JPH11269233A - Curable composition - Google Patents

Abstract

(57) [Summary] (with correction) [PROBLEMS] To obtain a composition excellent in operability such that a liquid curable composition can be easily obtained [Solution] (A) Formula (1) And a bifunctional polymerizable monomer represented by the formula: And 100 parts by weight of a polymerizable monomer having a proportion of the monomer of the formula (2) in the total amount of 5 to 50% by weight, and a formula (B) (1) A curable composition containing 1 to 1000 parts by weight of a polymerizable monomer other than the formula (2), and 0.001 to 10 parts by weight of a photochromic compound based on 100 parts by weight of the polymerizable composition. Curable composition containing a part, cured optical material

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a curable composition containing a polymerizable monomer having excellent operability due to its high solubility in a polymerizable monomer to be copolymerized and having high optical properties such as a high refractive index. More particularly, the present invention relates to a curable composition having a high coloring density when a photochromic compound is added and providing a cured product having high durability, and an optical material obtained by curing the curable composition.

[0002]

2. Description of the Related Art Conventionally, various studies have been made on an organic glass as a substitute for an inorganic glass, but there are many disadvantages and no satisfactory properties have yet been obtained. For example, a cured product obtained by polymerizing a monomer containing methyl methacrylate or diethylene glycol bis (allyl carbonate) as a main component is used as an optical material such as a lens, but has a low refractive index of about 1.50.

[0003] Various high-refractive-index resins have been proposed which have alleviated this disadvantage. For example, polycarbonate and polysulfone-based high refractive index resins have been proposed. Although these resins have a high refractive index of about 1.60, they have problems such as low light transmittance, lack of optical homogeneity, and coloring.

For this reason, various cross-linkable high refractive index resins have been proposed. For example, JP-A-56-166214 proposes a high refractive index resin containing a compound represented by the following formula (3).

[0005]

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The resin using this compound has a refractive index of about 1.
As high as 60, it is also optically homogeneous and shows excellent physical properties. In general, the curable composition used for eyeglass lenses and the like needs to be in a liquid state. However, since the properties of the compound represented by the formula (3) are solid, the curable composition is not suitable for other liquid polymerizable monomers. It is common to dissolve and use. However, this compound has low solubility in monomers other than specific polymerizable monomers such as styrene and benzyl methacrylate, and cannot sufficiently exhibit the physical properties such as a high refractive index of the compound represented by the formula (3). . At a high temperature of room temperature or higher, the solubility of the compound represented by the formula (3) in other liquid polymerizable monomers increases, but the polymerization reaction proceeds during the operation.
Alternatively, there is a problem that distortion occurs during polymerization.

Japanese Patent Application Laid-Open No. Sho 59-193915 describes a method for producing a cured product by irradiating a compound represented by the formula (3) with light in a molten state. However,
The above manufacturing method requires a special device for light irradiation, and has a problem that a thermopolymerization device generally used for molding an eyeglass lens or the like cannot be used.

[0008] By the way, photochromism is a phenomenon that has attracted attention in recent years. When a compound is irradiated with light containing ultraviolet light such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is performed. It is a reversible action that returns to its original color when it is stopped and placed in a dark place. A compound having this property is called a photochromic compound, and compounds having various structures have been conventionally synthesized and proposed.

There is a photochromic plastic lens utilizing photochromism.
No. 4790 discloses a photochromic curable composition in which a photochromic compound is dissolved in a radical polymerizable monomer, and a method for obtaining a photochromic resin by curing the composition is disclosed. In particular, it has been proposed to use this cured product as a photochromic lens. However, many of these inventions are materials with a refractive index less than 1.55.

By the way, the eyeglass lens is required to be thinner. For this reason, various studies have been made on increasing the refractive index of the resin used, and many cured products and monomer compositions for lenses have been studied and proposed. However, 1.5
There are few studies on photochromic lenses exceeding six, and there are few disclosures on active technical development other than those disclosed in Japanese Patent Application Laid-Open No. 8-169918. In addition, many styryl compounds have been studied as general high refractive index polymerizable monomers, but the photochromic properties of these high refractive index cured products are less durable than low refractive index cured products. It is not practical as a photochromic lens because it has the drawback of low color density.

The photochromic cured product obtained from the curable composition containing the compound represented by the above formula (3) as a main component has no problem in the durability of photochromic property and the color density, but the formula (3) It is difficult to increase the content of the compound represented by the formula (3) due to the low solubility of the compound represented by the formula (1), and to increase the content of the compound represented by the formula (3). When styrene is used as a polymerizable monomer, there is a problem that durability and color density are reduced. Further, when an attempt is made to obtain a photochromic cured product using the production method described in JP-A-59-193915, the photochromic compound is deteriorated by light irradiation, and practical durability cannot be obtained. Occurs.

[0012]

It has been desired to develop a new technique to compensate for the above-mentioned disadvantages of the prior art. That is, an object of the present invention is to improve the solubility of the compound represented by the above formula (3) and its analog in the polymerizable monomer to be copolymerized, and to increase the refractive index of the cured product with ease. The present invention is to propose a photochromic curable composition having a sufficiently practical coloring density and durability when a photochromic compound is added, and an optical material obtained by curing the curable composition. .

[0013]

Means for Solving the Problems The present inventors have increased the solubility of a specific bifunctional polymerizable monomer having a high refractive index and excellent optical homogeneity, and have set a cured product having a high refractive index as a conventional cured product. For compositions that can be obtained by the same simple method, and with regard to photochromic properties, intensive studies have been made on compositions for obtaining photochromic cured products represented by photochromic lenses, which are excellent in large color density and durability. Continued. As a result, they have found that a mixture of a specific bifunctional polymerizable monomer and a monofunctional polymerizable monomer is a composition suitable for the production of a cured product that satisfies the above required physical properties, and complete the present invention. Reached.

That is, the present invention provides (A) the following general formula (1)

[0015]

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(Provided that R ¹ and R ² are the same or different hydrogen atoms or methyl groups, X is a bromine atom, a chlorine atom or a hydrogen atom, p and q are each independently 1 or 2, m and n are each independently an integer of 1 to 4.) and a bifunctional polymerizable monomer represented by the following general formula (2)

[0017]

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Wherein R ¹ and R ² are the same or different hydrogen atoms or methyl groups, X is a bromine atom, chlorine atom or hydrogen atom, p and q are each independently 1 or 2, m and n are each independently an integer of 1 to 4), and the monofunctional polymerizable monomer represented by the general formula (2) accounts for the total amount of these monomers. 100 parts by weight of a polymerizable monomer having a body ratio of 5 to 50% by weight, and (B) a bifunctional polymerizable monomer represented by the above general formula (1) and a general formula (2) Polymerizable monomers 1 to 1 other than the polymerizable monomer composed of a monofunctional polymerizable monomer
It is a curable composition characterized by containing 000 parts by weight. Another invention relates to the curable composition 100 described above.
0.001 to 1 part by weight of the photochromic compound
It is a photochromic curable composition containing 10 parts by weight. Further, it is an optical material obtained by curing the curable composition.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION In the polymerizable monomers represented by the general formulas (1) and (2) in the present invention, the substituents R ¹ and R ² are the same or different hydrogen atoms or methyl groups, respectively. The substituent R ² is preferably a hydrogen atom for increasing the refractive index of the obtained cured product, but increases the solubility of the bifunctional polymerizable monomer represented by the general formula (1) in the component (B). To achieve this, a methyl group is preferred. Also, m, n
Is each independently an integer of 1 to 4, but is preferably 1 or 2 in order to increase the hardness and heat resistance of the obtained cured product and further increase the refractive index. X is a bromine atom, a chlorine atom or a hydrogen atom, but a bromine atom is preferable in order to increase the refractive index of the obtained cured product. P and q indicate the number of X,
Each is independently 1 or 2.

In the polymerizable monomers represented by the general formulas (1) and (2), the substituents R ¹ and R ² are the same or different hydrogen atoms or methyl groups, and m and n are 1 or 2. X is preferably a bromine atom, and p and q are preferably 1 or 2.

Specific examples of the bifunctional polymerizable monomer represented by the general formula (1) include 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane and 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane. Bis (4-methacryloyloxyethoxy-3,5-dichlorophenyl) propane, 2,2-
Bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-acryloyloxyethoxy-3,5-dibromophenyl) propane, 2,2-bis (4-methacryloyloxyethoxyethoxy-3,
5-dibromophenyl) propane, 2- (4-methacryloyloxyethoxyethoxyphenyl) -2- (4-
Methacryloyloxyethoxyphenyl) propane,
2,2-bis (4-methacryloyloxyisopropoxy-3,5-dibromophenyl) propane and the like can be mentioned.

In the present invention, the monofunctional polymerizable monomer represented by the general formula (2) need not be a monoester corresponding to the bifunctional polymerizable monomer represented by the general formula (1). Is represented by the general formula (1) in terms of ease of manufacture.
It preferably corresponds to a functional polymerizable monomer. Specific examples of the monofunctional polymerizable monomer represented by the general formula (2) include 2- (4-methacryloyloxyethoxy-).
3,5-dibromophenyl) -2- (4-hydroxyethoxy-3,5-dibromophenyl) propane, 2-
(4-methacryloyloxyethoxy-3,5-dichlorophenyl) -2- (4-hydroxyethoxy-3,5
-Dichlorophenyl) propane, 2- (4-methacryloyloxyethoxyphenyl) -2- (4-hydroxyethoxyphenyl) propane, 2- (4-acryloyloxyethoxy-3,5-dibromophenyl) -2-
(4-hydroxyethoxy-3,5-dibromophenyl) propane, 2- (4-methacryloyloxyethoxyethoxy-3,5-dibromophenyl) -2- (4-
Hydroxyethoxyethoxy-3,5-dibromophenyl) propane, 2- (4-methacryloyloxyethoxyethoxyphenyl) -2- (4-hydroxyethoxyphenyl) propane, 2- (4-methacryloyloxyethoxyphenyl) -2- ( (Hydroxyethoxyethoxyphenyl) propane, 2- (4-methacryloyloxyisopropoxy-3,5-dibromophenyl) -2-
(4-hydroxyisopropoxy-3,5-dibromophenyl) propane and the like.

The monofunctional polymer represented by the general formula (2) in the total amount of the bifunctional polymerizable monomer represented by the general formula (1) and the monofunctional polymerizable monomer represented by the general formula (2) The proportion of the water-soluble monomer is 5 to 50% by weight, but the solubility of the bifunctional polymerizable monomer represented by the general formula (1) in the component (B), the heat resistance and the hardness of the obtained cured product. Considering
It is preferably from 5 to 30% by weight, more preferably from 5 to 20% by weight. Monofunctional polymerizable monomer represented by the general formula (2) in the total amount of the bifunctional polymerizable monomer represented by the general formula (1) and the monofunctional polymerizable monomer represented by the general formula (2) When the proportion of the monomer is less than 5% by weight, the solubility of the bifunctional polymerizable monomer represented by the general formula (1) in the component (B) does not increase, so that the monofunctional polymerization represented by the general formula (2) It is necessary that the ratio of the reactive monomer is 5% by weight or more. Further, when the proportion of the monofunctional polymerizable monomer represented by the general formula (2) exceeds 50% by weight, the heat resistance and hardness of the obtained cured product are reduced, and thus the monofunctional polymerizable monomer represented by the general formula (2) is reduced. It is necessary that the ratio of the functional polymerizable monomer be 50% by weight or less.

The component (B) in the present invention is a polymerizable copolymerizable with the above-mentioned bifunctional polymerizable monomer represented by the general formula (1) and the monofunctional polymerizable monomer represented by the general formula (2). The compound is not particularly limited as long as it is a water-soluble monomer. Specific examples of compounds that can be suitably used as the component (B) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, and bisphenol A-monoglycidyl ether. -Methacrylate, 4-glycidyloxybutyl methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate,
3- (glycidyloxy-1-isopropyloxy)-
2-hydroxypropyl acrylate, 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) Acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, alkoxy polyethylene Monofunctional (meth) acrylate-based polymerizable monomers such as glycol (meth) acrylate, alkoxy polypropylene glycol (meth) acrylate, and trifluoromethyl (meth) acrylate; Tylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, tetradecaethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, nonapropylene glycol dimethacrylate, nonaethylene glycol di (meth) acrylate , Polybutylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Acrylic acid and methacrylic acid ester compounds of water-added bisphenol A ethylene oxide or propylene oxide adduct, dimethylol tricyclodecane di (meth) acrylate, dimethylol tricyclodecane polyethoxydi (meth) acrylate, trimethylol propane tri (meth) A) acrylate, pentaerythritol tetra (meth) acrylate, the reaction product of ethylene glycol or polyethylene glycol with glycidyl (meth) acrylate, the reaction product of propylene glycol or polypropylene glycol with glycidyl (meth) acrylate, bisphenol A ethylene oxide or propylene oxide Reaction product of adduct and glycidyl (meth) acrylate, water-added bisphenol A ethylene oxide or Reaction product of propylene oxide adduct and glycidyl (meth) acrylate, polyfunctional (meth) acrylate polymerizable monomer such as urethane acrylate; styrene, chlorostyrene, α-methylstyrene, α-methylstyrene dimer, vinyl Naphthalene,
Examples include styryl-based polymerizable monomers such as isopropenylnaphthalene, bromostyrene, and divinylbenzene. These (meth) acrylate-based polymerizable monomers and / or styryl-based polymerizable monomers can be used alone or in combination of two or more.

The curable composition of the present invention comprises the component (B)
1 to 1000 parts by weight based on 100 parts by weight of a polymerizable monomer composed of a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2) I do. When the component (B) is less than 1 part by weight, the compound represented by the general formula (1)
Does not dissolve, or the cured product obtained by curing the curable composition is not uniform. When the component (B) exceeds 1,000 parts by weight,
The bifunctional polymerizable monomer represented by the general formula (1) cannot exhibit sufficient physical properties such as a high refractive index. The content of the component (B) is preferably 10 in view of the solubility of the bifunctional polymerizable monomer represented by the general formula (1) and the increase in the refractive index of the cured product.
To 500 parts by weight, more preferably 30 to 300 parts by weight.

The method for producing the curable composition of the present invention is not particularly limited, and includes a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2) The polymerizable monomer comprising and the component (B) are mixed and stirred at room temperature,
It may be dissolved to form a uniform solution. At this time, a method for obtaining a polymerizable monomer comprising a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2) is not particularly limited. For example, (i) the esterification reaction for obtaining the bifunctional polymerizable monomer represented by the general formula (1) is stopped halfway, and the bifunctional compound represented by the general formula (1) having a desired monoester content is obtained. A method for obtaining a polymerizable monomer comprising a polymerizable monomer and a monofunctional polymerizable monomer represented by the general formula (2), (ii) a bifunctional polymerizable monomer represented by the general formula (1) To obtain a polymerizable monomer comprising a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2), (ii)
i) dissolving the bifunctional polymerizable monomer represented by the general formula (1) in the monofunctional polymerizable monomer represented by the general formula (2) and dissolving the bifunctional polymerizable monomer represented by the general formula (1) To obtain a polymerizable monomer comprising a monomer and a monofunctional polymerizable monomer represented by the general formula (2), (iv) a bifunctional polymerizable monomer represented by the general formula (1) and a general formula The monofunctional polymerizable monomer represented by (2) is once dissolved in a solvent to form a homogeneous solution, and then the solvent is distilled off to obtain a bifunctional polymerizable monomer represented by the general formula (1) and a general formula ( Examples of the method include a method for obtaining a polymerizable monomer composed of the monofunctional polymerizable monomer shown in 2).

Next, as the photochromic compound used in the present invention, a compound exhibiting a photochromic action can be employed without any limitation. For example, photochromic compounds such as fulgide compounds, chromene compounds and spirooxazine compounds are well known, and these photochromic compounds can be used in the present invention. As the above photochromic compound, US Pat. No. 4,882,438 and US Pat.
No. 60678, U.S. Pat.
U.S. Pat. No. 5,106,998, and International Publication No. 94
Compounds known in, for example, U.S. Pat. No. 22,854, International Publication No. 9505371, U.S. Pat. No. 4,913,544, and European Patent Application No. 0600669 can be suitably used. These photochromic compounds can be used singly or as a mixture of two or more, and the compounding ratio may be determined according to the intended use.

Among the photochromic compounds that can be suitably used in the present invention, the chromene compound is represented by the general formula (4)
Can be represented by

[0029]

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(Provided that R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different, respectively, a hydrogen atom, an alkyl group, an aryl group, a substituted amino group, a saturated heterocyclic group or an unsaturated heterocyclic group; ⁶ and R ⁷ may together form a ring,

[0031]

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The groups represented by are each a halogen atom,
An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 14 carbon atoms
A divalent aromatic hydrocarbon group or a divalent aromatic hydrocarbon group which may be substituted with at least one substituent selected from the group consisting of an alkoxyaryl group having 1 to 10 carbon atoms, a substituted amino group, a nitro group and a cyano group. It is a valent unsaturated heterocyclic group. In the above formula (4), the alkyl group represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ has 1 to 1 carbon atoms such as a methyl group and an ethyl group.
And an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the substituted amino group include an amino group in which at least one hydrogen atom has been substituted with the above-described alkyl group or aryl group, and a saturated heterocyclic group includes a pyrrolidine ring, an imidazolidine ring, and a piperidine. Examples thereof include a monovalent group derived from a 5- to 6-membered ring containing one or two nitrogen atoms, oxygen atoms, or sulfur atoms as ring atoms, such as a ring, a piperazine ring, and a morpholine ring. Also,
As the unsaturated heterocyclic group, a furan ring, a benzofuran ring,
Examples thereof include groups having 4 to 9 carbon atoms derived from a thiophene ring, a benzothiophene ring, a pyrrole ring, an indole ring, a pyridine ring, a quinoline ring, an isoquinoline ring, and the like.

In the above formula (4), the ring formed by R ⁶ and R ⁷ together includes a norbornylidene group, a bicyclo [3.3.1] 9-nonylidene group and the like.

In the above equation (4),

[0035]

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As the divalent aromatic hydrocarbon group represented by the formula (1), there can be mentioned a divalent group derived from one benzene ring or two to three condensed rings thereof. Examples of the saturated heterocyclic group include a 5- to 7-membered ring containing one or two oxygen atoms, nitrogen atoms, or sulfur atoms as ring-constituting atoms, or a divalent group derived from a condensed ring thereof with a benzene ring. be able to. Specific examples of the divalent aromatic hydrocarbon group include those having 6 carbon atoms derived from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, and the like.
To 14, and specific examples of the divalent unsaturated heterocyclic group include a furan ring, a benzofuran ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrrole ring, a thiophene ring, and a thiophene ring. And a group having 4 to 9 carbon atoms derived from a benzothiophene ring or the like.

In these divalent aromatic hydrocarbon groups or unsaturated heterocyclic groups, at least one of hydrogen atoms may be substituted, and the substituent is not particularly limited. For example, chlorine, bromine, Halogen atom such as iodine: C1-C10 alkyl group such as methyl group and ethyl group: C1-C10 alkoxy group such as methoxy group and ethoxy group: Carbon number such as phenyl group, tolyl group and xylyl group 6 ~
Aryl group having 10: alkoxyaryl group having 7 to 14 carbon atoms (aryl group having 6 to 10 carbon atoms substituted by alkoxy group having 1 to 4 carbon atoms): dimethylamino group, pyrrolidinyl group, piperidinyl group, morpholino group, etc. Has 1 to 1 carbon atoms
10 substituted amino groups: nitro groups: cyano groups and the like.

As the chromene compound, R ⁴ and R ⁵ are both hydrogen atoms, and R ⁶ and R ⁷ are the same or different aryl groups, unsaturated heterocyclic groups, or Is a bicyclo [3.3.1] 9-nonylidene group or a norbornylidene group formed together;

[0039]

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A compound which is a group derived from a naphthalene ring which may be substituted with an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms can be suitably used.

Specific examples of chromene compounds that can be suitably used in the present invention include the following compounds.

1) Spiro [norbornane-2,2'-
[2H] benzo [h] chromene 2) Spiro [bicyclo [3.3.1] nonane-9,2 '
-[2H] benzo [h] chromene] 3) 7'-methoxyspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [h] chromene] 4) 7'-methoxyspiro [ Norbornane-2,2'-
[2H] benzo [h] chromene] 5) 3,3-bis (3-fluoro-4-methoxyphenyl) -6-morpholino-3H-benzo [f] chromene 6) 3,3-bis (4-methoxyphenyl) ) -6-morpholino-3H-benzo [f] chromene 7) 3- (3-trifluoromethyl-4-methoxyphenyl) -3- (4-methoxyphenyl) -6-thiomorpholino-3H-benzo [f] Chromene A spirooxazine compound suitably used in the present invention can be represented by the general formula (5).

[0043]

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Here, in the general formula (5), R ⁸ and R ⁹
And R ¹⁰ are the same or different alkyl groups,
Cycloalkyl group, cycloaralkyl group, alkoxy group, alkoxyalkyl group, alkoxycarbonyl group,
An alkoxycarbonylalkyl group, an aryl group, an aralkyl group, an aryloxy group, an acyl group, an acyloxy group or an amino group, R ⁹ and R ¹⁰ may form a ring together, and R ⁸ , R ⁹ and R ¹⁰ may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, and a heterocyclic group in addition to the groups described above.

The alkyl group represented by R ⁸ , R ⁹ and R ¹⁰ in the above formula (5) includes carbon such as methyl, ethyl, propyl, butyl, isobutyl, pentyl and neopentyl. Examples of the alkyl group include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
And a cycloalkyl group such as a cyclopropylmethyl group, a cyclohexylmethyl group, or a cycloalkyl group having 4 to 11 carbon atoms such as a 2-cyclohexylethyl group.
Examples of the alkoxy group include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group, and examples of the alkoxyalkyl group include 2 to 11 carbon atoms such as a methoxymethyl group, an ethoxymethyl group and a t-butoxymethyl group. Examples of the alkoxycarbonyl group include, as the alkoxycarbonyl group, a methoxycarbonyl group and an alkoxycarbonyl group having 2 to 11 carbon atoms such as an ethoxycarbonyl group. As the alkoxycarbonylalkyl group, a methoxycarbonylmethyl group, Examples thereof include an alkoxycarbonylalkyl group having 3 to 12 carbon atoms such as a methoxycarbonylethyl group and an ethoxycarbonylmethyl group. Examples of the aryl group include a phenyl group, a tolyl group,
An aryl group having 6 to 12 carbon atoms, such as a xylyl group and a naphthyl group, can be mentioned. As the aralkyl group, a benzyl group, a phenethyl group, a naphthylmethyl group, etc.
And an aryloxy group having 6 to 1 carbon atoms such as a phenoxy group and a naphthoxy group.
An acyloxy group having 2 to 14 carbon atoms such as an acetyl group and a benzoyl group; and an acyloxy group having 2 carbon atoms such as an acetoxy group and a benzoyloxy group. To 14 acetoxy groups, and the amino group includes an amino group having 1 to 10 carbon atoms such as a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a piperidino group, and a morpholino group. Can be.

Also,

[0047]

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The group represented by is a divalent aromatic hydrocarbon group which may be substituted or a divalent unsaturated heterocyclic group, and is exemplified in the section of the chromene compound represented by the general formula (4). The same groups are employed.

[0049]

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The group represented by is a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group which may be substituted. Examples of the divalent aromatic hydrocarbon group include a divalent group derived from one benzene ring or two to three condensed rings thereof, and examples of the divalent unsaturated heterocyclic group include , A 5- to 7-membered ring containing one or two oxygen atoms, nitrogen atoms or sulfur atoms as ring-constituting atoms, or a divalent group derived from a condensed ring thereof with a benzene ring. Specific examples of the divalent aromatic hydrocarbon group include a group having 6 to 14 carbon atoms derived from a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, and the like. Specific examples of the saturated heterocyclic group include groups having 4 to 9 carbon atoms derived from a furan ring, a benzofuran ring, a pyridine ring, a quinoline ring, an isoquinoline ring, a pyrrole ring, a thiophene ring, a thiophene ring, and a benzothiophene ring. Can be mentioned.

The substituents of the above-mentioned divalent aromatic hydrocarbon group or divalent unsaturated heterocyclic group include the above-mentioned R ⁸ and R ⁹
And the same groups as those described for R ¹⁰ can be selected.

[0052]

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(Provided that R ¹¹ and R ¹² are the same or different and each may be an optionally substituted alkyl group, alkoxy group or allyl group, etc., and R ¹¹ and R ¹² are bonded to each other, cyclized, May form a nitrogen heterocyclic ring), because a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group substituted with a group represented by the following formula: It is suitable.

Specific examples of spirooxazine compounds which can be suitably used in the present invention include the following compounds.

1) 1'-methoxycarbonylmethyl-
8 "-methoxy-6"-(4-methylpiperazino) dispiro (cyclohexane-1,3 '-(3H) indole-2'-(1'H), 3 "-(3H) naphtho (3,2 −
a) (1,4) oxazine) 2) 6′-fluoro-1 ′, 5′-dimethyl-6 ″ -morpholinodispiro (cyclohexane-1,3 ′-(3
H) Indole-2 '-(1'H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine) 3) 6'-Fluoro-5'-methyl-1'- Isobutyl-6 ″ -morpholinodispiro (cyclohexane-1,
3 '-(3H) indole-2'-(1'H), 3 ''-
(3H) naphtho (3,2-a) (1,4) oxazine) 4) 3 ′, 3′-dimethyl-1′-isopropyl-6 ″
-Indolinospiro- (3H) indole-2'-
(1′H), 3 ″-(3H) naphtho (3,2-a)
(1,4) oxazine 5) 3 ′, 3′-dimethyl-1′-isobutylspiro-
(3H) indole-2 '-(1'H), 3''-(3
H) Naphtho (3,2-a) (1,4) oxazine The fulgide compound suitably used in the present invention can be represented by the general formula (6).

[0056]

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[However,

[0058]

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Is a divalent aromatic hydrocarbon group which may have a substituent or a divalent unsaturated heterocyclic group, and R ¹³ is an alkyl group, an aryl group or a monovalent heterocyclic group. And

[0060]

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Is a norbornylidene group or an adamantylidene group, and X is an oxygen atom, a group> NR ¹⁴ , a group> NA ¹ -B ^1- (A ² ) _m- (B ² ) _n- R ¹⁵ , a group> NA ³ -A ⁴ , or a group> NA ³ -R ¹⁶ (where R ¹⁴ is a hydrogen atom, an alkyl group or an aryl group, and A ¹ , A ² and A ³ is the same or different and is an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group;
¹ and B ² may be the same or different

[0062]

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And m and n each independently represent 0 or 1, but when m is 0, n is 0 and R
¹⁵ is an alkyl group, a naphthyl group or a naphthylalkyl group, A ⁴ is a naphthyl group, and R ¹⁶ is a halogen atom, a cyano group or a nitro group. ). In the above formula (6),

[0064]

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The divalent aromatic hydrocarbon group or the divalent unsaturated heterocyclic group represented by the formula is the same as the group in the above formula (4), and the substituent of each of these groups is not particularly limited. For example, halogen atoms such as chlorine, bromine and iodine: alkyl groups having 1 to 10 carbon atoms such as methyl group and ethyl group: alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group: phenyl group and tolyl group And an aryl group having 6 to 10 carbon atoms such as a xylyl group: an alkoxyaryl group having 7 to 14 carbon atoms (an aryl group having 6 to 10 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms): a dimethylamino group, Examples thereof include a substituted amino group having 1 to 10 carbon atoms such as a pyrrolidinyl group, a piperidinyl group, and a morpholino group: a nitro group: a cyano group.

In the above formula (6), the alkyl group, aryl group and heterocyclic group represented by R ¹³ are an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, an oxygen atom, a nitrogen atom, Atom or sulfur atom as a ring constituent atom
And a monovalent group derived from a 5- to 7-membered ring containing no more than 2 or a condensed ring of this and a benzene ring. Specific examples of the alkyl group include a methyl group, an ethyl group,
A propyl group, a butyl group, a cyclopropyl group, and the like can be given.Specific examples of the aryl group include:
Specific examples of the heterocyclic group include nitrogen-containing heterocyclic rings such as a pyrrole ring, a pyridine ring, a quinoline ring, and a piperidine ring; a furan ring and benzofuran. Oxygen-containing heterocycle such as a ring and an oxolane ring; a thiophene ring, a benzothiophene ring,
A group based on a sulfur-containing heterocycle such as a thiolane ring can be exemplified.

[0067] When the above formula (6) Medium X is> N-R ^14, an alkyl group represented by R ^14, an aryl group above R ¹³
Is the same as X is> N−A ¹ −B ¹ − (A ² ) _m − (B ² ) _n −
When R ¹⁵ ,> NA ³ -A ⁴ , or> NA ³ -R ¹⁶ , the alkylene group represented by A ¹ , A ² and A ³ is
It is preferably a group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group, and the alkylidene group is a group having 2 to 4 carbon atoms such as an ethylidene group, a propylidene group, and an isopropylidene group. The cycloalkylene group is preferably a cyclohexylene group, and the alkylcycloalkane-diyl group is more preferably a dimethylcyclohexane-diyl group.

[0068] Further, the equation (6) Medium X is> N-A ¹ -B ¹
When-(A ² ) _m- (B ² ) _n -R ¹⁵ , the alkyl group represented by R ¹⁵ is the same as the above R ¹³ , and the naphthylalkyl group is a carbon atom such as a naphthylmethyl group or a naphthylethyl group. Number 1
It is preferably a group of 1 to 14.

Among the fulgide compounds represented by the above formula (6), in consideration of the durability of the photochromic action, etc., R ¹³ is an alkyl group, and X is> NR—
R is a cyanoalkyl group having 1 to 4 carbon atoms, a nitroalkyl group having 1 to 4 carbon atoms, or an alkoxycarbonylalkyl group having 3 to 9 carbon atoms (an alkoxy group having 1 to 4 carbon atoms and an alkylene having 1 to 4 carbon atoms) Group). ]

[0070]

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Is an adamantylidene group,

[0072]

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Is an aryl group having 6 to 10 carbon atoms or an alkoxyaryl group having 7 to 14 carbon atoms (1 to 4 carbon atoms)
The compound is preferably a heterocyclic group which may be substituted with an aryl group having 6 to 10 carbon atoms and substituted with an alkoxy group, particularly a group derived from a thiophene ring.

Specific examples of fulgide compounds that can be suitably used in the present invention include the following compounds.

Furgide compound: 1) N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.
1.1] Decane) 2) N-cyanomethyl-6,7-dihydro-2- (p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 3) N-cyanomethyl-6,7-dihydro-4 -Methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 4) 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl- 2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 5) 6,7-dihydro-4-methyl-2- (p -Methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 6) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-3-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 7) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-spiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.
1) Decane) When the curable composition of the present invention is used for an eyeglass lens, a color tone such as gray or brown is preferred.
Since such a color tone cannot be obtained with a single photochromic compound, a method of mixing two or more different photochromic compounds is employed. The above-mentioned fulgide compound and spirooxazine compound generally develop an orange-blue color, but by mixing a chromene compound which develops a yellow-orange color, an intermediate color such as gray or brown can be obtained.

In the present invention, the mixing ratio of the photochromic compound is 0.1 to 100 parts by weight of the total polymerizable monomer.
The content is in the range of 001 to 10 parts by weight. When the amount is less than 0.001 part by weight, the durability of the photochromic property is impaired. The compounding ratio of the photochromic compound is preferably in the range of 0.01 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total polymerizable monomer. The best photochromic performance with a balance between properties and initial coloring is obtained.

The photochromic curable composition of the present invention further comprises a releasing agent, an ultraviolet absorber, an infrared absorber, an ultraviolet stabilizer, an antioxidant, a coloring inhibitor, an antistatic agent, a fluorescent dye, a dye, a pigment, Various stabilizers and additives such as fragrances can be mixed and used as needed.

It is preferable to use the photochromic curable composition of the present invention in combination with an ultraviolet stabilizer since the durability of the photochromic compound can be further improved. As the ultraviolet stabilizer, a hindered amine light stabilizer, a hindered phenol light stabilizer, and a sulfur-based antioxidant can be preferably used.

The amount of the UV stabilizer used is not particularly limited, but is usually 0.001 to 10 parts by weight of each UV stabilizer based on 100 parts by weight of the total polymerizable monomer. Further, the amount is preferably in the range of 0.01 to 1 part by weight.

Further, when a fulgide compound and a chromene compound are used in combination, a phosphite compound can be added to suppress the change over time of the mixed color of these photochromic compounds. Therefore, it is most preferred in the present invention to use both the above-mentioned ultraviolet stabilizer and phosphite compound in a system in which a fulgide compound and a chromene compound are used in combination. The compounding amount of the phosphite compound is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the whole polymerizable monomer.

Further, when an infrared absorbing agent is mixed and used, a photochromic cured product having an infrared absorbing ability in addition to the photochromic action can be obtained. As the infrared absorber, polymethine compounds, diimonium compounds, cyanine compounds, anthraquinone compounds, and aluminum compounds can be used, but diimonium compounds having a large molecular extinction coefficient and exhibiting an effect when added in a small amount are preferable. is there.

The compounding amount of the infrared absorber is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.01 part by weight, based on 100 parts by weight of the total polymerizable monomer.

The polymerization method for obtaining a cured product from the curable composition of the present invention is not particularly limited, and a known radical polymerization method can be employed. Polymerization initiation means, use of radical polymerization initiators such as various peroxides and azo compounds, or ultraviolet,
Irradiation with α-rays, β-rays, γ-rays or the like or a combination of both can be performed. Illustrating a typical polymerization method, between a mold held by an elastomer gasket or a spacer, inject the photochromic composition of the present invention mixed with a radical polymerization initiator, and after curing in an air oven, from the mold Detachable casting polymerization is employed.

The radical polymerization initiator is not particularly limited and known ones can be used. Representative examples thereof include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, and the like. Diacyl peroxides such as acetyl peroxide; peroxyesters such as t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate and t-butylperoxybenzoate; diisopropyl Percarbonates such as peroxydicarbonate and di-sec-butylperoxydicarbonate; azo compounds such as azobisisobutyronitrile;

The amount of the radical polymerization initiator used depends on the polymerization conditions, the type of the initiator, and the composition of the above-mentioned monomer.
Although it cannot be limited unconditionally, generally, all polymerizable monomers 1
The range is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight.

Among the polymerization conditions, especially the temperature affects the properties of the obtained cured product. The temperature condition is affected by the type and amount of the initiator and the type of the monomer, and thus cannot be unconditionally limited. Generally, the polymerization is started at a relatively low temperature, and the temperature is gradually increased. It is preferable to perform a so-called tapered two-stage polymerization in which the composition is cured at a high temperature at the time of completion. Since the polymerization time also varies depending on various factors like the temperature, it is preferable to determine an optimum time in advance according to these conditions, but in general, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

Further, the cured product obtained by the above method is
The following processing can be performed according to the use. That is, dyeing using a dye such as a disperse dye, a silane coupling agent, a hard coat agent containing a sol such as silicon, zirconium, antimony, aluminum, tin, and tungsten as a main component, and SiO ₂ , TiO ₂ , and ZrO ₂ . Processing such as antireflection treatment and antistatic treatment by vapor deposition of a metal oxide thin film or application of a thin film of an organic polymer, and secondary treatment can also be performed.

[0088]

According to the curable composition of the present invention, since the solubility of the bifunctional polymerizable monomer represented by the general formula (1) in the component (B) is high, the liquid curable composition can be easily prepared. And thus excellent operability. Moreover, it has excellent optical properties such as a high refractive index, and when a photochromic compound is added, both the color density and the durability are high,
It is practical enough. Therefore, a cured product obtained by polymerizing the curable composition of the present invention is useful as a high refractive index organic glass, particularly as an optical material, and when a photochromic compound is added, a cured product having photochromic properties is obtained. It is useful as a refractive index optical material, and can be suitably used for applications such as eyeglass lenses and photochromic lenses.

[0089]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

The compounds and abbreviations used in the following examples are as follows.

(1) Bifunctional polymerizable monomer represented by the general formula (1) TB: 2,2-bis (4-methacryloyloxyethoxy-3,5-dibromophenyl) propane TBA: 2,2-bis (4-acryloyloxyethoxy-3,5-dibromophenyl) propane TBP: 2,2-bis (4-methacryloyloxyisopropoxy-3,5-dibromophenyl) propane (2) 2 represented by the general formula (1) A polymerizable monomer comprising a functional polymerizable monomer and a monofunctional polymerizable monomer represented by the general formula (2) TB2: TB containing 2% by weight of a monoester of TB TB10: a monoester of TB 10 TB TB20 containing 20% by weight of TB TB20: TB containing 20% by weight of a monoester of TB TB50: TB containing 50% by weight of a monoester of TB TBTA10: Mono of TBA TBA containing 10% by weight of a ster body TBP10: TBP containing 10% by weight of a monoester of TBP (3) Polymerizable monomer of component (B) GMA: glycidyl methacrylate BzMA: benzyl methacrylate MS: α-methylstyrene St: Styrene 4G: Tetraethylene glycol dimethacrylate MPSM: 4,4'-bis (4-methacryloylthiophenyl) sulfide DVB: Divinylbenzene (4) Photochromic compound C1: Spiro [bicyclo [3.3.1] nonane-9,
2 '-[2H] benzo [h] chromene] S1: 6'-fluoro-1', 5'-dimethyl-6 "-
Morpholinodispiro (cyclohexane-1,3 ′-(3
H) Indole-2 '-(1'H), 3 "-(3H) naphtho (3,2-a) (1,4) oxazine) F1: N-cyanomethyl-6,7-dihydro-2- (p
-Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) Example 1 2 represented by the general formula (1) As a polymerizable monomer composed of a functional polymerizable monomer and a monofunctional polymerizable monomer represented by the general formula (2), T containing 10% by weight of a TB monoester is used.
10 g of a mixture of a monoester of B and TB (TB10)
The styrene as a component (B) is dissolved in a polymerizable monomer composed of a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2). Until,
It was added at room temperature (20 ° C.) with good stirring. In this case, the polymerizable monomer composed of a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2) dissolved in 100 g of the component (B) is used. The weight (g) is defined as the solubility of the component (A), and the polymerizability of the bifunctional polymerizable monomer represented by the general formula (1) and the monofunctional polymerizable monomer represented by the general formula (2) T contained in the monomer
The weight (g) of B was expressed as the solubility of the monomer (1).

Table 1 shows the results.

Examples 2 to 8 A polymerizable monomer comprising a bifunctional polymerizable monomer represented by the general formula (1) shown in Table 1 and a monofunctional polymerizable monomer represented by the general formula (2) Example 1 except for using body and component (B)
The solubility was measured in the same manner as described above. The results are shown in Table 1.

Comparative Examples 1 to 5 Polymerizable monomers comprising the bifunctional polymerizable monomer represented by the general formula (1) and the monofunctional polymerizable monomer represented by the general formula (2) in Examples 1 to 5 The solubility was measured in the same manner as in Example 1 using only the bifunctional polymerizable monomer represented by the general formula (1) used in the monomer. The results are shown in Table 1.

Examples 1 to 3 and Comparative Examples 1 to 3 compare the solubility of TB10 and TB with various copolymer monomers. In each case, TB10
Shows that the solubility is higher. It can be seen that Examples 4 and 5 also have higher solubility than Comparative Examples 4 and 5, respectively.

[0096]

[Table 1]

Example 9 44 parts by weight of TB10 as a polymerizable monomer comprising a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2) , (B) component G
5 parts by weight of MA and 51 parts by weight of BzMA were mixed and stirred at room temperature for 2 hours. 0.05 parts by weight of C1 as a photochromic compound and 1 part by weight of t-butylperoxy-2-ethylhexanate as a radical polymerization initiator were added to the mixed solution and mixed well. This mixture was poured into a mold composed of a glass plate and a gasket made of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out in an air oven at 30 ° C. to 90 ° C. for 18 hours,
The temperature was gradually increased and kept at 90 ° C. for 2 hours. After the polymerization was completed, the mold was removed from the air oven, and after cooling, the cured product was removed from the glass mold of the mold.

The resulting photochromic cured product (thickness 2
mm), a xenon lamp L-24 made by Hamamatsu Photonics
80 (300 W) SHL-100 was passed through an aeromass filter (manufactured by Corning Incorporated) at 20 ° C. ± 1 ° C., and the beam intensity on the surface of the cured product was 365 nm = 2.4 mW / cm ² , 2
Irradiation was performed at 45 nm = 24 μW / cm ² for 120 seconds to develop color, and the following various photochromic properties were measured.

Maximum absorption wavelength (λmax (nm)): λmax after color development of this cured product was determined using a spectrophotometer MCPD1000 manufactured by Otsuka Electronics Co., Ltd.

Coloring density: ε (120) −ε (0) was determined and defined as the coloring density. Here, ε (120) is the absorbance at the maximum absorption wavelength of the photochromic compound when light is irradiated for 120 seconds under the above conditions and the color is developed.
(0) is the absorbance at the same absorption wavelength as at the time of color development before light irradiation.

Photochromic durability: Xenon fade meter FA-25AX-H manufactured by Suga Test Instruments Co., Ltd.
C was used to measure the fatigue life, which was taken as the photochromic durability. Fatigue life, after irradiating the polymer to a xenon fade meter for 200 hours, the cured product is colored by the method described above, the absorbance at the maximum absorption wavelength based on the color of the photochromic compound at that time, the color development before irradiation with the fade meter And expressed as a ratio (%) to the absorbance.

The optical properties of the obtained cured product were measured by the following test methods.

Refractive index and Abbe number: The refractive index and Abbe number at 20 ° C. were measured using an Abbe refractometer manufactured by Atago Co., Ltd. Bromophthalene was used as the contact liquid.

Table 2 shows the measurement results.

Examples 10 to 20 A polymerizable monomer comprising a bifunctional polymerizable monomer represented by the general formula (1) shown in Table 2 and a monofunctional polymerizable monomer represented by the general formula (2) Polymerization was carried out in the same manner as in Example 9 except that the polymer, the component (B) and the photochromic compound were used. After obtaining a photochromic cured product, various photochromic properties were measured. The results are shown in Table 2.

[0106]

[Table 2]

Comparative Examples 6 to 13 Comparative Examples 6 to 13 were carried out in exactly the same manner as in Example 9 except that the compounds shown in Table 3 were used as the polymerizable monomers. The results are shown in Table 3.

Comparative Examples 6 and 7 are polymerizable monomers composed of a bifunctional polymerizable monomer represented by the general formula (1) and a monofunctional polymerizable monomer represented by the general formula (2) in the examples. Is replaced by TB, and the component (B) is to be polymerized with almost no change. When stirred at room temperature, the compositions of Comparative Examples 6 and 7 did not become a uniform solution, so that a transparent cured product could not be obtained, and the refractive index and other physical properties could not be measured. Further, when the mixture was heated to 60 ° C. and stirred to dissolve TB, polymerization proceeded during the stirring, and a uniform cured product could not be obtained, and physical properties could not be measured.

Comparative Examples 8 to 11 are cases where St was used to dissolve TB. When St is used, TB can be dissolved without using a monofunctional polymerizable monomer represented by the general formula (2). However, Examples 9 and Comparative Examples 8 and 10 can be used.
And Comparative Example 9, Example 11 and Comparative Example 10, and Example 19 and Comparative Example 11 reveal that Comparative Examples 8 to 11 all have reduced color density and durability in photochromic characteristics. .

Comparative Examples 12 and 13 are cases where a high refractive index cured product was produced without using TB. However, in both cases, compared with Example 9, both the color density and the durability in terms of photochromic characteristics were lowered. You can see that there is.

[0111]

[Table 3]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09K 9/02 C09K 9/02 B G02B 1/04 G02B 1/04 G03C 1/73 503 G03C 1/73 503

Claims (3)

[Claims] (A) The following general formula (1): (Provided that R ¹ and R ² are the same or different hydrogen atoms or methyl groups, X is a bromine atom, a chlorine atom or a hydrogen atom, p and q are each independently 1 or 2, m, n
Is each independently an integer of 1 to 4. A) a bifunctional polymerizable monomer represented by the following general formula (2): (Provided that R ¹ and R ² are the same or different hydrogen atoms or methyl groups, X is a bromine atom, a chlorine atom or a hydrogen atom, p and q are each independently 1 or 2, m, n
Is each independently an integer of 1 to 4. ), And the proportion of the monofunctional polymerizable monomer represented by the general formula (2) in the total amount thereof is 5 to 5
100 parts by weight of a polymerizable monomer that is 0% by weight, and
(B) a polymerizable monomer 1 other than the polymerizable monomer comprising the bifunctional polymerizable monomer represented by the general formula (1) and the monofunctional polymerizable monomer represented by the general formula (2) Curable composition characterized by containing -1000 parts by weight. 2. Photochromic compound 0.001 to 10 based on 100 parts by weight of the curable composition according to claim 1.
A photochromic curable composition containing parts by weight. 3. An optical material obtained by curing the curable composition according to claim 1.