰⁸ is a hydrogen atom or an alkyl group, it is an alkylene group having 1 to 6 carbon atoms, R ⁰⁸ is a hydroxyl group, a (meth) acryloyloxy group or a group capable of generating a silanol group by hydrolysis. Represents an alkylene group having 2 to 6 carbon atoms. }
Is more suitable as an amine compound having a strong basicity and a high effect of improving adhesion.

In R ⁰⁷ and R ⁰⁸ in the general formula (11), the group capable of generating a silanol group by hydrolysis has the same definition as the group defined in the organosilicon compound.
These amine compounds can be used alone or in combination. The compounding amount of the amine compound is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable component.

  The photochromic liquid further includes a surfactant, an antioxidant, a radical scavenger, an ultraviolet stabilizer, an ultraviolet ray for improving the durability of the photochromic dye, improving the color development speed, improving the fading speed and improving the moldability. Additives such as an absorbent, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, and a plasticizer may be added. 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. As the hindered amine light stabilizer, any known compound can be used without limitation as long as it is a compound defined as a hindered amine compound described as a compound excluded from the above-described amine compound. 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, 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 After applying the photochromic liquid on the lens substrate as described above, the photochromic liquid is irradiated with light to cure at least a part of the photochromic liquid, and the outermost surface has an ultrafine surface of 800 nm or more. A photochromic film having a small indentation hardness is formed. By adjusting the light irradiation conditions at this time, the cured state of the obtained photochromic film can be controlled.

  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. However, as the lens base material, a lens base material having transparency to the irradiated light is used to such an extent that the curing reaction can proceed. For example, when ultraviolet rays are used as the irradiation light, when the ultraviolet rays are irradiated through a lens base material including an ultraviolet absorber, most of the irradiated ultraviolet rays are absorbed by the lens base material, so that it faces the lens base material. It becomes difficult to cure the photochromic film surface to such an extent that adhesion can be secured. Therefore, in this case, it is preferable to use a lens substrate that does not contain an ultraviolet absorber.

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 irradiation surface, the irradiation energy, and the irradiation time are preferably adjusted in consideration of the composition of the photochromic liquid and the coating amount. Specifically, the irradiation energy of the light irradiated through the lens substrate can be a 1~100J / cm ^2, it is preferable to 1~75J / cm ^2. What is necessary is just to set the distance of the surface which opposes a light source and a lens base material suitably, considering the thickness of a lens base material, for example, it can be set as 100-300 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. In this way, a photochromic film can be obtained in which the vicinity of the surface facing the lens substrate is appropriately cured, the inside is in an uncured state, and an appropriate flexibility is imparted to one surface (outermost surface). In order to increase the curing efficiency, it is preferable to perform light irradiation in an inert atmosphere.

In the present invention, photoirradiation is performed on the lens base material without performing light irradiation on the photochromic liquid application surface of the lens base material, or in addition to light irradiation via the lens base material, It intends line light irradiation with respect to the surface. Thereby, the hardness of the outermost surface of the photochromic film can be adjusted, and the durability of the photochromic film can be ensured. However, when performing both the light irradiation to the photochromic liquid application surface and the light irradiation through the lens substrate so that the ultra fine indentation hardness of the outermost surface of the photochromic film is 800 nm or more , the lens substrate is light irradiation through, it intends row at a higher dose than the light irradiation to the photochromic solution-coated surface. Light irradiation to the photochromic liquid application surface can be performed, for example, at an irradiation dose of 0.1 to 30 J / cm ² .
Further, as described later, when a hard coat or an antireflection film is provided on the photochromic film, the surface of the photochromic film is protected by them, so that durability can be ensured without performing light irradiation on the outermost surface. .

(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 outermost surface of the photochromic film. 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.

Lens Substrate As the lens substrate, various substrates that are usually used as plastic lenses 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 addition, as mentioned above, when irradiating a photochromic liquid with an ultraviolet-ray, it is preferable to use the lens base material which does not contain an ultraviolet absorber. As the lens substrate, one having a transmittance of about 85 to 95% for light (for example, ultraviolet rays) irradiated for forming a photochromic film can be used.

Hard coat, antireflection film In the photochromic lens, a hard coat layer can be formed on the photochromic film. Furthermore, an antireflection film can be formed on the hard coat layer.
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

  The hard coat and antireflection film can be formed on a photochromic film formed on a lens substrate by a known method. The thickness of the lens substrate, and the hard coat and antireflection film provided as necessary are not particularly limited, but the thickness of the lens substrate is 1 to 30 mm, for example, and the thickness of the hard coat is 0. The thickness of the antireflection film can be 5 to 10 μm, 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]
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 In addition, to 100 parts by mass of a radical polymerizable monomer composed 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 LS765 (bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate) 5 parts by mass, CGI- as an ultraviolet polymerization initiator 1 84 parts by weight of 84 (1-hydroxycyclohexyl phenyl ketone) and 0.1 part by weight of CGI403 (bis (2,6-dimethoxybenzoyl-2,4,4-trimethylpentylphosphine oxide)) were added. In addition, 4.8 parts by mass of an organosilicon compound having an epoxy group (γ-glycidoxypropyltrimethoxysilane) as an adhesive, and γ-methacryloyloxypropyltrimethoxysilane 1 as an organosilicon compound having a radical polymerizable functional group After stirring sufficiently, 1.4 parts by mass of N-methyldiethanolamine was added dropwise and further stirred and mixed.After that, silicone leveling agent Y-7006 ( Polyoxyalkylene / dimethylpolysiloxane copolymer: Nippon Unicar Co., Ltd. )) Was added and mixed, and then defoamed for 2 minutes with a rotation and revolution type stirring deaerator (AR-250, manufactured by Shinky Corporation) to obtain a photochromic liquid. The viscosity of the liquid was 140 mPa · s.

2. Formation of Photochromic Lens A lens obtained by removing an ultraviolet absorber from a trade name EYAS (center thickness: 2.0 mm) manufactured by HOYA Co., Ltd. was used as a plastic lens substrate. This lens base material was immersed in a 10% by mass sodium hydroxide aqueous solution at 60 ° C. for 5 minutes, sufficiently washed with pure water and dried, and then 1. Using the photochromic solution prepared in step 1, the substrate was coated on the convex surface side of the substrate by spin coating.
Thereafter, the photochromic film was cured by irradiating light from the concave surface side of the lens with a UV lamp (wavelength 150 to 380 nm) manufactured by Toshiba Lilac in a nitrogen atmosphere. The irradiation distance (distance between the photochromic film surface facing the lens substrate and the light source) was 330 mm, and the irradiation time was 185 seconds. The film thickness of the photochromic film was measured and found to be 30 microns. About the obtained photochromic film | membrane, the hardness of the object side surface was measured with the following method. The results are shown in Table 1.

(i) Ultrafine indentation hardness The ultrafine indentation hardness of the object-side surface of the photochromic film of Example 1 was measured by the above method.

(ii) Indentation hardness Using an ultra indentation hardness tester ENT-2100 manufactured by Elionix, a load of 100 mgf is applied, and an indentation corresponding to the indentation load P (mgf) is applied throughout the entire process from the start of loading to unloading. The depth h (nm) was measured continuously to create a Ph curve. The indentation hardness H was determined from the formula (1) described above from the created Ph curve.

(iii) Composite Young's Modulus From the Ph curve created in (ii) above, the composite Young's modulus was determined by the above-described formula (2).

(iv) Martens Hardness Using an ultra-fine indentation hardness tester ENT-2100 manufactured by Elionix, the indenter was pushed in with a load of 100 mgf. At this time, the surface area penetrated by the indenter was measured from the indentation depth, and the Martens hardness was determined as “load / surface area penetrated by the indenter”.

[Example 2]
A photochromic lens was formed in the same manner as in Example 1 except that the light irradiation time during the photochromic film curing treatment was 80 seconds. The film thickness of the photochromic film was measured and found to be 30 microns. About the obtained photochromic film | membrane, the hardness of the object side surface was measured with the following method. The results are shown in Table 1.

[Example 3]
A photochromic lens was formed in the same manner as in Example 1 except that the light irradiation time during the photochromic film curing treatment was 320 seconds. The film thickness of the photochromic film was measured and found to be 30 microns. About the obtained photochromic film | membrane, the hardness of the object side surface was measured with the following method. The results are shown in Table 1.

[Example 4]
After 165 seconds of light irradiation from the lens concave surface side, light irradiation (irradiation distance 330 mm, irradiation time 40 seconds) from the convex surface side (photochromic liquid application surface side) of the lens with a Toshiba Lilac UV lamp in a nitrogen atmosphere. A photochromic lens was obtained in the same manner as in Example 1 except that the photochromic film was cured. The film thickness of the photochromic film was measured and found to be 30 microns. About the obtained photochromic film | membrane, the hardness of the object side surface was measured with the following method. The results are shown in Table 1.

[Example 5] (Hard layer, antireflection layer formation)
The meniscus-shaped photochromic lens having a photochromic film on the convex surface formed in Examples 1 to 4 was subjected to the following treatment 4.5 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 vapor deposition 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.
Through the above steps, a photochromic lens having a photochromic film, a hard coat layer, and an antireflection layer in this order on the convex surface of the lens substrate was obtained.

[Reference example]
The convex surface side of the substrate is the same as in Example 1, except that polythiourethane (trade name EYAS (containing UV absorber), center thickness 2.0 mm thickness) manufactured by HOYA Co., Ltd. is used as the plastic lens substrate. Was coated with a photochromic solution.
Thereafter, the photochromic film was cured by irradiating light from the convex surface side (photochromic liquid application surface side) of the lens with a UV lamp manufactured by Toshiba Lilac in a nitrogen atmosphere. The irradiation distance was 330 mm and the irradiation time was 165 seconds. The thickness of the cured film was measured and found to be 30 microns.
Further, curing was performed at 110 ° C. for 100 minutes to obtain a plastic lens having a photochromic film. About the obtained photochromic film | membrane, the hardness of the object side surface was measured by the said method. The results are shown in Table 1.

Dimming performance evaluation (change in transmittance)
Photochromic evaluation was performed by the following method according to JIS T7333. For the photochromic films on the photochromic lenses obtained in Examples 1 to 4 and Reference Example, a xenon lamp was used for 15 minutes (900 seconds) through an aeromass filter, and the surface of the photochromic film (surface facing the lens substrate) The photochromic film was colored by irradiating light on the opposite surface). 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 2 below as defined in JIS T7333. 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. The results are shown in FIG. FIG. 3 shows the light transmittance (550 nm) of the photochromic lens after irradiation (0 to 15 minutes), irradiation completion (15 minutes), and irradiation completion (15 minutes to).

As shown in FIG. 3, the transmittances of the lenses of Examples 1 to 4 changed greatly immediately after the start of irradiation and immediately after the end of irradiation. This indicates that the reaction rate of the color development is high. Further, after completion of irradiation, the lenses of Examples 1 to 4 returned to their original transmittance earlier than the reference example lens, and had excellent photochromic properties. As can be seen from the above results, the lenses of Examples 1 to 4 had excellent photoresponsiveness.
Moreover, when the lenses of Examples 1 to 4 were visually observed, the transparency of the lens substrate was as good as before the photochromic film was formed. From this result, it can be seen that according to the present invention, a photochromic film can be formed without damaging the lens substrate.

  According to the present invention, a photochromic lens having excellent light control performance and optical characteristics can be provided. The photochromic lens obtained by the present invention is suitable as a spectacle lens.

An example of the photochromic lens which has a photochromic film | membrane on a lens base material is shown. The schematic of the measuring method of super micro indentation hardness is shown. The measurement result of the color development density | concentration of the photochromic film | membrane on the photochromic lens obtained in Examples 1-4 and the reference example, and a color release rate is shown.

Claims (3)

A method for producing a photochromic lens having a photochromic film on a lens substrate,
Apply a photochromic liquid containing a photochromic dye and a photocurable component on one side of the lens substrate,
By curing at least a part of the previous SL-curable component irradiated with light with respect to the photochromic liquid, to form a photochromic film outermost surface has a hardness indentation ultrafine above 800 nm,
Irradiation of light to the photochromic liquid is performed through the lens base material without performing the photochromic liquid application surface of the lens base material, or light irradiation to the photochromic liquid is performed on the photochromic liquid application surface of the lens base material. The method for producing a photochromic lens according to claim 1, wherein the photochromic lens is formed through a lens base material, wherein the light irradiation through the lens base material is performed at a higher dose than the light irradiation on the photochromic liquid application surface. The method for producing a photochromic lens according to claim 1, wherein the wavelength of the irradiated light is in a range of 150 to 380 nm. The method for producing a photochromic lens according to claim 1, wherein the lens substrate does not contain an ultraviolet absorber.