JP2014056140A - Method of manufacturing photochromic lens and precursor composition of photochromic coating liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a photochromic lens with a photochromic coating layer containing a high concentration of a photochromic compound.SOLUTION: A method of manufacturing a photochromic lens with a photochromic coating layer on a surface of a lens substrate includes the steps of: preparing a precursor composition of a coating liquid containing a radical polymerizable component, a halogenated organic solvent, and a photochromic compound; distilling the halogenated organic solvent from the precursor composition to obtain a photochromic coating liquid containing the radical polymerizable component and the photochromic compound; applying the photochromic coating liquid to the surface of the lens substrate and then hardening the coating liquid to form a photochromic coating layer on the surface of the lens substrate.

Description

  The present invention relates to a novel method for producing a photochromic lens in which a photochromic coating layer is laminated. Moreover, this invention relates to the novel precursor composition of the photochromic coating liquid used for the manufacturing method.

  Photochromic glasses are ordinary glasses that are colored and function as sunglasses when they are exposed to light containing ultraviolet rays such as sunlight, and the lenses quickly color and function as sunglasses. Glasses that function as In recent years, the demand for photochromic glasses having such characteristics has increased.

  As photochromic eyeglass lenses, those obtained by imparting photochromic performance to a plastic lens are widely used from the viewpoint of lightness and safety. In order to impart photochromic performance to a plastic lens, generally, an organic photochromic compound is used, and photochromic properties are imparted to the plastic lens by various methods. For example, a photochromic spectacle lens is manufactured by a method called a coating method. Specifically, it is a method for producing a photochromic lens having a photochromic coating layer by applying a photochromic coating liquid containing a radically polymerizable component and a photochromic compound to the surface of a plastic lens substrate and curing it.

  This coating method is an excellent method in that photochromic performance can be imparted regardless of the material of the plastic lens. However, in this method, since it is necessary to exhibit excellent photochromic characteristics in a thin photochromic coating layer, it is necessary to contain a large number of photochromic compounds in the coating layer. That is, it is necessary to relatively increase the concentration of the photochromic compound in the photochromic coating solution.

  Naturally, when the concentration of the photochromic compound is increased, it becomes difficult to dissolve in the radically polymerizable component and it cannot be used as a coating solution, and various improvements have been made. For example, a method is known in which an organic solvent having a boiling point exceeding 100 ° C., such as N-methylpyrrolidone, is added to the photochromic coating solution (see Patent Document 1). Moreover, in order to improve the solubility of a photochromic compound, the method of improving solubility by using the molecular compound of a photochromic compound and an aromatic compound is also known (refer patent document 2).

  However, these conventional methods have room for improvement in the following points. For example, in the method described in Patent Document 1, it is considered to improve the solubility of the photochromic compound, but in the examples, an organic solvent having a high boiling point such as N-methylpyrrolidone is used. Therefore, an organic solvent may remain in the photochromic coating layer, and there is room for improvement.

  On the other hand, in the method described in Patent Document 2, solubility in a radical polymerizable monomer having an aromatic ring can be improved by using a molecular compound. However, in this case, there is a room for improvement because the radical polymerizable monomer to be used may be limited.

  Further, in recent years, thin plastic lenses are frequently used from the viewpoint of design. In such lens coating, deformation of the lens is likely to occur due to polymerization shrinkage of the photochromic coating layer. Photopolymerization is used for coating such a lens, but in order to prevent deformation of the lens, temperature and light irradiation are highly controlled (for example, Patent Documents 3 and 4) or holding to hold the lens. It was necessary to improve the tool (for example, see Patent Document 5). Therefore, it has been desired to develop a method having a photochromic coating layer that is a thinner film and contains a photochromic compound at a higher concentration by improving the coating liquid itself than the conventional technique.

US Publication 2002-0076549 JP 2003-342310 A JP 2009-237003 A JP 2004-12857 A International Publication WO2006-132200 Pamphlet

  Accordingly, an object of the present invention is to form a photochromic coating layer containing a photochromic compound at a high concentration. In particular, it can be suitably applied to a lens substrate having a thin central portion, and further to produce a photochromic lens having excellent photochromic characteristics even when the photochromic coating layer is thin.

  The present inventors have made extensive studies to solve the above problems. As a result, it has been found that the above problem can be solved by the following method. That is, first, a precursor composition of a photochromic coating solution containing a halogen-based organic solvent is once prepared. Then, the photochromic coating liquid obtained by distilling off the organic solvent from the precursor composition has an action of the organic solvent in which the photochromic compound is supersaturated with respect to the radical polymerizable monomer component or a small amount remains. However, it has been found that a solution in which the photochromic compound is dissolved is obtained for a short time (during the coating operation). Furthermore, it discovered that the said subject could be solved by using this photochromic coating liquid, and came to complete this invention.

That is, the present invention is a method for producing a photochromic lens having a photochromic coating layer on the surface of a lens substrate,
A step of preparing a precursor composition of a coating liquid containing a radical polymerizable monomer component, a photochromic compound, and a halogen-based organic solvent (hereinafter, also referred to as “preparation step”),
A step of preparing a photochromic coating solution containing a radical polymerizable monomer component and a photochromic compound by distilling off the halogen-based organic solvent from the precursor composition (hereinafter sometimes referred to as “coating solution production step”). ), And a step of forming a photochromic coating layer on the surface of the lens substrate by applying the photochromic coating solution to the surface of the lens substrate and then curing the coating solution (hereinafter referred to as “coating step”). There is also)
It is a manufacturing method of the photochromic lens characterized by including.

  According to the present invention, once a precursor composition of a coating liquid containing a radical polymerizable monomer component, a photochromic compound, and a halogen-based organic solvent is prepared, a photochromic compound for the radical polymerizable monomer component is prepared. The concentration of can be increased. Moreover, even if it is a photochromic compound with low solubility with respect to a radically polymerizable monomer component by using a halogen-type organic solvent, it can be prepared as a precursor composition. Furthermore, the coating liquid obtained by distilling off the halogen-based organic solvent from this precursor composition can form a photochromic coating layer containing a high concentration photochromic compound. Even if the photochromic coating layer is thin, sufficient photochromic properties can be exhibited. As a result, even if a photochromic coating layer is laminated on a lens substrate having a thin central portion, a photochromic lens having no photodeformation and good photochromic characteristics can be manufactured. In the present invention, the methods described in Patent Documents 3 and 4 and Patent Document 5, specifically, the light irradiation method, the method for controlling the temperature, and the method for improving the lens holding member in the coating process. By adopting, a higher quality photochromic lens can be manufactured.

  Furthermore, long-term preservation | save becomes possible by preparing the precursor composition containing a high concentration photochromic compound by a preparatory process. Further, the photochromic compound can be dissolved in a simple operation and in a short time.

  The present invention is a method for producing a photochromic lens having a photochromic coating layer on the surface of a lens substrate. First, the lens substrate that can be used in the present invention will be described.

(Lens base material)
The lens substrate of the present invention may be made of plastic or glass. In particular, the method of the present invention can be suitably applied when using a plastic lens substrate that is easily deformed by heat.

  The reason why the lens substrate is particularly useful for a plastic substrate is as follows. When the photochromic coating solution of the present invention is applied to the surface of the lens substrate to form a photochromic coating layer, the photochromic coating solution is cured by light irradiation or the like. At this time, the photochromic coating layer contracts due to polymerization, whereas the lens base material is heated by the infrared rays contained in the light source used for polymerization heat generation or light irradiation, and therefore has a thermal expansion or heat resistance. Softening occurs if the substrate is low. As a result, particularly in a lens having low heat resistance and a thin center thickness, there is a possibility that the lens cannot withstand the stress of the shrinking photochromic coating layer and deform. Under this condition, if the photochromic lens manufacturing method of the present invention is employed, the photochromic coating layer can be laminated thinner than the conventional one, so that the stress due to the shrinkage of the photochromic coating layer can be reduced. As a result, it is possible to suppress deformation of the lens base material.

Typical plastic materials for forming the lens substrate include (meth) acrylic resins, polycarbonate resins, allyl resins, thiourethane resins, urethane resins, and thioepoxy resins. The method of the present invention is useful when using a material with low possibility of deformation and low heat resistance. Specifically, it is useful when using a material having a softening point of 100 ° C. or less that serves as an index of heat resistance. Examples of such a material having low heat resistance include allyl resins, thiourethane resins, and urethane resins.
Further, the method of the present invention can be suitably applied to a lens base material in which the thickness (center thickness) of the center portion of the lens is thin. When a lens having a thin center thickness is used, the lens base material is easily deformed, so that the method of the present invention can be suitably employed for the same reason. Specifically, the method of the present invention can be applied to a lens having a center thickness in the range of 0.5 to 5.0 mm, and more preferably in a range of 0.5 to 2.0 mm. In particular, it can be applied to the range of 0.5 to 1.5 mm.

  Moreover, the lens base material used by this invention may laminate | stack the primer layer on the surface from a viewpoint of improving adhesiveness. Among them, a thermoplastic resin such as a polycarbonate-based resin may be dissolved when the photochromic coating liquid in the present invention is applied. In this case, it is preferable to laminate a solvent-resistant layer (such as a primer layer or a hard coat layer) on the surface of the thermoplastic resin.

  In this invention, it is a manufacturing method of the photochromic lens which has a photochromic coating layer on the surface of the said lens base material, Comprising: The following processes are included. That is, this invention is a manufacturing method of the photochromic lens characterized by including a preparatory process, a coating liquid manufacturing process, and a coating process. Hereinafter, each step will be described in order.

(Preparation process)
In the present invention, the preparation step is a step of preparing (manufacturing) a precursor composition of a coating liquid containing a radical polymerizable monomer, a photochromic compound, and a halogen-based organic solvent. This precursor composition will be described.

(Precursor composition)
The precursor composition contains a radical polymerizable monomer component (I), a photochromic compound (II), and a halogen-based organic solvent (III). Each component will be described.

<(I) Radical polymerizable monomer component>
What is necessary is just to determine suitably as a radically polymerizable monomer component used for this invention according to the lens base material to be used, the desired physical property, etc. Specifically, a (meth) acrylic polymerizable monomer having a methacryl group or an acrylic group, a styrene polymerizable monomer, an allyl polymerizable monomer, a polymerizable monomer having a vinyl group, Etc. These polymerizable monomers can also be used in combination of a plurality of types of polymerizable monomers. Among these, it is preferable to use a (meth) acrylate polymerizable monomer as a main component.

  When a (meth) acrylyl polymerizable monomer is used, a monofunctional polymerizable monomer, a bifunctional polymerizable monomer, and a trifunctional or higher functional polymerizable monomer can be used. A plurality of these polymerizable monomers can be used in combination. Among these, it is preferable to include a bifunctional polymerizable monomer (I-1) represented by the following formula (1).

((I-1): bifunctional polymerizable monomer represented by formula (1))
The bifunctional polymerizable monomer (I-1) is represented by the following general formula (1).

  In the general formula (1), a is a number from 0 to 30 and b is a number from 0 to 30 on condition that the average value of a + b is 2 to 30.

R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom or a methyl group.

  Furthermore, A is a divalent organic group selected from the following group on condition that the carbon number is 1-20. An alkylene group; an unsubstituted phenylene group; a phenylene group having a halogen atom or an alkyl group having 1 to 4 carbon atoms as a substituent; and a divalent group represented by the following formula (1a), (1b) or (1c) Group;

式（１ｃ）中、
Ｒ^５及びＲ^６は、炭素数１〜４のアルキル基又はハロゲン原子、
ｃ及びｄは、０〜４の整数、
六員環Ｂは、ベンゼン環又はシクロヘキサン環、
前記六員環Ｂがベンゼン環であるときには、Ｘは、−Ｏ−、−Ｓ−、
−Ｓ(Ｏ)_２−、−Ｃ(Ｏ)−、−ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ(ＣＨ_３)_２−、
−Ｃ(ＣＨ_３)(Ｃ_６Ｈ_５)−または下記式（１ｃ−１）；

In formula (1c),
R ⁵ and R ⁶ are each an alkyl group having 1 to 4 carbon atoms or a halogen atom,
c and d are integers of 0 to 4,
The six-membered ring B is a benzene ring or a cyclohexane ring,
When the six-membered ring B is a benzene ring, X is -O-, -S-,
_{-S (O) 2 -, -} C (O) -, - CH 2 -, - CH = CH -, - C (CH 3) 2 -,
_{-C (CH 3) (C 6} H 5) - or the following formula (1c-1);

で示される２価の基、
前記六員環Ｂが、シクロヘキサン環であるときは、Ｘは、−Ｏ−、−Ｓ−、
−ＣＨ_２−または−Ｃ(ＣＨ_３)_２−で示される２価の基である。

A divalent group represented by
When the six-membered ring B is a cyclohexane ring, X is —O—, —S—,
A divalent group represented by —CH ₂ — or —C (CH ₃ ) ₂ —.

  In the general formula (1), the divalent group A is an organic group having 1 to 20 carbon atoms, and the alkylene group in the organic includes an ethylene group, a propylene group, a butylene group, and a nonylene group. Can be mentioned.

  Examples of the phenylene group having a halogen atom or an alkyl group having 1 to 4 carbon atoms as a substituent include a dimethylphenylene group, a tetramethylphenylene group, a dibromophenylene group, and a tetrabromophenylene group.

  When the photochromic curable composition of the present invention is used as a coating agent, the bifunctional radical polymerizable monomer (I-1) is a long chain having an average value of a + b in the general formula (1) of 6 to 30. It is particularly preferable that the bifunctional polymerizable monomer (I-1) is included. By using the long-chain bifunctional polymerizable monomer (I-1), the free space in the cured product becomes even wider. As a result, the blending ratio of the photochromic compound (II) is large, and excellent photochromic properties can be exhibited in a cured product (photochromic coating layer) that is a thin film.

  The long-chain bifunctional polymerizable monomer (I-1) used in the present invention is particularly excellent when belonging to a low-hardness monomer in which the L-scale Rockwell hardness of the homopolymer is 40 or less. It is preferable for ensuring high photochromic properties.

  The L scale Rockwell hardness means a hardness measured according to JIS-B7726, and the L scale Rockwell hardness of a homopolymer (polymerized by 90% by mass or more of the monomer) is 40 or less. Low hardness monomers are known and are described in detail, for example, in Japanese Patent No. 4016119.

Examples of the long-chain bifunctional radically polymerizable monomer (I-1) preferably used in the present invention include the following monomers.
Polyethylene glycol dimethacrylate (average molecular weight 536)
(Average chain length of ethylene glycol chain: 9 (average value of a + b: 8, A is ethylene group))
Polyethylene glycol dimethacrylate (average molecular weight 736)
(Average chain length of ethylene glycol chain: 14 (average value of a + b 13, 13 is ethylene group))
Polyethylene glycol dimethacrylate (average molecular weight 1136)
(Average chain length of ethylene glycol chain: 23 (average value of a + b 22, A is ethylene group))
Polypropylene glycol dimethacrylate (average molecular weight 662)
(Average chain length of propylene glycol chain: 9 (average value of a + b: 8, A is propylene group))
Polyethylene glycol diacrylate (average molecular weight 508)
(Average chain length of ethylene glycol chain: 9 (average value of a + b: 8, A is ethylene group))
Polyethylene glycol diacrylate (average molecular weight 708)
(Average chain length of ethylene glycol chain: 14 (average value of a + b 13, 13 is ethylene group))
Polypropylene glycol diacrylate (average molecular weight 536)
(Average chain length of propylene glycol chain: 7 (average value of a + b, 6, A is propylene group))
Polypropylene glycol diacrylate (average molecular weight 808)
(Average chain length of propylene glycol chain: 12 (average value 11 of a + b, A is propylene group))
2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 10);
2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 20);
2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 30);
2,2-bis [4-acryloxy (polyethoxy) phenyl] propane (a + b = 10).

  Among the monomers exemplified above, the divalent organic group A in the general formula (1) is represented by the following formula (1c ′);

And those in which the divalent group A is an ethylene group, a propylene group, or a butylene group are photochromic coating agents because the solubility of the photochromic compound is relatively high and a high color density can be secured. It is suitable for the use as.

Examples of such monomers are as follows.
2,2-bis [4-acryloxy (polyethoxy) phenyl] propane (a + b = 10);
2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 10);
2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 20);
2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 30);
Polyethylene glycol dimethacrylate (average molecular weight 536)
(Average chain length of ethylene glycol chain: 9 (average value of a + b: 8, A is ethylene group))
Polyethylene glycol dimethacrylate (average molecular weight 736)
(Average chain length of ethylene glycol chain: 14 (average value of a + b 13, 13 is ethylene group))
Polypropylene glycol dimethacrylate (average molecular weight 662)
(Average chain length of propylene glycol chain: 9 (average value of a + b: 8, A is propylene group))
Polyethylene glycol diacrylate (average molecular weight 508)
(Average chain length of ethylene glycol chain: 9 (average value of a + b: 8, A is ethylene group))
Polypropylene glycol diacrylate (average molecular weight 536)
(Average chain length of propylene glycol chain: 7 (average value of a + b is 6, A is propylene group)).

Furthermore, in the general formula (1), a monomer having a hydrogen atom in R ¹ , R ² , R ³ and R ⁴ , that is, a monomer having an ethylene glycol part as a main chain has a relatively high solubility of the photochromic compound, This is useful for exhibiting excellent photochromic properties. Among them, 2,2-bis [4-methacryloxy (polyethoxy) phenyl] propane (a + b = 10) and polyethylene glycol diacrylate (average chain length of ethylene glycol chain: 9 (average value of a + b: 8, A is ethylene group)) Is preferred.

  It is preferable to use the radical polymerizable monomer component (I) containing the bifunctional polymerizable monomer (I-1) represented by the above formula (1). In order for the photochromic coating layer to be formed to exhibit an excellent effect, the radical polymerizable monomer component (I) contains silsesquioxane (I-2) having at least one radical polymerizable group. It is preferable. Next, the silsesquioxane (I-2) will be described.

(I-2) Silsesquioxane;
The silsesquioxane (I-2) used as the radical polymerizable component in the present invention contains a silsesquioxane having at least one radical polymerizable group (hereinafter simply referred to as “silsesquioxane component ( I-2) may be a polymerizable silsesquioxane component (I-2) ").

That is, silsesquioxane is a polysiloxane whose basic structural unit is a T unit, and has the following composition formula (2);
(R-SiO _3/2 ) g (2)
It is represented by

  In the composition formula (3), g is a number indicating the degree of polymerization, and is generally a number in the range of 4 to 100.

  R represents a substituent bonded to a silicon atom.

  The silsesquioxane component (I-2) used in the present invention is composed of an organopolysiloxane represented by the basic composition formula (2) as described above, but at least one of the above groups R is radical polymerization. It contains silsesquioxane molecules that are functional groups.

  Examples of the radical polymerizable group include groups having a (meth) acryl group such as a (meth) acryloxypropyl group and (3- (meth) acryloxypropyl) dimethylsiloxy group; allylpropyl group, allylpropyldimethyl A group having an allyl group such as a siloxy group; a group having a vinyl group such as a vinylpropyl group, a vinyloctyl group or a vinyldimethylsiloxy group; a group having a cyclohexenyl group such as a (4-cyclohexenyl) ethyldimethylsiloxy group; In particular, a group having a (meth) acrylic group is preferable from the viewpoint that a cured product having high hardness can be formed.

  The radical polymerizable group as described above is 10 to 100%, more preferably 30 to 100%, particularly 70 to 100% of the total number of substituents R contained in the silsesquioxane component (I-2). In order to obtain a cured product having excellent hardness and photochromic properties, it is desirable that

  In the compositional formula (2), a plurality (g) of groups R present in the molecule may be the same or different from each other, and further, a silsesquioxy having at least one radical polymerizable group. It may be a group other than a radical polymerizable group, provided that it contains a sun molecule.

  Examples of the group R other than the radical polymerizable group include a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms. And a halogenated alkyl group, an unsubstituted phenyl group, a halogenated phenyl group, or a hydroxyl group.

  Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. Is mentioned.

  Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclooctyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, and tert-butoxy group.

  Examples of the halogenated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a pentafluoroethyl group, a chloromethyl group, a 2-chloroethyl group, and a bromomethyl group.

  Examples of the halogenated phenyl group include 4-chlorophenyl group and 4-bromophenyl group.

  The above-mentioned radical polymerizable silsesquioxane component (I-2) is a silsesquioxane having various structures such as a ladder structure, a cage structure and a random structure as long as the condition that a radical polymerizable group is present is satisfied. Oxane may be contained, and silsesquioxanes having various structures may be mixed.

  As the radically polymerizable silsesquioxane component (I-2) described above, a commercially available product produced by a known method can be used.

For example, as the radical polymerizable silsesquioxane component (I-2) containing silsesquioxane having a cage structure, there are the following commercially available products.
Toagosei Co., Ltd. AC-SQ TI-100:
Polyacryloxypropyl polyorganosiloxane (weight average molecular weight 2100)
Toagosei Co., Ltd. MAC-SQ TM-100:
Polymethacryloxypropyl polyorganosiloxane (weight average molecular weight 2500)
Toagosei Co., Ltd. Q-8:
Octa [(3-methacryloxypropyl) dimethylsiloxy] silsesquioxane Toagosei Co., Ltd. Q-6:
Octa [2- (vinyl) dimethylsiloxy] silsesquioxane.

  Silsesquioxane can be produced by hydrolyzing and condensing a predetermined silyl compound. For example, a high molecular weight silsesquioxane can also be produced according to a method described in a cited document (Appl. Organometal. Chem. 2001, p. 683-692).

  Further, the high molecular weight silsesquioxane component (I-2) used in the present invention is composed of 1 to 3 equivalents of water with respect to a silyl compound (for example, 3-trimethoxysilylpropyl methacrylate) as a raw material, and It can also be produced by mixing a base such as sodium hydroxide as a catalyst and reacting at a temperature of 0 to 40 ° C. In addition, the organic solvent (for example, alcohol etc.) which melt | dissolves a raw material and a product can also be used at the time of reaction. However, when using an organic solvent, in order to obtain a high molecular weight silsesquioxane component (I-2), the amount used is preferably 4 times the amount (vol / wt) or less of the raw material. . The high molecular weight silsesquioxane component (I-2) obtained by such a method is a mixture of a silsesquioxane having a cage structure, a ladder structure, a random structure and an incomplete cage structure.

  This silsesquioxane component (I-2) is blended in order to form an excellent photochromic coating layer. However, the photochromic coating solution containing the silsesquioxane component (I-2) may reduce the solubility of the photochromic compound. Therefore, the method of the present invention exhibits an excellent effect when the radical polymerizable monomer component (I) contains the silsesquioxane component (I-2).

  The radical polymerizable monomer component (I) includes a photochromic coating layer exhibiting excellent performance in addition to the bifunctional polymerizable monomer (I-1) and the silsesquioxane component (I-2). In order to form, it is preferable to include a polyfunctional polymerizable monomer represented by the following formula (3). The trifunctional or higher polyfunctional polymerizable monomer (I-3) represented by the formula (3) will be described.

((I-3): polyfunctional polymerizable monomer represented by formula (3))
The polyfunctional polymerizable monomer (I-3) is represented by the following general formula (3).

Where
R ⁷ and R ⁸ are each independently a hydrogen atom or a methyl group,
R ⁹ is a trivalent to hexavalent organic group having 1 to 10 carbon atoms,
e is an average value of 0 to 3;
f is an integer of 3-6.

  The polyfunctional polymerizable monomer represented by the general formula (3) is effective not only for increasing the hardness of the obtained photochromic cured product but also for improving the photochromic properties, particularly the color density and the fading speed.

  Examples of the polyfunctional polymerizable monomer represented by the general formula (3) include, for example, the following, and these polyfunctional radical polymerizable monomers may be used alone or in combination of two kinds. It can be used in combination of the above. Specifically, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane tetramethacrylate, tetramethylol methane tetraacrylate, trimethylol propane triethylene glycol trimethacrylate, Trimethylolpropane triethylene glycol triacrylate, ditrimethylolpropane tetramethacrylate, ditrimethylolpropane tetraacrylate, polyester oligomer having 4 (meth) acryl groups, polyester oligomer having 6 (meth) acryl groups, (meth) acryl group Polyurethane oligomer having 4 and 6 (meth) acrylic groups Polyurethane oligomer that, among these, trimethylol propane trimethacrylate are especially preferred.

  By combining such a polyfunctional polymerizable monomer (I-3), the hardness of the cured product can be further improved without impairing photochromic properties. That is, the use of such a polyfunctional polymerizable monomer (I-3) is advantageous for the production of a photochromic lens having a photochromic coating layer, and is extremely advantageous for improving the processability of such a photochromic lens. It is.

  The radical polymerizable monomer component (I) can also contain polymerizable monomers other than the components (I-1), (I-2), and (I-3). Next, the other radical polymerizable monomer component (I-4) will be described.

((I-4) Other radical polymerizable monomer)
The radical polymerizable monomer (I) used in the present invention includes the above-mentioned bifunctional polymerizable monomer (I-1), radical polymerizable silsesquioxane component (I-2), polyfunctional polymerizable monomer. A polymerizable monomer other than the monomer (I-3) can also be contained. Hereinafter, these other radically polymerizable monomers will be described.

  First, as another radical polymerizable monomer, a monofunctional polymerizable monomer represented by the following formula (4) may be mentioned.

  In the above general formula (4), j is a number from 0 to 25, k is a number from 0 to 25, and the value of j + k averages from 0 to 25, particularly from 0 to 15. Is preferred.

Moreover, in General formula (4), R <^11> , R < ¹² > and R < ¹³ > are a hydrogen atom or a methyl group, respectively.

R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group, or a glycidyl group.

In the above group R ¹⁴ , each of the phenyl group and the naphthyl group may have an alkyl group having 1 to 20 carbon atoms as a substituent.

  Preferable examples of the monofunctional radically polymerizable monomer represented by the general formula (4) include the following, and these can be used alone or in combination of two or more. Specifically, methoxydiethylene glycol methacrylate; methoxytetraethylene glycol methacrylate; isostearyl methacrylate; isobornyl methacrylate; phenoxyethylene glycol methacrylate; phenoxyethyl acrylate; phenoxydiethylene glycol acrylate; naphthoxyethylene glycol acrylate; isostearyl acrylate; Acrylate; Glycidyl methacrylate; Methoxy polyethylene glycol methacrylate (average chain length of ethylene glycol chain (j + k): 9, average molecular weight: 468); Methoxy polyethylene glycol methacrylate (average chain length of ethylene glycol chain (j + k): 23, average molecular weight: 1068); phenoxypolyethylene glycol Acrylate (average chain length of ethylene glycol chains (j + k): 6, average molecular weight: 412) and the like. By using the monofunctional polymerizable monomer represented by the formula (4), physical properties such as the viscosity of the photochromic coating solution can be adjusted.

Among the above, those in which the group R ¹⁴ in the general formula (4) is a glycidyl group (for example, glycidyl methacrylate) is advantageous in improving the repeated durability of the photochromic characteristics, and is hardened to any of the molding materials of the photochromic lens. Even when an adhesive composition is used, excellent photochromic properties can be ensured.

  Furthermore, in this invention, it aims at ensuring the adhesiveness of a hard-coat film | membrane in the hardening body obtained by using the 1 type (s) or 2 or more types of the silane type | system | group monofunctional radical polymer represented by following General formula (5). It can also be used as

  In the general formula (5), l is an integer of 1 to 3 and m is an integer of 0 to 2 on condition that l + m = 3.

R ¹⁵ is a hydrogen atom or a methyl group.

R ¹⁶ is an alkylene group having 1 to 10 carbon atoms, such as an ethylene group, a propylene group, or a butylene group.

R ¹⁷ is an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, or a propoxy group.

R ¹⁸ is an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, or a propyl group.

  Specific examples of such a silane monofunctional radical polymerizable monomer include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and the like.

  Furthermore, the following alkanediol di (meth) acrylates can also be used. Specifically, 1,3-butanediol dimethacrylate; 1,6-hexanediol dimethacrylate; 1,9-nonanediol dimethacrylate; 1,10-decanediol dimethacrylate; neopentyl glycol dimethacrylate; Candimethanol dimethacrylate; 1,6-hexanediol diacrylate; 1,9-nonanediol diacrylate; 1,10-decanediol diacrylate; neopentyl glycol diacrylate; tricyclodecane dimethanol diacrylate.

  Further, as the other polymerizable monomer (I-4), a radical polymerizable monomer having a urethane bond in the molecule, for example, urethane (meth) acrylate can also be suitably used. Urethane (meth) acrylate is a polymer synthesized by reacting an OH group-containing (meth) acrylate with a urethane prepolymer obtained by the reaction of diisocyanate and polyol, and the light resistance of the cured product is particularly good. From the viewpoint that yellowing due to light irradiation is prevented, an aliphatic one having no aromatic ring such as a benzene ring in the molecule is preferable.

  For example, in the above aliphatic urethane (meth) acrylate, the diisocyanate used for the production of the urethane prepolymer is hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate. Isopropylidenebis-4-cyclohexyl isocyanate, dicyclohexylmethane diisocyanate, norbornene diisocyanate, methylcyclohexane diisocyanate, or the like is used.

  Further, polyols to be reacted with diisocyanate are roughly classified into high molecular weight and low molecular weight. Among these, as the high molecular weight polyol, polyalkylene glycol having 2 to 6 alkylene oxides (ethylene oxide, propylene oxide, hexamethylene oxide, etc.) as a repeating unit; polyester diol such as polycaprolactone diol; polycarbonate diol; polybutadiene diol And the like. Examples of low molecular weight polyols include pentaerythritol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9 -Nonanediol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, glycerin, trimethylolpropane, pentaerythritol, etc. it can.

  Furthermore, as the OH group-containing (meth) acrylate to be reacted with the urethane polymer, 2-hydroxyethyl (meth) acrylate or (meth) acrylic acid in which the OH group is linked to the (meth) acryloyl group via an alkylene oxide chain Examples include esters. Any of these urethane (meth) acrylates can be used alone or in combination of two or more.

  The aliphatic urethane (meth) acrylate as described above preferably has a molecular weight of 400 or more and less than 20,000 from the viewpoint of imparting a suitable viscosity as a coating agent to the photochromic curable composition.

  As other radical polymerizable monomers (I-4), monofunctional polymerizable monomers represented by general formulas (4) and (5), urethane (meth) acrylate, alkanediol di (meth) acrylate, By using them individually or in combination, the hardness and photochromic properties of the cured product can be further improved, or the physical properties such as the viscosity of the photochromic curable composition can be adjusted to an appropriate range. In addition, styrenic monomers can also be blended.

(Preferred blending ratio of radical polymerizable monomer component (I))
The bifunctional polymerizable monomer (I-1) represented by the formula (1) can be used alone or in combination of two or more kinds. When mixed and used, the total mass may be the reference mass of the bifunctional polymerizable monomer (I-1). Further, when two or more kinds of other silsesquioxane components (I-2) and polyfunctional polymerizable monomers (I-3) are used, the total mass may be used as a reference. . Other radical polymerizable monomers may be based on the total mass when two or more types are used.

  In the present invention, the radically polymerizable monomer component (I) can be appropriately determined in an optimum blending ratio depending on the lens base material, photochromic compound and the like to be used. Among them, per 100 parts by mass of the bifunctional polymerizable monomer (I-1), the silsesquioxane component (I-2), the polyfunctional polymerizable monomer (I-3), and other radical polymerizable monomers It is preferable that the total of the monomer (I-4) is 0 to 300 parts by mass. As a more detailed preferred blend, 0 to 150 parts by mass of the silsesquioxane component (I-2) per 100 parts by mass of the bifunctional polymerizable monomer (I-1), the polyfunctional polymerizable monomer (I -3) It is preferable to set it as 10-100 mass parts and 0.5-50 mass parts of other radically polymerizable monomers (I-4). Furthermore, considering the hardness, scratch resistance, and moldability of the formed photochromic coating layer, the silsesquioxane component (I-2) 10 per 100 parts by mass of the bifunctional polymerizable monomer (I-1) To 50 parts by mass, 10 to 50 parts by mass of the polyfunctional polymerizable monomer (I-3), and 0.5 to 20 parts by mass of the other radical polymerizable monomer (I-4).

  In addition, the compounding ratio of the halogen-type organic solvent, photochromic compound, and other additive which are explained in full detail below is the value which converted the said radical polymerizable monomer component (I) as 100 mass parts. That is, bifunctional polymerizable monomer (I-1), silsesquioxane component (I-2), polyfunctional polymerizable monomer (I-3), and other radical polymerizable monomers (I -4) is referred to as a reference mass (100 parts by mass), and is described as a blending ratio thereof.

<(II) Photochromic compound>
Typical photochromic compounds used in the present invention are fulgide compounds, spirooxazine compounds and chromene compounds, but any of these known photochromic compounds can be used in the present invention.

  For example, fulgide compounds include, but are not limited to, those listed in US Pat. No. 4,882,438, US Pat. No. 4,960,678, US Pat. No. 5,130,058, etc. Can be used.

  Further, the spirooxazine compound is not limited to this, but those disclosed in JP-A-2006-335024, JP-A-2010-59288, JP-A-2010-59289, etc. should be used. Can do.

  Further, the chromene compound is not particularly limited, but what has been proposed so far, for example, U.S. Pat. No. 5,106,998, JP-A No. 2001-114775, JP-A No. 2001-031670, JP-A No. 2001-011067, JP2001-011066, JP2000-347346, JP2000-344762, JP2000-344761, JP2000-327676, JP2000-327675, JP2000-256347, Special JP 2000-229976, JP 2000-229975, JP 2000-229974, JP 2000-229993, JP 2000-229972, JP 2000-219687, JP 2000-219686, JP 2000-19685, JP-A-11-32 739, JP 11-286484, JP 11-279171, JP 10-298176, JP 09-218301, JP 09-124645, JP 08-295690, JP 08-176139. No., Japanese Patent Application Laid-Open No. 08-157467, etc. are preferably used.

  In the present invention, among the above-mentioned photochromic compounds, a chromene compound is preferably used in that not only the repeated durability of the photochromic reversible reaction is excellent, but also the photochromic color density is high and the fading speed is fast.

  Among chromene compounds, those having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton, for example, chromene compounds represented by the following general formula (6) are most preferable.

In the formula, n is an integer of 0 to 4,
o is an integer from 0 to 4,
R ^{19 to} R ²⁴ are substituents.

  That is, those having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton exhibit excellent photochromic properties (color density and fading speed) when combined with the radical polymerizable component of the present invention. .

Incidentally, each group ^R 19 ^{to R 24} in the general formula (6) are as follows.
(Group R ¹⁹ and Group R ²⁰ )
The group R ¹⁹ and the group R ²⁰ are a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group in which the nitrogen atom is directly bonded to a carbon atom of the benzene ring, cyano Group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, aralkyl group, aryl group or aryloxy group.

When n or “o” is a number of 2 or more and the group R ¹⁹ or the group R ²⁰ is present at a position adjacent to each other, the group R ¹⁹ or the group R ²⁰ is bonded to each other to form a carbon number. May form an alkylenedioxy group having 1 to 8 (for example, a methylenedioxy group or an ethylenedioxy group). Further, when n or “o” is a number of 2 or more, the plurality of groups R ¹⁹ or groups R ²⁰ may be the same as or different from each other.

  As said alkyl group, a C1-C6 alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl. Group, n-hexyl group and the like are preferable.

  The halogen atom of the haloalkyl group is preferably a fluorine atom, a chlorine atom or a bromine atom, and the haloalkyl group preferably has 1 to 6 carbon atoms. For example, suitable haloalkyl groups include trifluoromethyl group, pentafluoroethyl group, chloromethyl group, 2-chloroethyl group, bromomethyl group and the like.

  As the cycloalkyl group, those having 3 to 8 carbon atoms, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like are preferable.

  As an alkoxy group, a C1-C6 thing, for example, a methoxy group, an ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group etc. are preferable.

The amino group is not limited to an unsubstituted group (—NH ₂ ), and one or two hydrogen atoms bonded to a nitrogen atom may be substituted. Examples of the substituent that the amino group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aryl group having 6 to 14 carbon atoms. And a heteroaryl group having 4 to 12 carbon atoms.

  As said alkyl group, an alkoxy group, and a cycloalkyl group, the group similar to what was illustrated above can be mentioned, respectively. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the heteroaryl group include thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, and benzopyrrolinyl group.

In the present invention, amino groups suitable as the group R ¹⁹ and the group R ²⁰ include, in addition to an unsubstituted amino group, a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a phenylamino group, a diphenylamino group, and the like. Can be mentioned.

  The heterocyclic ring includes a nitrogen atom and the nitrogen atom is directly bonded to a carbon atom of the benzene ring. Preferred examples include a morpholino group, a piperidino group, a pyrrolidinyl group, a piperazino group, an N-methylpiperazino group. Group, indolinyl group and the like.

  Moreover, this heterocyclic group may have a C1-C6 alkyl group (for example, methyl group) as a substituent. Examples of the heterocyclic group having such a substituent include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, 2,2,6,6-tetramethylpiperidino group and the like. it can.

  As the alkylcarbonyl group, an acetyl group, an ethylcarbonyl group and the like are preferable.

  As the alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group and the like are preferable.

The halogen atom as the group R ¹⁹ and the group R ²⁰ may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

  As the aralkyl group, those having 7 to 11 carbon atoms, for example, benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group and the like are preferable.

  As the aryl group, those having 6 to 14 carbon atoms, for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like are preferable.

  As the aryloxy group, those having 6 to 14 carbon atoms such as phenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like are preferable.

  In the aralkyl group, aryl group, and aryloxy group, 1 to 13 hydrogen atoms such as a benzene ring or a naphthalene ring, particularly preferably 1 to 4 hydrogen atoms are the above hydroxyl group, alkyl group, haloalkyl group. A group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group, a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a halogen atom.

(Group R ²¹ and Group R ²² )
In the general formula (6), the groups R ²¹ and R ²² may be a hydrogen atom or the same group as the groups R ¹⁹ and R ²⁰ . In this case, the heterocyclic ring contains a nitrogen atom and the nitrogen atom is directly bonded to a carbon atom of the indene ring.

R ²¹ and R ²² may be combined with each other to form a ring together with the carbon atom of the indene ring. Examples of such a ring include an aliphatic ring having 3 to 20 ring atoms, a condensed polycycle in which an aromatic ring or an aromatic heterocycle is condensed to the aliphatic ring, and a ring atom number of 3 to 3. 20 or a condensed polycyclic ring in which an aromatic ring or an aromatic heterocycle is condensed to the heterocyclic ring. Particularly preferred rings are shown below. The position indicated by Z in the formula corresponds to the carbon atom of the indene ring to which the group R ²¹ and the group R ²² are bonded.

(Group R ²³ and Group R ²⁴ )
In the general formula (6), the groups R ²³ and R ²⁴ are an aryl group, a heteroaryl group, and an alkyl group.

As said aryl group and alkyl group, the same thing as the aryl group illustrated regarding group R ¹⁹ can be mentioned.

As said heteroaryl group, a C4-C12 thing, for example, a thienyl group, a furyl group, a pyrrolinyl group, a pyridyl group, a benzothienyl group, a benzofuranyl group, a benzopyrrolinyl group etc. are preferable. Further, in such a heteroaryl group, 1 to 7, particularly 1 to 4 hydrogen atoms may be substituted. Examples of such a substituent include an alkyl group having 1 to 6 carbon atoms, carbon A C1-C6 alkoxy group, a C3-C8 cycloalkyl group, or a halogen atom can be mentioned. These substituents may be the same as illustrated for the group R ¹⁹ .

Further, the groups R ²³ and R ²⁴ in the general formula (6) may be groups represented by the following formula (7) or (8).

In the above formula,
p and q are each an integer of 1 to 3 (usually 1 for easy availability of raw materials),
R ²⁵ is an aryl group or a heteroaryl group,
R ²⁶ represents a hydrogen atom, an alkyl group or a halogen atom,
R ²⁷ is an aryl group or a heteroaryl group.

The aryl group, heteroaryl group and alkyl group in the groups R ^{25 to} R ²⁷ are the same as those exemplified for the groups R ²³ and R ²⁴ .

  The halogen atom may be any of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Further, the groups R ²³ and R ²⁴ in the general formula (6) may be bonded to each other to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.

In particular, in order to exhibit excellent photochromic properties, at least one of the groups R ²³ and R ²⁴ , preferably both groups are aryl groups or heteroaryl groups, in particular the aryl groups of the following (a1) to (a4): It is preferably a heteroaryl group.
(A1) An aryl group or heteroaryl group having an alkyl group or an alkoxy group as a substituent.
(A2) An aryl group or heteroaryl group having an amino group as a substituent.
(A3) An aryl group or heteroaryl group having a heterocyclic group as a substituent, the heterocyclic group having a nitrogen atom as a heteroatom, and the nitrogen atom directly bonded to the aryl group or heteroaryl group What you are doing.
(A4) An aryl group or heteroaryl group having, as a substituent, a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the heterocyclic group in (a3).

  In the aryl groups (a1) to (a4), the position of the substituent is not particularly limited, and the total number is not particularly limited. However, in order to exhibit excellent photochromic properties, the substitution position is preferably the 3-position or the 4-position when the aryl group is a phenyl group. Moreover, it is preferable that the number of the substituents in that case is 1-2.

  As such a suitable aryl group, 4-methylphenyl group, 4-methoxyphenyl group, 3,4-dimethoxyphenyl group, 4-n-propoxyphenyl group, 4- (N, N-dimethylamino) phenyl group 4- (N, N-diethylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 4-morpholinophenyl group, 4-piperidinophenyl group, 3- (N, N-dimethylamino) A phenyl group, 4- (2,6-dimethylpiperidino) phenyl group, etc. can be mentioned.

  In the heteroaryl groups (I) to (d), the position of the substituent is not particularly limited. The total number of substituents is not particularly limited, but is preferably 1. Suitable heteroaryl groups include 4-methoxythienyl group, 4- (N, N-dimethylamino) thienyl group, 4-methylfuryl group, 4- (N, N-diethylamino) furyl group, 4- (N, N-diphenylamino) thienyl group, 4-morpholinopyrrolinyl group, 6-piperidinobenzothienyl group, 6- (N, N-dimethylamino) benzofuranyl group and the like can be mentioned.

  The chromene compound represented by the general formula (6) described above exhibits particularly excellent photochromic properties and is most preferably used in the present invention as follows.

One kind of the various photochromic compounds described above can be used, but two or more kinds can be appropriately mixed with the radical polymerizable component described above from the viewpoint of color tone adjustment and the like.
In the photochromic coating solution of the present invention, the blending amount of the photochromic compound may be appropriately determined according to the use,
Next, the halogen type organic solvent contained in the precursor composition will be described.

<(III) Halogen-based organic solvent>
The halogen-based organic solvent used in the present invention is not particularly limited as long as it is an organic solvent having a halogen atom such as fluorine, chlorine, bromine or iodine. Among these, from the viewpoint of solubility of the radical polymerizable monomer component, the photochromic compound, and other components added as necessary, a halogen-based organic solvent having a chlorine atom is preferable. Since the halogen-based organic solvent has low flammability, problems such as explosion can be avoided even if an operation of distilling off in the coating liquid production process is performed.

  The photochromic compound depends on the type, amount used, and type of the radical polymerizable monomer component (I) used. However, if the concentration is high or the molecular weight of the photochromic compound is increased, the radical polymerizable monomer There exists a tendency for solubility with respect to component (I) to fall. Further, when the silsesquioxane component (I-2) is contained in the radical polymerizable monomer component (I), the solubility of the photochromic compound may be lowered. The method of the present invention can solve such problems. That is, the method of this invention implements the preparatory process which mix | blends a halogen-type organic solvent in order to improve the solubility of a photochromic compound to the precursor composition of a photochromic coating liquid. By preparing this precursor composition, the solubility of the photochromic compound is improved, so that a higher concentration photochromic compound can be prepared. Furthermore, by storing the precursor composition, precipitation of the photochromic compound during storage is suppressed, and storage stability is improved.

  The boiling point of the halogen-based organic solvent of the present invention is preferably 35 to 90 ° C. from the viewpoint that the halogen-based organic solvent can be easily distilled off from the precursor composition of the coating solution in the coating solution production process.

  Specific examples of the halogen-based organic solvent used in the present invention include dichloromethane, chloroform, carbon tetrachloride, dichloroethylene, and trichloroethylene. Of these, dichloromethane and chloroform are particularly preferable.

<Blend ratio of precursor composition>
In the method of the present invention, the blending ratio of each component in the precursor composition is the type of the radical polymerizable monomer component (I) to be used, the composition of the component, the type of halogenated organic solvent, the type of photochromic compound, What is necessary is just to determine the optimal range suitably according to the preservation | save conditions of a precursor composition, its usage method, etc. Among them, considering the solubility of the photochromic compound, the storage stability of the precursor composition, the operability in the coating liquid production process, the film thickness distribution of the coating layer to be formed, etc., 100 parts by mass of the radical polymerizable monomer component In contrast, the halogen-based organic solvent is preferably 10 to 100 parts by mass and the photochromic compound is preferably 1 to 20 parts by mass. When the precursor composition has this blending ratio, the photochromic compound can be dissolved in a short time with a simple operation. Furthermore, the halogen-based organic solvent can be easily distilled off in the coating liquid production process. Therefore, More preferably, it is 20-50 mass parts of halogen-type organic solvents, and 1-20 mass parts of photochromic compounds with respect to 100 mass parts of radically polymerizable monomer components.

  In the coating step, when the thickness of the photochromic coating layer is 10 to 30 μm, 20 to 50 parts by mass of a halogen-based organic solvent and 100% by mass of the radical polymerizable monomer component and photochromic are used. It is preferable to make a compound into 5-20 mass parts. Moreover, when it is going to make the thickness of a photochromic coating layer into 30-50 micrometers, 20-50 mass parts of halogen-type organic solvents with respect to 100 mass parts of radically polymerizable monomer components, and 1-1 of photochromic compounds. 5 parts by mass is preferable.

  The precursor composition contains the radical polymerizable monomer component, the halogen-based organic solvent, and the photochromic compound as essential components, but may contain other known additive components. Next, the additive component will be described.

<Other additive components>
In the precursor composition, generally, various additives known per se can be blended in addition to the above-mentioned radical polymerizable component, halogen-based organic solvent, and photochromic compound component, depending on the application. .

  For example, in order to form a polymerized cured product, an appropriate radical polymerization initiator can be blended according to the polymerization means. Such radical polymerization initiators include photopolymerization initiators and thermal polymerization initiators.

  The photopolymerization initiator is used for polymerizing and curing the photochromic coating liquid by irradiation with light such as ultraviolet rays. Add photoinitiator for reasons such as curing the photochromic coating solution of the present invention on the substrate lens in a relatively short time so that it does not flow, and preventing thermal deformation of the lens. It is common to use it.

  The following can be illustrated as such a photoinitiator. Specifically, benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, aethofenone 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthiooxane, bis (2,6-dimethoxybenzoyl-2,4, 4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 2-benzyl-2-dimethyl And rumino-1- (4-morpholinophenyl) -butanone 1. The above-described photopolymerization initiators can be used alone or in combination of two or more, and are generally radically polymerizable monomers. It is used in an amount of 0.001 to 5 parts by mass per 100 parts by mass of the monomer component.

  The thermal polymerization initiator is used for polymerizing and curing the photochromic coating solution by heating. Moreover, you may add and use the following thermal polymerization initiator as needed.

  The following can be mentioned as a typical thing of such a thermal-polymerization initiator. Specifically, diacyl peroxide such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide; t-butylperoxy-2-ethylhexanoate, t-butyl Peroxyesters such as peroxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate; peroxyesters such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butyloxycarbonate 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (Cyclohexane 1-carbonitrile) azo compounds such like. The above-mentioned thermal polymerization initiators can be used alone or in combination of two or more, and the amount used varies depending on the type and polymerization conditions, the composition and type of the radical polymerizable component, etc. In general, it is in the range of 0.01 to 10 parts by mass per 100 parts by mass of the radical polymerizable monomer component.

  In addition, the photochromic coating solution of the present invention includes a surfactant, an antioxidant, a radical scavenger, an improvement in repetition durability of the photochromic compound, an improvement in color development speed, an improvement in fading speed and an improvement in moldability. An ultraviolet stabilizer and an ultraviolet absorber can be blended.

  As the surfactant, any of a nonionic surfactant, an anionic surfactant, and a cationic surfactant can be used, but it is preferable to use a nonionic surfactant because of its solubility in a radical polymerizable component.

  Suitable nonionic surfactants include sorbitan fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, and the like. 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 per 100 parts by mass of the radical polymerizable monomer component, and two or more surfactants can be used in combination within this range. .

  Antioxidants, radical scavengers, ultraviolet stabilizers and ultraviolet absorbers are so-called stabilizers. As these stabilizers, hindered amine light stabilizers, hindered phenol antioxidants, phenol radical scavengers, sulfur antioxidants, benzotriazole compounds, benzophenone compounds, etc. are suitable, and these stabilizers are used in combination. It is also possible to do. The amount of such a stabilizer added is preferably in the range of 0.001 to 20 parts by mass per 100 parts by mass of the radical polymerizable monomer component.

  In addition, the precursor composition of the coating liquid of the present invention includes a hindered amine light stabilizer and a hindered phenol antioxidant from the viewpoint of preventing deterioration of the photochromic compound upon polymerization and curing or improving repeated durability of photochromic properties. Preferably used.

  The hindered amine light stabilizer is not particularly limited, but bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate is particularly preferable from the viewpoint of preventing deterioration of the photochromic compound. In addition, hindered amine light stabilizers marketed under the trade names such as ADK STAB LA-52, LA-62, LA-77, LA-82 by Asahi Denka Kogyo Co., Ltd. can also be suitably used.

Although it does not restrict | limit especially as a hindered phenol antioxidant, The following hindered phenol is suitable at the point of deterioration prevention of a photochromic compound. In particular,
IRGANOX245 from Ciba Specialty Chemicals: Ethylene bis (oxyethylene) bis [3,5-tert-butyl-4-hydroxy-m-toluyl] propionate] IRGANOX1076 from Ciba Specialty Chemicals: Octadecyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate IRGANOX1010 manufactured by Ciba Specialty Chemicals: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] It is done.

  The blending amount of the hindered amine light stabilizer and the hindered phenol antioxidant blended in the precursor composition of the coating liquid of the present invention is also within the range of the amount of stabilizer used (0.001 to 20 parts by mass). However, it is particularly preferable that the amount be in the range of 0.1 to 10 parts by mass, most preferably 1 to 10 parts by mass per 100 parts by mass of the radical polymerizable monomer component.

  Further, in the precursor composition of the coating liquid of the present invention, in addition to the various additives described above, a release agent, an anti-coloring agent, an antistatic agent, a fluorescent dye, a dye, a pigment, a fragrance, a plasticizer, and the like May be blended.

  As described above, various additives can be added to the precursor composition of the coating liquid of the present invention in addition to the radical polymerizable component, the halogen-based organic solvent, and the photochromic compound described above. The total amount must be set so that the total amount does not become unnecessarily excessive and the photochromic properties and the hardness of the cured product are not impaired.

  The precursor composition can also contain the additive components as described above. Next, a method for producing a precursor composition, that is, a preparation step will be described.

(Precursor composition production: preparation step)
The precursor composition weighs and mixes predetermined amounts of various radical polymerizable monomer components (I-1 to I-4), a halogenated organic solvent, a photochromic compound, and various additives appropriately blended. It is prepared by. The order of addition of each component is not particularly limited, and all the components may be added at the same time, or a photochromic compound in which only the radically polymerizable monomer component (I) is mixed in advance and then dissolved in a halogen-based organic solvent. Other additives may be added and mixed. It is also possible to mix the radical polymerizable monomer component (I), the photochromic compound (II), and the halogen-based organic solvent (III), and finally add other additive components, particularly a polymerization initiator. it can.

  In the present invention, since a halogen-based organic solvent is used, the photochromic compound can be dissolved at room temperature and only by a simple operation (mixing). However, in this invention, when manufacturing a precursor composition, it can also heat (70 degreeC) and can also perform ultrasonic irradiation etc.

  By the above method, each component is mixed and a precursor composition is manufactured (prepared). In this preparation step, by preparing the precursor composition, a photochromic coating solution containing a high concentration photochromic compound can be produced.

  Next, the coating liquid manufacturing process will be described.

<Coating solution manufacturing process>
In the present invention, the coating liquid production process is a process for producing a photochromic coating liquid by performing an operation of distilling off the halogen-based organic solvent from the precursor composition. In this step, only the halogen-based organic solvent is distilled off from the precursor composition, and other components are not removed.

  The method for distilling off the halogen-based organic solvent from the precursor composition is not particularly limited, and a known method is employed. Among these, it is preferable to distill off under reduced pressure. When depressurizingly distilling, a well-known apparatus should just be used, for example, an evaporator etc. can be used. The conditions for distillation under reduced pressure may be appropriately determined according to the type and amount of the halogen-based organic solvent to be used, but are preferably distilled off at 20 to 70 ° C. under a reduced pressure of 0.1 to 50 kPa. It is preferable to distill off at 20 to 50 ° C. under a reduced pressure of 0.5 to 20 kPa. The time required for the distillation may be appropriately determined depending on the amount of the precursor composition, the amount and type of the halogen-based organic solvent, and the conditions for the distillation, but usually about 1 to 30 minutes is sufficient.

  If this coating liquid manufacturing process is before the coating process explained in full detail below, implementation time will not be restrict | limited. However, in order to avoid the precipitation of the photochromic compound in the photochromic coating solution, it is desirable to distill off the halogen-based organic solvent immediately before the coating process.

  In the coating liquid production process, the amount of the halogen-based organic solvent to be distilled off may be an amount such that the amount of the halogen-based organic solvent contained in the photochromic coating solution is less than the amount of the halogen-based organic solvent in the precursor composition. . However, in order to make the film thickness of the formed photochromic coating layer more uniform, the blending ratio of the obtained photochromic coating solution is 1 to 20 mass of photochromic compound per 100 mass parts of the radical polymerizable monomer component. Parts and the halogen-based organic solvent are preferably less than 10 parts by mass. More preferably, the blending ratio of the halogen-based organic solvent is preferably 5.0 parts by mass or less, and particularly preferably 0.5 parts by mass or less. The lower limit of the amount of the halogen-based organic solvent contained in the photochromic coating solution is not particularly limited, but is 0.2 parts by mass per 100 parts by mass of the radically polymerizable monomer component, and most preferably 0.8. 0 parts by mass.

  The amount of the halogen-based organic solvent in this photochromic coating solution can be determined from the difference between the mass of the precursor composition and the mass of the photochromic coating solution obtained by distilling off the halogen-based organic solvent.

  In addition, the photochromic coating liquid has a viscosity at 25 ° C. of preferably 20 to 500 cPs, more preferably 50 to 400 cPs, and most preferably 80 to 300 cPs. If it is this viscosity range, the operativity in the case of coating will be favorable, and control of a film thickness can be implemented easily. Such viscosity adjustment can be performed by adjusting the blending ratio of the radical polymerizable component (I) described above.

  In the present invention, even if the halogen-based organic solvent is distilled off from the precursor composition in this coating liquid production process, it cannot be stored for a long period of time. However, in the following coating process, the photochromic compound in which the photochromic compound is dissolved is used. It can be set as a coating liquid. Although the time varies depending on the composition, concentration, etc. of the photochromic coating solution, according to the study by the present inventors, at 23 ° C., the photochromic compound is precipitated in the obtained photochromic coating solution for at least 1 hour. There wasn't. Some of them had no photochromic compound precipitation for 48 hours. If no precipitation of the photochromic compound is observed for this amount of time, a photochromic lens can be manufactured stably.

  The present inventors presume that a coating liquid in which a photochromic compound is dissolved is obtained in order to distill off the halogen-based organic solvent from the precursor composition. Depending on the radically polymerizable monomer component used, the type and concentration of the photochromic compound, the conventional technology that does not use a halogen-based organic solvent requires that the photochromic compound does not dissolve or is not heated or irradiated with ultrasonic waves. In some cases, the photochromic compound did not dissolve. In the present invention, since a precursor composition containing a halogenated organic solvent is prepared, the photochromic compound can be easily dissolved, and the halogenated organic solvent can be easily distilled off. As a result, it is possible to produce a photochromic coating solution in which a photochromic compound having a higher concentration than the conventional one is dissolved, or a combination photochromic coating solution in which the photochromic compound is not dissolved in the conventional composition. This is because the photochromic coating solution obtained in the present invention is dissolved in the photochromic compound due to the action of the halogen-based organic solvent in which the photochromic compound is supersaturated with respect to the radical polymerizable monomer component or a small amount remains. It is estimated that

  Next, the coating process using this photochromic coating solution will be described.

<Coating process>
In the present invention, the lens substrate for forming the photochromic coating layer is not particularly limited as long as it requires reversible color change by light irradiation. Specifically, spectacle lenses are typical.

  In order to form a photochromic coating layer on the surface of the lens substrate, the photochromic coating solution obtained in the coating production process may be applied to the surface of the lens substrate and then polymerized and cured.

  Prior to applying the photochromic coating solution to the surface of the lens substrate, it is preferable to pretreat the surface of the lens substrate. Thereby, the wettability with a photochromic coating liquid and the lens base material surface can be improved, and the adhesive strength of a photochromic coating layer and a lens base material can be improved.

  Examples of such pretreatment include chemical treatment using a basic aqueous solution or acidic aqueous solution, polishing treatment using an abrasive, plasma treatment using atmospheric pressure plasma and low pressure plasma, corona discharge treatment, UV ozone treatment, and the like. be able to. Of course, these pretreatments can be used in combination.

  When a spectacle lens is used as the lens substrate, chemical treatment with a basic solution is preferable among the above pretreatments. This is because the processing operation is simple, and in particular, the adhesion between the coating layer formed using the photochromic coating solution of the present invention and the spectacle lens can be strengthened.

  The pretreatment by the basic treatment is generally performed by impregnating the lens substrate in an alkaline solution, an alcohol solution, or a mixed solution thereof. After the treatment, the surface of the optical substrate may be dried after rinsing with water such as pure water, ion exchange water, or distilled water.

  After the pretreatment, the primer layer can be coated for the purpose of further improving the adhesion. The primer layer is formed by applying a primer composition containing a reaction product that is normally cured to form a urethane resin, a solvent, and the like to the lens surface, and then removing the solvent and curing the reaction product. The primer composition can be applied by a known means such as spin coating, spray coating, dip coating, or dip-spin coating.

  The photochromic coating solution can also be applied by known means such as spin coating, spray coating, dip coating, dip-spin coating.

  The polymerization and curing is generally performed by light irradiation (ultraviolet irradiation). When a photopolymerization initiator is blended as a radical polymerization initiator, polymerization and curing can be performed by irradiation with ultraviolet rays, α rays, β rays, γ rays, etc., or a combination of both. When polymerization is carried out by ultraviolet irradiation, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, a carbon arc, a germicidal lamp, a metal halide lamp, an electrodeless lamp, or the like can be used as the light source.

  Furthermore, when a radical polymerization initiator is not blended, it can be polymerized and cured by electron beam irradiation to form a photochromic coating layer.

  In addition, it is also possible to use the above means in combination, for example, curing can be performed by irradiation with ultraviolet rays or the like, and heating can be completed as necessary to complete the polymerization.

  The temperature for the polymerization and curing is not particularly limited, and a temperature in a known method may be adopted. Specifically, the temperature of the lens surface is preferably 100 ° C. or lower. Further, the temperature may be controlled by intermittently irradiating light as in Patent Documents 2 and 3, or a silicon pad (about 10− 20 mm) may be applied to release heat.

  The thickness of the photochromic coating layer formed by application of the photochromic coating solution and polymerization and curing is preferably 10 to 50 μm. If the photochromic coating layer is too thin, durability is repeatedly impaired. On the other hand, if the coating layer is too thick, the initial yellow color may increase.

  Other known layers such as a hard coating layer may be formed on the photochromic coating layer. As the coating agent (hard coating agent) for forming the hard coating layer, known ones can be used without any limitation. Specifically, a hard coat agent mainly composed of a silane coupling agent or an oxide sol such as silicon, zirconium, antimony, aluminum, titanium, or a hard coat agent mainly composed of an organic polymer can be used. .

  The formation of the hard coating layer using the hard coating agent can be performed by the same means as the formation of the photochromic coating layer. For example, after performing a pretreatment by a basic treatment using an alkaline solution or the like, A coating agent is applied, for example, heated to a temperature at which the lens base material is not deformed and cured to form a hard coating layer.

In addition to the hard coating layer, the surface of an optical article such as a lens to which photochromic properties are imparted by the method of the present invention may further include a thin film of a metal oxide such as SiO ₂ , TiO ₂ , or ZrO _{2 if} necessary. Processing such as antireflection treatment or antistatic treatment such as vapor deposition or coating of a thin film of an organic polymer, and secondary treatment can also be performed.

  Next, the present invention will be described in detail using examples and comparative examples, but the present invention is not limited to the examples.

  Moreover, the measurement of the physical property of the precursor composition of the photochromic coating liquid produced in the following examples and the evaluation of the photochromic lens was performed as follows.

(1) Color density From a xenon lamp {L-2480 (300W) SHL-100, manufactured by Hamamatsu Photonics) to a photochromic lens through an aeromass filter (manufactured by Corning) at 20 ° C. ± 1 ° C. on the surface of the photochromic coating The color was developed by irradiating with ultraviolet rays at a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² for 300 seconds. It was calculated | required by the electronics industry}.
From the measurement results, the color density was calculated by the following formula.
Color density = ε (300) −ε (0)
ε (300) is a value of absorbance at the maximum absorption wavelength after light irradiation for 300 seconds, and ε (0) is a value of absorbance at the wavelength of the cured body in a state where light is not irradiated. The higher this value, the better the photochromic characteristics.

(2) Fading half-life After irradiating the photochromic lens with light for 300 seconds, light irradiation was stopped, and the absorbance at the maximum wavelength of the cured product was a value of {ε (300) −ε (0)} 1/2. The time {t1 / 2 (min)} required to decrease to a maximum value was measured and evaluated as the fading half-life. The shorter this time, the faster the fading speed and the better the photochromic characteristics.

(3) Repeated durability In order to evaluate the repeated durability of color development by light irradiation, a deterioration acceleration test was conducted. The test method is as follows. The photochromic lens was accelerated and deteriorated by a xenon weather meter {X25, manufactured by Suga Test Instruments Co., Ltd.} for 200 hours. Before and after this deterioration, the above-described color density was evaluated, and the color density before the test (A ₀ ) and the color density after the test (A ₂₀₀ ) were measured.

  From this measurement result, a residual rate that is a measure of repeated durability was calculated.

Residual rate (%) = (A ₂₀₀ / A ₀ ) × 100
A ₀ is the value of the color density before the test,
A ₂₀₀ is a color density value after the test.
A lens with a higher remaining rate has higher repetition durability and better photochromic properties.

(4) Film thickness of photochromic coating layer The film thickness of the coating layer after spin-coating and curing the photochromic coating solution was measured using a film thickness meter (Filmtrics F20, manufactured by FILMETRICS).

(5) Deformation of lens The photochromic coating solution was spin-coated by the above method, and the change in refractive power before and after curing was measured using an auto lens meter (LM1800-P, manufactured by Nidec Co.) and evaluated according to the following criteria.
○: Less than 0.03.
Δ: 0.03 or more and less than 0.06.
X: 0.06 or more.

(6) Coating property The appearance of the photochromic coating layer after spin-coating and curing the photochromic coating solution was visually evaluated according to the following criteria.
○: No problem.
Δ: Some unevenness.
X: Coating film defect.

(7) Storage stability of precursor composition The precursor composition was stored at room temperature for 6 months, and the presence or absence of precipitation of the photochromic compound was visually evaluated according to the following criteria.
○: No precipitation at 6 months.
Δ: Precipitation at 6 months
X: Precipitation occurs at 3 months.
In the comparative example, no halogen-based organic solvent is blended. Therefore, in the comparative example, this storage stability was evaluated by evaluating the storage stability of the halogen-free organic solvent (photochromic coating solution) using the above items.

(8) Solubility of Precursor Composition In the preparation step, the solubility of the precursor composition was evaluated by the following operation required for the photochromic compound to be completely dissolved by visual observation.
A: Dissolved by stirring at room temperature for 30 minutes.
○: Dissolved by stirring for 30 minutes at room temperature and then stirring for 30 minutes at room temperature with ultrasonic irradiation.
△: Dissolved by stirring for 30 minutes at room temperature and stirring for 30 minutes at room temperature with ultrasonic irradiation followed by stirring for 30 minutes at 70 ° C while applying ultrasonic waves.
In the comparative example, no halogen-based organic solvent is blended. Therefore, in the comparative example, this storage stability was evaluated by evaluating the storage stability of the halogen-free organic solvent (photochromic coating solution) using the above items.

<Radically polymerizable monomer component (I)>
<Bifunctional polymerizable monomer (I-1)>
BPE500:
2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane
Average chain length of ethylene glycol chain (a + b): 10
Average molecular weight: 804
L-scale Rockwell hardness of homopolymer <40
A-BPE:
2,2-bis (4-acryloyloxypolyethoxyphenyl) propane
Average chain length of ethylene glycol chain (a + b): 10
Average molecular weight: 776
L-scale Rockwell hardness of homopolymer <20
9G:
Polyethylene glycol dimethacrylate
Average chain length of ethylene glycol chain (a + b): 8, A = ethylene group
Average molecular weight: 536
L-scale Rockwell hardness of homopolymer <20
14G:
Polyethylene glycol dimethacrylate
Average chain length of ethylene glycol chain (a + b): 13, A = ethylene group
Average molecular weight: 770
L-scale Rockwell hardness of homopolymer <20
A400:
Polyethylene glycol diacrylate
Average chain length of ethylene glycol chain (a + b): 8, A = ethylene group
Average molecular weight: 508
L-scale Rockwell hardness <20 for homopolymer.

<Silsesquioxane component (I-2)>
MAC-SQ TI-100: Polyacryloxypropyl polyorganosiloxane {manufactured by Toagosei Co., Ltd.}. ^{From 29} Si-NMR, it was confirmed to be a mixture of a cage structure, a ladder structure and a random structure. The ratio of radically polymerizable groups is 100%, and the weight average molecular weight is 2100.

<Polyfunctional polymerizable monomer (I-3)>
TMPT: trimethylolpropane trimethacrylate.

<Other polymerizable monomer (I-4)>
GMA: glycidyl methacrylate.

  <Photochromic compound (II)>

Other additive components <polymerization initiator>
CGI819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide <Hindered amine light stabilizer>
Tinuvin 765: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate <hindered phenol antioxidant>
IRGANOX245: ethylene bis (oxyethylene) bis [3,5-tert-butyl-4-hydroxy-m-toluyl] propionate].

Example 1
(Preparation process)
The following components were mixed at room temperature to prepare radical polymerizable monomer component (I).

Bifunctional polymerizable monomer (I-1) BPE500: 100 parts by mass,
Polyfunctional polymerizable monomer (I-3) TMPT: 25 parts by mass,
3 parts by mass of other polymerizable monomer (I-4) GMA was mixed at room temperature.

  The total mass of the obtained radical polymerizable monomer component (I) was 100 parts by mass, and the following components were added thereto to obtain a precursor composition.

Photochromic compound (II)
PC1 (photochromic compound (PC1)) 2 parts by mass Other additive components Tinuvin 765 (light stabilizer) 5 parts by mass,
IRGANOX245 (antioxidant) 3 parts by mass CGI819 (polymerization initiator) 0.5 parts by mass Halogen-based organic solvent (III)
Halogen-based dichloromethane 20 parts by mass These components were simultaneously added to the radical polymerizable monomer component (I) and stirred at room temperature for 30 minutes to confirm that the photochromic compound was visually dissolved.

(Coating liquid production process)
The precursor composition was transferred to an eggplant flask and distilled off under reduced pressure for 10 minutes in a 40 ° C. water bath and about 0.1 kPa using an evaporator to confirm that the residual amount of dichloromethane was 0.1 parts by mass. . The amount of the halogen-based organic solvent remaining was calculated from the mass difference between the coating solution after distillation and the precursor composition. A photochromic coating solution was obtained by the above operation.

(Coating process)
As a lens substrate, a thioepoxy resin plastic lens having a center thickness of 1 mm, an apex refractive power of -2.0, and a refractive index of 1.74 was prepared. Using a spin coater (1H-DX2, manufactured by MIKASA), the moisture-curing primer TR-SC-P was coated on the surface of the plastic lens for 15 seconds at a rotation speed of 70 rpm and subsequently at 1000 rpm for 10 seconds. Then, after standing for 10 minutes, about 2 g of the photochromic coating solution obtained in the coating solution production process was spin-coated for 40 seconds at 60 rpm and then for 8 seconds at 600 rpm (a coating film was formed). A silicon pad is affixed to the back surface of the lens base material on which the photochromic coating solution is applied, and light is irradiated for 90 seconds in a nitrogen gas atmosphere using a metal halide lamp with an output of 200 mW / cm ² to cure the coating film. I let you. It was confirmed that the surface temperature of the lens immediately after photocuring was in the range of 50-60 ° C. Then, it further heated at 110 degreeC for 1 hour, and produced the photochromic lens which has a photochromic coating layer. The thickness of the photochromic coating layer was 15 μm.

  The photochromic lens produced above was evaluated for color density, fading half-life, repetition durability (residual rate), coating layer thickness, coating properties, and lens deformation. Moreover, the storage stability and solubility of the precursor composition were evaluated. The compositions of the precursor composition and the photochromic coating solution are shown in Table 1, and the evaluation results are shown in Table 2.

Example 2-12
Preparation of the precursor composition with the blending ratio shown in Table 1 was performed. Other additive components were the same as in Example 1. The preparatory process was implemented similarly to Example 1, and the precursor composition was obtained. Subsequently, the coating liquid manufacturing process and the coating process were carried out in the same manner as in Example 1 for evaluation. However, in Example 11, the time for distilling off the halogen-based organic solvent was 5 minutes in the coating liquid production process, and in Example 12, the time for distilling off the halogen-based organic solvent was 3 minutes in the coating liquid production process. It was. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Examples 13-25
Preparation of the precursor composition shown in Table 3 was carried out. The other additive components were the same as those in Example 1 (however, in Examples 22 and 23, the blending of other additive components was as shown in Table 3). The preparation process was carried out in the same manner as in Example 1. In the case where the photochromic compound was not visually dissolved, the precursor composition was obtained by dissolving the photochromic compound according to the solubility item of the precursor composition.

  Subsequently, the coating liquid manufacturing process and the coating process were carried out in the same manner as in Example 1 for evaluation. However, Examples 20 and 21 were adjusted so that the thickness of the photochromic coating layer was 10 μm, and Examples 24 and 25 were adjusted so that the thickness of the photochromic coating layer was 40 μm.

  In Examples 24 and 25, a thiourethane resin plastic lens having a center thickness of 2 mm, an apex refractive power of −2.0, and a refractive index of 1.60 was used as a lens substrate. The composition is shown in Table 3, and the evaluation results are shown in Table 4.

Comparative Example 1-4
Preparation of the precursor composition of the compounding ratio shown in Table 5 was performed. Other additive components were the same as in Example 1. The preparation process was carried out in the same manner as in Example 1. In the case where the photochromic compound was not visually dissolved, the precursor composition was obtained by dissolving the photochromic compound according to the solubility item of the precursor composition. However, since Comparative Example 1-4 does not use a halogen-based organic solvent, the precursor composition and the photochromic coating solution have the same composition. Therefore, the evaluation of solubility and storage stability was targeted at the photochromic coating solution. Using the obtained photochromic coating liquid (precursor composition), a coating process was performed and evaluated (however, in Comparative Examples 3 and 4, the thickness of the photochromic coating layer was adjusted to 40 μm). ). The composition is shown in Table 5, and the evaluation results are shown in Table 6.

  In Comparative Example 1-4, no halogen-based solvent was added. In Comparative Example 1, precipitation occurred during storage. In Comparative Example 2 in which the photochromic compound concentration was reduced, the storage stability was improved, but naturally the color density of the photochromic lens was reduced. Further, in order to improve the color density, the lens was deformed in Comparative Example 3 in which a 40 μm coating layer was formed on a lens having a thin center thickness. Also in Comparative Example 4, precipitation occurred during storage.

Claims (9)

A method for producing a photochromic lens having a photochromic coating layer on the surface of a lens substrate,
Preparing a precursor composition of a coating liquid containing a radical polymerizable monomer component, a photochromic compound, and a halogen-based organic solvent;
A step of distilling off the halogen-based organic solvent from the precursor composition to form a photochromic coating solution containing a radical polymerizable monomer component and a photochromic compound; and applying the photochromic coating solution to the surface of the lens substrate And a step of forming a photochromic coating layer on the surface of the lens substrate by curing the coating solution. A method for producing a photochromic lens, comprising:   The method for producing a photochromic lens according to claim 1, wherein the halogen-based organic solvent has a boiling point of 35 to 90 ° C.   The precursor composition contains 1 to 20 parts by mass of a photochromic compound and 10 to 100 parts by mass of a halogenated organic solvent per 100 parts by mass of the radical polymerizable monomer component. Manufacturing method of photochromic lens.   The photochromic coating liquid according to claim 1, wherein the photochromic coating liquid contains 1 to 20 parts by mass of a photochromic compound and less than 10 parts by mass of a halogen-based organic solvent per 100 parts by mass of the radical polymerizable monomer component. Lens manufacturing method. The radical polymerizable monomer component is
Following formula (1)

{Wherein R ¹ , R ² , R ³ and R ⁴ are each a hydrogen atom or a methyl group, and A is an alkylene group; an unsubstituted phenylene group; a halogen atom or a carbon number of 1 to 4 A phenylene group having an alkyl group of
The following formula (1a)

A group represented by formula (1b):

A group represented by formula (1c)

(Where
R ⁵ and R ⁶ are each an alkyl group having 1 to 4 carbon atoms or a halogen atom,
c and d are integers of 0 to 4,
The six-membered ring B is a benzene ring or a cyclohexane ring,
When the six-membered ring B is a benzene ring, X is -O-, -S-,
_{-S (O) 2 -, -} C (O) -, - CH 2 -, - CH = CH -, - C (CH 3) 2 -,
_{-C (CH 3) (C 6} H 5) - or the following formula (1c-1);

A divalent group represented by
When the six-membered ring B is a cyclohexane ring, X is —O—, —S—,
A divalent group represented by —CH ₂ — or —C (CH ₃ ) ₂ —),
A is an organic group having 1 to 20 carbon atoms, and a is a number of 0 to 30 and b is a number of 0 to 30 provided that the average value of a + b is 2 to 30. The bifunctional polymerizable monomer represented by the number} and the photochromic compound include a compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton. A method for producing the photochromic lens according to 1.   The method for producing a photochromic lens according to claim 1, wherein the radical polymerizable monomer component contains silsesquioxane having a radical polymerizable group.   The method for producing a photochromic lens according to claim 1, wherein the photochromic compound includes a compound having an indeno [2,1-f] naphtho [1,2-b] pyran skeleton.   The method for producing a photochromic lens according to claim 1, wherein the lens base material has a thickness of a central portion of 0.5 to 5.0 mm.   The precursor composition of a photochromic coating liquid containing 1 to 20 parts by mass of a photochromic compound and 10 to 100 parts by mass of a halogen-based organic solvent per 100 parts by mass of the radical polymerizable monomer component.