JP2008030439A - Method for manufacturing photochromic lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a photochromic lens which is excellent in optical responsivity and optical characteristics. <P>SOLUTION: A photochromic solution including a photochromic dye and a curing component is applied on one side of a first mold which forms one side of the lens, and a curing treatment is conducted on the photochromic liquid, thereby a photochromic film is formed with its outermost surface having a nanoindentation hardness of 500 to 5,000 nm, the indentation hardness being lower than the nanoindentation hardness of the surface facing the first mold, thereafter the a photochromic lens with the photochromic film formed on the lens base material is formed by cast polymerization. <P>COPYRIGHT: (C)2008,JPO&INPIT

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. The photochromic film used here is required to quickly respond when predetermined light is incident and develop a color at a high density, and to quickly fade when placed in an environment without the light.

As a method for producing a photochromic lens having the above structure, Patent Document 1 discloses that when a plastic lens is produced by cast polymerization, a coating solution containing a photochromic dye is applied in advance to the inner surface of the mold, thereby curing the lens. A method (cast polymerization method) for simultaneously forming a photochromic film has been proposed.
Japanese Patent Laid-Open No. 10-231331

  In the manufacturing method described in Patent Document 1, the photochromic liquid applied to the inner surface of the mold is unpolymerized or partially cured before injecting the lens monomer in order to ensure adhesion between the photochromic layer and the lens substrate. The photochromic solution and the lens substrate are sequentially cured after the lens monomer injection. The method described in Patent Document 1 has the advantage of excellent workability because it can simultaneously cure the lens base material and provide the photochromic film, but because the lens base material and the photochromic layer are mixed, There is a problem that the optical characteristics of the lens deteriorate (cloudiness, striae). Further, the response (reaction speed and color density) of the photochromic lens obtained by the method described in Patent Document 1 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 method for producing 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.
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 further studies by the present inventors, if the photochromic film is not completely cured but has flexibility (fluidity), the dye can move easily in the film, and the reaction speed and color density of the color development can be reduced. It turns out that it improves greatly.
However, when the flexibility (fluidity) of the entire photochromic film is increased, there is a problem that mixing of the lens raw material liquid and the uncured portion of the photochromic film occurs during casting polymerization, resulting in a decrease in optical characteristics.
Therefore, the present inventors have further studied, and by increasing the hardness of the contact surface side of the photochromic film with the lens base material more than the hardness of the object side, the interface between the lens base material and the photochromic film in the casting polymerization method. It is possible to ensure photoresponsiveness by making the dye move easily on the object side without causing deterioration in optical characteristics due to mixing in the photochromic lens, and by this means that a photochromic lens excellent in photoresponsiveness and optical characteristics can be obtained. I found it. 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 liquid containing a photochromic dye and a curable component is applied to one side of the first mold for forming one side of the lens,
By applying a curing treatment to the photochromic liquid, the outermost surface has an ultrafine indentation hardness of 500 to 5000 nm, and the ultrafine indentation hardness of the surface facing the first mold is the ultrafine indentation of the outermost surface. Form a photochromic film smaller than the small indentation hardness,
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 faces the second mold surface, and an annular gasket is provided around the two molds. To form a cavity in which the photochromic film is located by the two molds and gasket,
A photochromic lens characterized by injecting a lens raw material solution containing a curable component into the cavity and performing a curing reaction of the curable component in the cavity to obtain a photochromic lens having a photochromic film on a lens substrate. Manufacturing method.
[2] The method for producing a photochromic lens according to [1], wherein the curing treatment is performed such that an ultra fine indentation hardness of a surface of the photochromic film facing the first mold is in a range of 800 to 5000 nm.
[3] The production of the photochromic lens according to [1] or [2], wherein the outermost surface of the photochromic film is subjected to a dry etching process using UV ozone or plasma after the formation of the photochromic film and before the formation of the cavity. Method.
[4] The method for producing a photochromic lens according to any one of [1] to [3], wherein the curable component contained in the photochromic film is a photocurable component, and the curing treatment is performed by light irradiation.
[5] The photochromic lens manufacturing method according to [4], wherein the light irradiation includes performing light irradiation on a photochromic liquid application surface of the first mold.
[6] The first mold is light transmissive,
The method for producing a photochromic lens according to [4] or [5], wherein the light irradiation includes performing light irradiation on a photochromic liquid applied to the first mold via the first mold.
[7] The photochromic lens manufacturing method according to any one of [4] to [6], wherein the wavelength of the irradiated light is in a range of 150 to 380 nm.
[8] The method for producing a photochromic lens according to [6] or [7], wherein the light irradiation through the first mold is performed with a lower dose than the light irradiation on the photochromic liquid application surface.
[9] Light irradiation through the first mold is carried out in irradiation amount of 0.1~30J / cm ^2, light irradiation of the photochromic solution-coated surface, the row in the dose of 1~100J / cm ² The manufacturing method of the photochromic lens as described in [8].
[10] The method for producing a photochromic lens according to any one of [1] to [9], wherein the curable component contained in the lens raw material liquid is a thermosetting component, and the curing reaction is performed by heating.
[11] The method for producing a photochromic lens according to any one of [1] to [10], wherein the lens raw material liquid includes an ultraviolet absorber.

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

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.
(First Step) A photochromic liquid containing a photochromic dye and a curable component is applied to one side of a first mold for forming one side of a lens.
(Second step) By applying a curing treatment to the photochromic liquid, the outermost surface has an ultra-fine indentation hardness of 500 to 5000 nm, and the ultra-fine indentation hardness of the surface facing the first mold is A photochromic film smaller than the outermost ultra indentation hardness is formed.
(Third step) 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 faces the second mold surface, and the two molds By disposing an annular gasket around, a cavity in which the photochromic film is located is formed by the two molds and the gasket.
(Fourth Step) 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.

In the present invention, before the casting polymerization, the outermost surface of the photochromic film in contact with the lens raw material liquid is cured to have a predetermined hardness. Thereby, it is possible to prevent the lens raw material liquid and the uncured portion of the photochromic film from being mixed in the vicinity of the outermost surface of the photochromic film during cast polymerization. Since mixing at the interface causes fogging and striae, a photochromic lens having excellent optical characteristics can be obtained by preventing mixing at the interface as described above.
Furthermore, in the present invention, the hardness of the surface facing the first mold of the photochromic film is lowered from the hardness of the other surface, and appropriate flexibility (fluidity) is imparted in the vicinity of the surface that becomes the incident surface side in use. This point will be described below.

FIG. 1 shows an example of a lens manufactured by the manufacturing method of the present invention.
A photochromic lens having a photochromic film on a lens substrate is usually irradiated with light from the photochromic film side as shown in FIG.
As described above, as a result of the study by the present inventors, if the photochromic film is not completely cured but has flexibility (fluidity), the dye can move easily in the film, and the reaction speed and color density of the color change Was found to improve significantly. However, when the flexibility (fluidity) of the entire photochromic film is increased, there is a problem that mixing of the lens raw material liquid and the uncured portion of the photochromic film occurs during casting polymerization, resulting in a decrease in optical characteristics. As a result of further investigations by the present inventors based on these points, the photoresponsiveness of the photochromic lens is mainly expressed in the object-side surface layer portion where light enters, and therefore, the dye existing in the object-side surface layer portion is not used. It has been found that a photochromic lens with excellent photoresponsiveness can be obtained by making it easy to move.
Therefore, in the present invention, the hardness of the surface facing the first mold of the photochromic film is lowered from the hardness of the other surface, and appropriate flexibility (fluidity) is imparted in the vicinity of the surface that becomes the incident surface side in use. Thereby, the photoresponsiveness in the object side surface layer part of a photochromic film | membrane can be improved notably.
Thus, according to the present invention, a photochromic lens having both excellent photoresponsiveness and optical characteristics can be obtained.
Details of the first to fourth steps will be described below.

(First step)
In this step, a photochromic liquid is applied to one side of a mold (first mold) for forming one side of the lens.
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 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.

(Second step)
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. By adjusting the cured state at this time, the cured state of the resulting photochromic film can be controlled, and each surface can have a desired hardness (ultra-indentation hardness).

  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 In the present invention, a curable component that can be used for forming a photochromic film is not particularly limited, and includes a (meth) acryloyl group, a (meth) acryloyloxy group, a vinyl group, Known photopolymerizable monomers and oligomers having radically polymerizable groups such as allyl groups and styryl 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. 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 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. 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 the present invention, by controlling the cured state of the photochromic film as described above, the ultra-fine indentation hardness of the outermost surface of the photochromic film is set to 500 to 5000 nm. If the ultra-fine indentation hardness of the outermost surface (the surface in contact with the photochromic liquid during casting polymerization) is less than 500 nm, there is a problem that the adhesion between the lens substrate and the photochromic film is weakened and the durability of the photochromic lens is lowered. On the other hand, if the ultra-fine indentation hardness of the outermost surface exceeds 5000 nm, the uncured portion of the photochromic film and the lens raw material liquid are mixed during cast polymerization, thereby causing fogging and striae in the lens. As a result, there is a problem that the optical characteristics are deteriorated. The lower limit of the ultra fine indentation hardness of the outermost surface of the photochromic film is preferably 600 nm, more preferably 1000 nm, particularly preferably 2500 nm, and the upper limit thereof is preferably 3500 nm.

  In the present invention, the ultra fine indentation hardness of the outermost surface of the photochromic film is set in the above range, and the ultra fine indentation hardness of the opposite surface (the surface facing the first mold surface) is made smaller than that of the outermost surface. . Thus, by making the surface on the object side (incident surface side) flexible during use, the photochromic dye can move easily in the vicinity of the surface. Thus, it is possible to obtain a photochromic film that quickly responds when light of a predetermined wavelength is incident and develops color at a high concentration and quickly fades when placed in an environment where there is no light of a predetermined wavelength.

  As described above, in the second step, the ultra-fine indentation hardness of the surface facing the first mold of the photochromic film is made smaller than that of the opposite surface. The ultra fine indentation hardness of this surface is preferably in the range of 800 to 5000 nm. Since this surface is disposed on the object side during normal use, the photochromic dye can be easily moved in the vicinity of the object-side surface by setting the ultra-fine indentation hardness of this surface to 800 nm or more. Accordingly, it is possible to obtain a photochromic lens that quickly responds when light of a predetermined wavelength is incident and develops color at a high density and quickly fades when placed in an environment where there is no light of a predetermined wavelength. The ultra-fine indentation hardness of the surface facing the first mold of the photochromic film is more preferably 4000 nm or less, and even more preferably 3500 nm or less. Further, the ultra fine indentation hardness of the surface of the photochromic film facing the first mold is more preferably 900 nm or more, further preferably 1200 nm or more, and still more preferably 2000 nm or more.

  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.

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 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.

  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 portion, 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.

  In terms of indentation hardness, the surface facing the first mold of the photochromic film in the second step is preferably 0.5 or more, more preferably 1.2 to 10, and the outermost surface of the photochromic film is preferably It is 1.0 or more, More preferably, it is 1.5-20. In terms of the composite Young's modulus, the surface facing the first mold of the photochromic film in the second step is preferably 1.0 or more, more preferably 3 to 150, and the outermost surface of the photochromic film is preferably 3 0.0 or more, more preferably 6 to 300. In terms of Martens hardness, the surface facing the first mold of the photochromic film in the second step is preferably 0.1 or more, more preferably 0.2 to 5, and the outermost surface of the photochromic film is preferably 0. .3 or more, more preferably 0.5 to 10. The hardness of the outermost surface of the photochromic film after the second step and the hardness of the surface facing the first mold are the same as those on the final product when the photochromic film does not substantially cure in the step after the second step. It can be regarded as the same as the measured value in the photochromic film. Moreover, after implementing to a 2nd process on the same conditions as real product manufacture, the photochromic film | membrane formed on the 1st mold can also be used as a sample for hardness measurement.

(Third process)
In the third step, the first mold having the photochromic film formed on the surface in the second step is disposed so as to face the other surface of the lens, and an annular gasket is disposed around these two molds. A cavity is formed by two molds and a 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. 3 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. 3, 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. 4 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. 4 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.

(Fourth process)
The fourth step is a step of injecting the lens raw material solution into the cavity formed in the third step, and polymerizing the lens base material and forming 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 addition, in the conventional method of applying a coating liquid containing a photochromic dye on a plastic lens and curing the coating liquid to obtain a lens with a photochromic film, when a photochromic film is formed by ultraviolet irradiation, If the lens substrate contains an ultraviolet absorber, 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 photochromic lens manufacturing method of the present invention, the photochromic film can be preliminarily subjected to a desired curing treatment. Therefore, even if the lens base material contains an ultraviolet absorber, it is desired on the base material. Can be formed. Therefore, the method of the present invention is particularly suitable as a method for obtaining a photochromic lens containing a UV 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. After the polymerization is completed, the lens-shaped molded body coated with the photochromic film is released from the mold.
Through the above steps, a photochromic lens having a photochromic film on the lens substrate can be obtained. In addition, various coatings such as a hard coat and an antireflection film can be formed on the obtained photochromic lens by a known method. For example, a hard coat layer can be formed on the photochromic film, and 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

  In the photochromic lens obtained by the method of the present invention, the thickness of the lens substrate and the hard coat provided as necessary and the antireflection film are 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]
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. Was defoamed for 2 minutes using a rotation and revolution type stirring deaerator (AR-250, manufactured by Shinky Corp.), and a photochromic liquid was obtained with a viscosity of 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.

[Example 2] (Formation of photochromic film having a film thickness of 60 μm)
Example 1-2. The number of rotations in the spin coating method in (1) was 300 rotations, and the time was 10 seconds. Other treatments were performed in the same manner as in Example 1 to form a photochromic film having a thickness of 60 microns.

[Example 3] (UV irradiation from both sides of the mold)
Example 1-2. In the nitrogen atmosphere in (2), ultraviolet rays were irradiated from both sides of the mold using a Toshiba Lilac UV lamp to cure the photochromic liquid. The ultraviolet irradiation was performed at an irradiation distance of 330 mm, and the irradiation time was 165 seconds on the concave surface side and 90 seconds on the convex surface side. Other treatments were performed in the same manner as in Example 1 to form a photochromic film having a thickness of 30 microns.

[Reference example] (Photochromic liquid is applied to the convex surface of the lens substrate, and UV irradiation is applied from the convex surface side)
1. Preparation of photochromic liquid In addition to the components of Example 1, 4.8 parts by mass of an organosilicon compound having an epoxy group (γ-glycidoxypropyltrimethoxysilane) as an adhesive, and organosilicon having a radical polymerizable functional group As a compound, 1.6 parts by mass of γ-methacryloyloxypropyltrimethoxysilane was added dropwise with stirring. After sufficiently stirring, 1.4 parts by mass of N-methyldiethanolamine was weighed and dropped, and further sufficiently stirred and mixed. Thereafter, 0.1 part by mass of silicone leveling agent Y-7006 (polyoxyalkylene / dimethylpolysiloxane copolymer: Nippon Unicar Co., Ltd.) was added and mixed. A photochromic solution was obtained by defoaming for 2 minutes using AR-250).

2. Formation of photochromic lens Polythiourethane (trade name EYAS (containing UV absorber), center wall thickness: 2.0 mm) manufactured by HOYA Co., Ltd.) as a plastic lens base material at 60 ° C. and 10% by mass sodium hydroxide aqueous solution After immersing for 5 minutes and thoroughly washing with pure water and drying, the above 1. Using the photochromic solution prepared in (1), the coating on the convex surface side of the substrate was performed by spin coating.
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 film thickness of the photochromic film was measured and found to be 30 microns.
Further, curing was performed at 110 ° C. for 100 minutes to obtain a plastic lens lens having a photochromic film.

Evaluation of Photochromic Lens (1) Adhesion Evaluation Each of the photochromic lenses obtained in Examples 1, 2, and 3 was cross-cut with 100 stitches at intervals of 1 mm, and an adhesive tape (trade name; Cellotape, Nichiban Co., Ltd.) was used. It was strongly applied and peeled off rapidly, and the presence or absence of peeling of the photochromic film was examined. In Table 2, those that were not peeled off at all were shown as 100/100, and those that were all peeled off were shown as 0/100.

(2) Appearance The photochromic lenses obtained in Examples 1, 2, and 3 were visually determined under a fluorescent lamp in a dark room. A coating film surface that was not distorted and was uniformly applied was judged good. The results are shown in Table 2.

(3) Dimming performance
(i) Change in transmittance The photochromic property was evaluated by the following method according to JIS T7333. For the photochromic film on the photochromic lens obtained in Examples 1 and 2 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 became values shown in Table 1 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. The results are shown in FIG. The upper diagram in FIG. 5 shows the light transmittance (550 nm) of the photochromic lens after irradiation (0 to 15 minutes), the end of irradiation (15 minutes), and the end of irradiation (15 minutes to), and the lower diagram in FIG. 2 and the light transmittance of the photochromic lens for each different wavelength when the photochromic film on the photochromic lens obtained in Reference Example is irradiated with light by the above method for 930 seconds.

(ii) Measurement of relaxation time The photochromic lenses obtained in Examples 1 and 2 and the reference example were irradiated with light in the same manner as in the above (i), and the photochromic dye was found in the light control characteristic curve shown in the upper diagram of FIG. The relaxation time during color development and color fading was determined as the time required to reach a certain equilibrium state during color development or color fading. Here, the “constant equilibrium state” is defined as 90 seconds during color development and 360 seconds during discoloration as the measurement time, indicating the change in the state of the dye during that time, and the relaxation time (reaching a constant equilibrium state). Time) was calculated by the following method.
First, after obtaining an initial value, a color change saturation value, and a change amount (initial value−color change saturation amount), a numerical value after each time has passed = ln ((transmission after each time −color change saturation value) / change amount) Was plotted every elapsed time (for example, 30 seconds) to create a linear approximation curve. After calculating the slope (1 / τ) of the created linear approximation curve, its reciprocal τ (sec) was determined and used as the relaxation time.
The results are shown in Table 3. The relaxation time is an index indicating dimming characteristics, and the smaller the value, the shorter the time required for the change, that is, the faster the color development speed and the color fading speed. Regarding color development, usually, if the relaxation time is different by about 3 seconds, the difference in color development rate can be visually confirmed. Further, for fading, normally, if the relaxation time is different by about 20 seconds, the difference in fading speed can be visually confirmed.

(4) Hardness measurement of photochromic film
(i) Ultra-fine indentation hardness The photochromic film was peeled off from the photochromic lenses obtained in Examples 1, 2, and 3 and Reference Example. By the method described above, the ultra-fine indentation hardness on both sides of the photochromic films of Examples 1, 2, and 3 was measured. In the same manner, the indentation hardness of the object side surface of the photochromic film of the reference example was measured. The results are shown in Table 2.

(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”.

(5) Presence or absence of striae About the photochromic lenses of Examples 1, 2, and 3, the presence or absence of striae was visually observed by the Schlieren method using an ultrahigh pressure mercury lamp. The results are shown in Table 2.

As shown in the upper diagram of FIG. 5, the transmittances of the lenses of Examples 1 and 2 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, as shown in the upper and lower diagrams of FIG. 5, the lenses of Examples 1 and 2 had lower light transmittance during irradiation than the lenses of the reference example. This indicates that the color density at the time of light irradiation is high.
Further, after the irradiation, the lenses of Examples 1 and 2 returned to their original transmittance earlier than the reference example lens, and had excellent photochromic properties.
When the rate of color change of the photochromic film on the lenses of Examples 1 and 2 and the reference example was quantified by the relaxation time, the color change rate of the lenses of Examples 1 and 2 as shown in Table 3 is the lens of the reference example. It was confirmed that it was faster.
Further, when the lens of Example 3 was measured in the same manner as described above, it exhibited excellent light control performance similar to the lenses of Examples 1 and 2.
As can be seen from the above results, the photochromic lenses of Examples 1 to 3 whose surface on the object side was softer than the lens of the reference example had excellent light control characteristics. Moreover, in Examples 1-3, since the hardness of the photochromic film surface which contacts a lens base material at the time of casting superposition | polymerization was controlled, an optical characteristic fell by mixing at the interface of a lens base material and a photochromic film | membrane during cast superposition | polymerization. It was possible to prevent the occurrence of striae.

[Example 4] (Hard layer, antireflection layer formation)
The meniscus-shaped photochromic lens having a photochromic film on the convex surface formed in Example 1 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 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.
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. As a result of evaluating the obtained photochromic lens, it was confirmed that a lens having no problem in adhesion and appearance and having no striae was obtained. The light control performance of the lens was evaluated by the same method as described above. The results are shown in FIG.
FIG. 6 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. 6, the lens of Example 4 had a high reaction speed and color development density, and excellent photoresponsiveness.

  The photochromic lens of the present invention has excellent light control performance and optical characteristics, and is suitable as a spectacle lens.

An example of the photochromic lens which has a photochromic film | membrane is shown. The schematic of the measuring method of super micro indentation hardness is shown. 1 shows a schematic diagram of a lens mold that can be used in the present invention. An example of UV ozone treatment is shown. The measurement result of the color development density of the photochromic film | membrane on the photochromic lens obtained in Example 1, 2 and the reference example, and a color-release rate is shown. The measurement result of the light control performance of the photochromic lens obtained in Example 4 is shown.

Claims (11)

A photochromic liquid containing a photochromic dye and a curable component is applied to one side of the first mold for forming one side of the lens,
By applying a curing treatment to the photochromic liquid, the outermost surface has an ultrafine indentation hardness of 500 to 5000 nm, and the ultrafine indentation hardness of the surface facing the first mold is the ultrafine indentation of the outermost surface. Form a photochromic film smaller than the small indentation hardness,
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 faces the second mold surface, and an annular gasket is provided around the two molds. To form a cavity in which the photochromic film is located by the two molds and gasket,
A photochromic lens characterized by injecting a lens raw material solution containing a curable component into the cavity and performing a curing reaction of the curable component in the cavity to obtain a photochromic lens having a photochromic film on a lens substrate. Manufacturing method. 2. The method for producing a photochromic lens according to claim 1, wherein the curing treatment is performed such that an ultra fine indentation hardness of a surface of the photochromic film facing the first mold is in a range of 800 to 5000 nm. The method for producing a photochromic lens according to claim 1 or 2, wherein a dry etching process using UV ozone or plasma is performed on the outermost surface of the photochromic film after the formation of the photochromic film and before the formation of the cavity. The curable component contained in a photochromic film | membrane is a photocurable component, The said hardening process is a manufacturing method of the photochromic lens of any one of Claims 1-3 performed by light irradiation. The said light irradiation is a manufacturing method of the photochromic lens of Claim 4 including performing light irradiation with respect to the photochromic liquid application surface of said 1st mold. The first mold has optical transparency,
The photochromic lens manufacturing method according to claim 4, wherein the light irradiation includes performing light irradiation on a photochromic liquid applied to the first mold via the first mold. The method for producing a photochromic lens according to claim 4, 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 6 or 7, wherein the light irradiation through the first mold is performed at a lower dose than the light irradiation on the photochromic liquid application surface. Wherein the light irradiation through an mold is carried out in irradiation amount of 0.1~30J / cm ^2, claim light irradiation to the photochromic solution-coated surface is carried out by irradiation of 1~100J / cm ² A method for producing the photochromic lens according to claim 8. The curable component contained in the said lens raw material liquid is a thermosetting component, The said hardening reaction is a manufacturing method of the photochromic lens of any one of Claims 1-9 performed by heating. The method for producing a photochromic lens according to claim 1, wherein the lens raw material liquid contains an ultraviolet absorber.