JPH08272036A - Photochromic composition and photochromic resin using the composition - Google Patents

Abstract

PURPOSE: To obtain a photochromic compsn. excellent in heat resistance, mechanical strength, adhesiveness of a hard coat, formability, etc., having satisfactory light resistance of photochromic performance can capable of attaining light in weight and thin in thickness. CONSTITUTION: This photochromic compsn. contains 100 pts.wt. di(meth)-acrylate compd. represented by the formula and 0.01-5 pts.wt. photochromic compd. In the formula, R<1> is H or methyl, each of R<2> and R<3> is 1-4C alkylene, X is halogen other than F, Y is O or S and (m) is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composition and a photochromic resin using the same.

BACKGROUND research techniques photochromism has been many prior art, the use is recording materials are diverse, such as optical lenses. In particular, spectacle lenses with photochromic properties
It is popular as a lens with high added value because it remains colorless or light indoors and tints under outdoor sunlight to function as sunglasses. Early photochromic lenses used glass containing silver halide,
At the time of color development, it developed a calm color such as gray or brown. However, the glass lens itself is very heavy and easily broken, and resin-made ones have become the mainstream because of the demand for safety and weight reduction. Furthermore, in the photochromic lens made of glass, color development occurs even in the interior, so that an apparent density difference occurs in portions having different lens thicknesses, which is unnatural to the eye.

A resin photochromic lens is manufactured by kneading a photochromic compound into a resin for a lens and molding the compound. Various photochromic compounds to be kneaded into a resin for use have been proposed. For example, JP-A-61-161286 discloses a spirooxazine compound, and JP-B-3-43315 discloses a photochromic composition containing a spirooxazine photochromic composition and a hindered amine light stabilizer. Has been done.

Further, as an example of a photochromic composition obtained by incorporating a photochromic compound into a resin, chromene or its derivative, fulgide compound or fulgimide compound, and an ultraviolet stabilizer are disclosed in JP-A-3-121188. A photochromic composition that develops a color such as gray, amber, or brown is disclosed. Further, JP-A-61-233079 discloses a specific spirooxazine compound,
A resin obtained by dissolving this compound in methyl methacrylate and casting polymerization is exemplified.

Unlike a glass photochromic lens, unlike a glass photochromic lens, the difference in color density due to the thickness is unlikely to occur. However, it has been pointed out that since the photochromic compound is kneaded into the resin, the photochromic compound is likely to be deteriorated by the action of the radical species generated during the polymerization of the resin and the action of the polymer matrix itself. This tends to cause a marked decrease in initial color development performance and a decrease in color formation due to repeated use or long-term use.

This means that the monomer species that can be used for producing the photochromic resin are limited, and in a resin system that emphasizes photochromic performance, physical properties other than photochromic (for example, specific gravity, mechanical strength, refractive index, etc.) It can be said that he had no choice but to sacrifice. In particular, photochromic compounds that develop a subdued color such as gray or brown have poor durability in many resins. Therefore, it can be said that it was difficult to obtain a practical photochromic resin in the system using these photochromic compounds. For example, it is said that a photochromic lens having excellent light resistance cannot be obtained from allyldiglycol carbonate widely used as a spectacle lens and the above photochromic compound.

From such a background, in the above-mentioned known art,
As a usable resin, only a general transparent resin which is inferior in refractive index such as polymethylmethacrylate is disclosed.

Further, at present, it is widely practiced to obtain a thin and lightweight lens using a resin having a high refractive index. Most high refractive index resins are obtained from monomers containing aromatic rings. In a photochromic lens, if a resin containing an aromatic ring is used to increase the refractive index, the adhesion of the hard coat is likely to decrease, and the coating film may peel off during use in spectacle lenses used under severe conditions. Was observed.

On the other hand, when urethane or thiourethane resin having a high refractive index was used, it was observed that the isocyanate as a resin raw material reacts with the photochromic compound at the stage of the monomer and no photochromic performance is exhibited.

Under the circumstances as described above, it can be said that there is still a need for an excellent photochromic resin.

[0011]

SUMMARY OF THE INVENTION The present inventors have now identified a specific di (meta)
It has been found that a photochromic composition using an acrylate compound can provide a photochromic resin excellent in various properties. The present invention is based on such findings.

Therefore, an object of the present invention is to provide a photochromic composition which can realize a photochromic resin excellent in various characteristics.

Another object of the present invention is to provide a photochromic resin excellent in various characteristics.

The photochromic composition according to the present invention is a photochromic composition polymerized into a photochromic resin,

[0015]

Embedded image (In the formula, two R ¹ 's each independently represent a hydrogen atom or a methyl group, and two R ^2's and two R ^3's are
Independently, each represents an alkylene group having 1 to 4 carbon atoms, X represents a halogen atom other than fluorine, and two Y
Each independently represent an oxygen atom or a sulfur atom, and m represents an integer of 0 to 4. ) Di (meta)
An acrylate compound and (b) a photochromic compound in an amount effective for imparting a photochromic function to the photochromic resin.

The photochromic resin according to the present invention comprises a polymer of this photochromic composition.

[0017]

DETAILED DESCRIPTION OF THE INVENTION Definitions In the present specification, an alkyl group or an alkyl group as a part of a group may be linear or branched. Further, in the present specification, the halogen atom represents fluorine, chlorine, bromine, or iodine unless otherwise specified. Further, the halogenoalkyl group refers to an alkyl group in which one or more hydrogen atoms are substituted with a halogen atom.

Photochromic Composition The photochromic composition according to the present invention comprises a di (meth) acrylate compound (component (a)) represented by the above general formula (I) and a photochromic compound (component (b)). The one. The term "comprising" as used herein includes not only the components (a) and (b) but also a third component other than the components (a) and (b). Also means. Examples of such a third component include, for example, a polymerizable monomer other than the component (a), an ultraviolet stabilizer, a polymerization initiator, and the like (the details will be described later).

Component (a): Compound of di (meth) acrylate
Things di (meth) acrylate compound used in the present invention has a structure in which the acrylic acid or methacrylic acid represented by the general formula (I) linked by thioether chain, and nuclear halogen-substituted or during the thioether chain It has an unsubstituted phenylene group.

By using the polymerizable monomer represented by the general formula (I), photochromic excellent in heat resistance, mechanical strength, impact resistance, low water absorption, hard coat adhesion, moldability, etc. A resin can be obtained. Further, the photochromic resin according to the present invention has a good photochromic performance and is characterized in that the performance is maintained even when it is used for a long period of time. Further, the photochromic composition according to the present invention has an advantage that it can realize a photochromic resin having a high refractive index, which can make the lens lightweight and thin.

In particular, the photochromic composition and resin according to the present invention are excellent in original photochromic performance, and in addition to being excellent in moldability and hard coat adhesion, can realize a high refractive index. It can be said that these advantages are surprising from the conventional knowledge that the adhesion of the hard coat becomes poor when a resin containing an aromatic ring is used to increase the refractive index.

In the formula (I), two R ^1's independently, that is, the same or different, each represents a hydrogen atom or a methyl group. That is, in the present specification, the “di (meth) acrylate compound” means 2
One of R ¹ are both of those i.e. dimethacrylate compound methyl group, and two R ¹ are added to both those i.e. diacrylate compound is a hydrogen atom, two R ¹
Are a methyl group and a hydrogen atom, respectively.

In the di (meth) acrylate compound represented by the general formula (I), the bonding position of the thioether chain to the phenylene group may be any of o-position, m-position and p-position. The m-position and the p-position are representative and preferred. Further, it is preferable that R ² and R ³ are alkylene groups having 1 to ³ carbon atoms. R ² is particularly preferably an ethylene group or a propylene group, and R ³ is particularly preferably a methylene group or an ethylene group. Further, as X, each atom of chlorine, bromine, and iodine is adopted. The preferred X is bromine. The number of X, that is, m is 0 to
4, especially 0-2 is preferable.

Specific examples of the di (meth) acrylate compound represented by the general formula (I) which is preferably used in the present invention include p-bis (2-methacryloyloxyethylthio) xylylene and p-bis. (3-methacryloyloxypropylthio) xylylene, p-bis (2-methacryloyloxyethylthioethyl) phenylene, p-bis (3-methacryloyloxypropylthioethyl) phenylene and the like can be mentioned. In the present invention, these di (meth) acrylate compounds may be used alone or in combination of two or more.

In the photochromic composition according to the present invention, only the di (meth) acrylate compound represented by the general formula (I) may be used as the polymerizable monomer.
According to a preferred embodiment of the present invention, other polymerizable monomer may be used in combination.

The polymerizable monomer used in combination with the compound of formula (I) is a polymerizable monomer which gives a homopolymer having a high refractive index of 1.55 or more, and a refractive index of 1.
Polymerizable monomers that give homopolymers with a medium or low refractive index of less than 55 are included. In the present invention, any monomer can be used without any limitation as long as it does not violate the spirit of the present invention.

As the polymerizable monomer which gives a homopolymer having a refractive index of 1.55 or more, a mono (meth) acrylate compound represented by the following general formula (II) and the following general (III) di (meth) Acrylate compounds are mentioned.

[0028]

[Chemical 6] (In the formula (II), R ¹ has the same meaning as defined in the formula (I), and R ⁴ is a phenyl group, a benzyl group,
Alternatively, it represents a 2-phenoxyethyl group, or a group in which a part of hydrogen atoms in those substituents is substituted with a halogen atom other than fluorine.

In the above formula (III), R ¹ is the formula (I)
Has the same meaning as defined in the above, two R ³⁰ 's each independently represent a hydrogen atom or a methyl group,
^{R 5, R 6, R 7} , and R ^8, independently each represent a halogen atom exclusive of a hydrogen atom or fluorine, and m and n represent an integer of m + n = 0. ) The combined use of the mono (meth) acrylate compound represented by the general formula (II) with the compound of the formula (I) is preferable from the viewpoint that the refractive index of the resin can be increased and the mechanical strength can be improved. Specific preferred examples of the (meth) acrylate compound include phenyl (meth) acrylate, benzyl (meth) acrylate, and 2-phenoxyethyl (meth).
Acrylate, 1,3,5-tribromophenyl (meth) acrylate, 2- (1 ', 3', 5'-tribromophenyl) oxyethyl (meth) acrylate and the like can be mentioned.

When the di (meth) acrylate compound represented by the general formula (III) is used in combination with the compound of the formula (I), the resin can have a high refractive index and the heat resistance and mechanical strength can be improved. It is preferable in terms. Specific preferred examples of this di (meth) acrylate compound include 2,2′-bis [4- (methacryloyloxyethoxy) phenyl]
Propane, 2,2'-bis [(3,5-dibromo-4-
Methacryloyloxyethoxy) phenyl] propane and the like can be mentioned.

Next, as the polymerizable monomer which gives a homopolymer having a refractive index of less than 1.55, the following general formula (I
V) or a mono (meth) acrylate compound of the general formula (V), or a di (meth) acrylate compound of the general formula (VI).

[0032]

[Chemical 7] (In the formula (IV), R ¹ has the same meaning as defined in the formula (I), and R ⁹ represents an alkyl group having 1 to 4 carbon atoms.) In the formula (V), R ¹ has the same meaning as defined in formula (I), and R ¹⁰ represents an alicyclic hydrocarbon group having 5 to 16 carbon atoms. ) In the formula (VI), R1 represents the same meaning as defined in formula (I), R ³⁰ represents the same meaning as defined above formula (III), n 10 Represents the integer. The combined use of the mono (meth) acrylate compound represented by the general formula (IV) with the compound of the formula (I) is advantageous in that the photochromic color development performance and the photochromic durability of the resin can be improved. Preferred specific examples of the compound of the formula (IV) include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth). ) Acrylate, t-butyl (meth) acrylate and the like.
From the viewpoint of improving the strength and photochromic durability of the resin composition, methyl (meth) acrylate and ethyl (meth) acrylate are more preferable.

When the mono (meth) acrylate compound represented by the general formula (V) is used in combination with the compound of the formula (I), the moldability of the resin, the low water absorption, the heat resistance, the impact resistance, and the mechanical strength are obtained. Is advantageous in that The alicyclic hydrocarbon group having 5 to 16 carbon atoms represented by R ¹⁰ in the formula (V) is preferably a cyclomonocycle having 5 to 8 carbon atoms, and further 6 carbon atoms.
~ 12 bridged rings (eg, norbornyl group, adamantyl group, isobornyl group, etc.). One or more hydrogen atoms of these alicyclic hydrocarbon groups may be substituted, and specific examples of the substituent include, for example, hydroxy group; substituted amino group such as methylamino group and diethylamino group; C1-C4 alkoxy groups such as methoxy, ethoxy and tert-butoxy groups; C7-C15 aralkoxy groups such as benzyloxy; C6-C16 phenoxy and 1-naphthoxy groups Aryloxy group; lower alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group and t-butyl group; halogen atom such as fluorine, chlorine and chlorine; cyano group: carboxyl group; carbon number such as ethoxycarbonyl group 2-10 alkoxycarbonyl group; halogen-substituted alkyl group having 1 or 2 carbon atoms such as trifluoromethyl group; nitro group; phenyl group, tolyl group, etc. Aryl group; a benzyl group, phenylethyl group, and aralkyl groups such as phenylpropyl group. Specific preferred examples of the compound of formula (V) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate,
Examples include norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate,
In particular, cyclohexyl (meth) acrylate, norbonyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be mentioned.

Further, the di (meth) acrylate compound represented by the general formula (VI) is a compound having a crosslinkability, and when it is used in combination with the compound of the formula (I), the mechanical strength of the resin can be improved. It is advantageous in terms. The n of the ethylene glycol chain or the propylene glycol chain contained in the structural formula is 1 to 10, but 3 to 5 is particularly preferable from the viewpoint of heat resistance, brittleness, water absorption of the resin and the like.

The above other polymerizable monomers may be used alone or in a mixture of two or more in each group and / or between each group.

In the present invention, when the other polymerizable monomer described above is used in combination with the di (meth) acrylate compound represented by the general formula (I), the blending amount of each monomer component is Although it may be appropriately determined in consideration of the combination, the refractive index, the adhesion of the coating film, the photochromic color development performance, and in consideration of the effect of durability, usually in the total amount of these polymerizable monomers, the above formula The content of the di (meth) acrylate compound represented by (I) is preferably 20% by weight or more, more preferably 20 to 70% by weight.

In particular, it is preferable to adjust the amount of the polymerizable monomer used in combination to give a homopolymer having a refractive index of 1.55 or more, so that the resin obtained has a refractive index of 1.54 or more. preferable. Further, in the case of a polymerizable monomer in which the refractive index of another polymerizable monomer homopolymer used in combination is less than 1.55, the di (meth) acrylate compound represented by the formula (I) is a polymerizable monomer. From the viewpoint of the refractive index, it is preferably 40% by weight or more in the total amount of the body.

On the other hand, when the mono (meth) acrylate compound represented by the general formula (II) is used in combination, the blending amount thereof is usually a polymerization amount in consideration of improvement of mechanical strength of the resin, maintenance of heat resistance and the like. 5 to 4 in the total amount of the polymerizable monomer
It is preferably 0% by weight. When the di (meth) acrylate represented by the general formula (III) is used in combination, the compounding amount thereof is 5 to 40% by weight in consideration of the improvement of the mechanical strength of the resin, the maintenance of the adhesiveness of the coat film, and the like. Is preferred.

Further, when the mono (meth) acrylate compound represented by the above general formula (IV) is used in combination, the blending amount is determined in consideration of the photochromic color development performance of the resin, the improvement of durability, and the maintenance of polymerization moldability. Then 5-30
Preferably, it is weight%. Further, when the mono (meth) acrylate compound represented by the general formula (V) is used in combination, the blending amount thereof is 5 to 30 weight in consideration of the improvement of the mechanical strength of the resin and the maintenance of photochromic durability. % Is preferred. Furthermore, when the di (meth) acrylate compound represented by the general formula (VI) is used in combination,
The blending amount thereof is preferably 5 to 40% by weight in consideration of the improvement of the mechanical strength of the resin and the maintenance of the photochromic coloring performance.

In the present invention, the most preferable combination of the above-mentioned polymerizable monomers is specifically exemplified, and the di (meth) acrylate compound 40 to 40 represented by the general formula (I) is used.
70% by weight, 5 to 30% by weight of the mono (meth) acrylate compound represented by the general formula (IV), 5 to 30% by weight of the mono (meth) acrylate compound represented by the general formula (V), and the general formula (VI). The composition is composed of 5 to 40% by weight of the di (meth) acrylate compound represented by.

Other suitable combinations include di (meth) acrylate compounds 20 to 20 represented by the general formula (I).
60% by weight, mono (meth) acrylate compound represented by the general formula (II) and / or mono (meth) acrylate compound represented by the general formula (III) 5-40% by weight, mono represented by the general formula (IV) (Meth) acrylate compound 5 to 30% by weight, mono (meth) represented by the general formula (V)
Acrylate compound 5 to 30% by weight, and the general formula (V
5-40 di (meth) acrylate compounds represented by I)
It is a composition consisting of parts by weight.

Component (b): Photochromic compound In the present invention, known compounds can be used as the photochromic compound without any limitation. An advantage of using the compounds of formula (I) above is that the limitation of the combined photochromic compound is essentially eliminated.

Specific examples of the photochromic compound preferably used in the present invention include spirooxazine compounds, fulgide compounds, fulgimide compounds, spiropyran compounds, and chromene compounds.

Among these photochromic compounds, the coloring properties and durability in the resin composition are good, and when considering the use for a photochromic lens such as spectacles, the temperature dependence of coloring is small, and gray and gray Those that develop a color such as brown are particularly preferable. Examples of particularly preferred photochromic compounds include spirooxazine compounds and fulgide compounds as compounds that develop a blue to orange color.
Alternatively, one or more selected from fulgimide compounds may be mentioned. Moreover, a chromene compound is mentioned as a compound which develops orange to yellow. All of these photochromic compounds combined with the compound of formula (I) exhibit good color development and durability in the resin composition.

These photochromic compounds may be used alone or in combination of two or more. Particularly, for intermediate colors such as gray and brown, it can be realized by mixing a spirooxazine compound, a fulgide compound, or a fulgimide compound that develops blue to orange, and a chromene compound that develops orange to yellow. Is.

In the present invention, the compounding ratio of the photochromic compound is not limited as long as it is an amount effective for imparting a photochromic function to the resin when it is made into a photochromic resin, but it is represented by the general formula (I). With respect to 100 parts by weight of the di (meth) acrylate compound,
0.01 to 5 parts by weight is preferable, and 0.1 is more preferable.
~ 1 part by weight. When the mixing ratio of the photochromic compound is within the above range, good and stable photochromic durability can be obtained, and a phenomenon such as aggregation of the photochromic compound can be effectively prevented.

Examples of the spirooxazine compound that can be preferably used in the present invention include those represented by the following general formula (VI
Examples thereof include compounds represented by I). These are compounds that develop from purple to blue-violet.

[0048]

Embedded image (In the formula, one of A and B represents N, the other represents CH, n is an integer of 4 to 6, R ¹¹ represents a hydrocarbon group or an alkoxycarbonylalkyl group, and R ¹²
And R ¹³ independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxyl group, a nitro group, a cyano group, a halogenoalkyl group, or an alkoxycarbonyl group, and R ¹⁴ and R ¹⁵ independently represent each other. , A hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxyl group, respectively. In the formula (VII), the hydrocarbon group represented by R ¹¹ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to
A C4-10 alkyl group, a C6-10 aryl group, and a C7-14 aralkyl group. Specific examples of the alkyl group include a methyl group, an ethyl group and an isopropyl group. Further, examples of the aryl group include a phenyl group and a naphthyl group. Further, as the aralkyl group, a benzyl group, a phenylethyl group, a phenylpropyl group,
Examples thereof include a naphthylmethyl group.

In formula (VII), the alkoxyl group in the alkoxycarbonylalkyl group represented by R ¹¹ is
It is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkylene group in the alkoxycarbonylalkyl group is preferably an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the alkoxycarbonylalkyl group include a methoxycarbonylmethyl group, a methoxycarbonylethyl group, a methoxycarbonylpropyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, an ethoxycarbonylbutyl group and a butoxycarbonylethyl group.

The halogen atom represented by R ¹² and R ¹³ in the general formula (VII) is preferably chlorine and bromine. Preferred examples of the hydrocarbon group represented by R ¹² and R ¹³ include the hydrocarbon groups described for R ¹¹ above. The alkoxyl group represented by R ¹² and R ¹³ is preferably an alkoxyl group having 1 to 10 carbon atoms, and more preferably an alkoxyl group having 1 to 4 carbon atoms. Specific examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. The alkyl group portion of the halogenoalkyl group represented by R ¹² and R ¹³ is preferably an alkyl group having 1 to 4 carbon atoms. Specific examples of the halogenoalkyl group include a trifluoromethyl group, a trichloromethyl group and a tribromomethyl group. The alkoxycarbonyl group represented by R ¹² and R ¹³ is not particularly limited, but is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group and the like.

In the general formula (VII), R ¹⁴ and R
¹⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxyl group. These halogen atoms, hydrocarbon groups,
And preferred examples of the alkoxyl group include R ¹²
And the atoms or groups described for R ¹³ .

The compound represented by the general formula (VII) may be used alone or in a mixture of two or more kinds.

The compound represented by the general formula (VII) is known and is described in, for example, JP-A-5-112777.

Examples of fulgide compounds and fulgimide compounds preferably used in the present invention include compounds represented by the following general formula (VIII). These are compounds that develop a blue to orange color.

[0055]

[Chemical 9] (In the formula, the ring represented by Y represents an aromatic hydrocarbon group which may have a substituent or an unsaturated heterocyclic group which may have a substituent, and R ¹⁶ represents an alkyl group, An aryl group,
Or a heterocyclic group, the ring represented by Z represents a norbornylidene group or an adamantylidene group, and X represents an oxygen atom, a group> N—R ¹⁷ , a group> N—A ¹ -B <sup>1
- (A 2) M- (B</sup> 2) N-R 18, group> N-A ³ -
A ^4, represent a group -A ³ -R ¹⁹ or a group> N-R,, wherein, R ¹⁷ represents a hydrogen atom, an alkyl group or an aryl group,, A ^1, A ^2, and A ³ are independently And an alkylene group, an alkylidene group, a cycloalkylene group,
Or an alkylcycloalkane-diyl group, B ¹
And B ^2, independently, each -O -, - C (=
O)-, -OC (= O)-, -OC (= O) O-, -C
Represents (= O) NH-, or -NHC (= O)-, and m
And n independently represent 0 or 1, respectively,
When m is 0, n is also 0, R ¹⁸ represents an alkyl group, a naphthyl group or a naphthylalkyl group, A ⁴ represents a naphthyl group, R ¹⁹ represents a halogen atom, a cyano group or a nitro group. R represents a cyanoalkyl group, a nitroalkyl group, or an alkoxycarbonylalkyl group. In the general formula (VIII), a preferable example of the aromatic hydrocarbon group as the ring represented together with Y is one benzene ring or a condensed ring thereof. Specific examples of the aromatic hydrocarbon group include rings having 6 to 10 carbon atoms such as benzene ring, naphthalene ring, phenanthrene ring and anthracene ring. Moreover, as a preferable example of the unsaturated heterocycle as a ring represented together with Y, a 5- to 7-membered ring containing 1 to 2 oxygen atoms, nitrogen atoms, or sulfur atoms, or a benzene ring Examples include condensed rings. Further, specific examples thereof include rings having 4 to 9 carbon atoms such as furan ring, benzofuran ring, pyridine ring, quinoline ring, isoquinoline ring, pyrrole ring, thiophene ring and benzothiophene ring.

One or more hydrogen atoms on these rings may be substituted, and examples of the substituent include a halogen atom; a methyl group, an ethyl group and the like having 1 to 1 carbon atoms.
Alkyl group of 4; carbon number 1 such as methoxy group and ethoxy group
~ 4 alkoxyl group; C6-10 aryl group such as phenyl group, tolyl group, xylyl group; C7-14
And an alkoxy group (having 6 to 10 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms); an amino group; a nitro group; and a cyano group.

In the general formula (VIII), the alkyl group, aryl group and heterocyclic group represented by R ¹⁶ are preferably an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and Y. 1 oxygen, nitrogen, or sulfur atom similar to that described for the represented ring is used.
An alkyl group represented by R ¹⁷ in the general formula (VIII), including a 5- to 7-membered ring containing 2 to 5 or a condensed ring thereof with a benzene ring;
Examples of the aryl group are the same as those described for R ¹⁰ above.

The alkylene group represented by A ¹ , A ² and A ³ is preferably a group having 1 to 4 carbon atoms such as methylene group, ethylene group, propylene group, trimethylene group and tetramethylene group, and an alkylidene group. Is preferably a group having 2 to 4 carbon atoms such as ethylidene group, propylidene group and isopropylidene group. Further, the cycloalkylene group is
It is preferably a cyclohexylene group, and the alkylcycloalkane-diyl group is preferably a dimethylcyclohexane-diyl group.

In the general formula (VIII), examples of the alkyl group represented by R ¹⁸ include the same as those described for R ¹⁶ , and the naphthylalkyl group is preferably a naphthylmethyl group or a naphthylethyl group. Carbon number 1
1 to 14 groups.

The cyanoalkyl group represented by R is preferably a cyanoalkyl group having 1 to 4 carbon atoms (ie, cyano C _1-3 alkyl), and the nitroalkyl group is preferably nitroalkyl group having 1 to 4 carbon atoms. And an alkoxycarbonylalkyl group preferably has 3 to 9 carbon atoms.
Is an alkoxycarbonylalkyl group (i.e., containing an alkoxyl group having 1 to 4 carbon atoms and an alkylene group having 1 to 4 carbon atoms).

Among the compounds represented by the general formula (VIII),
Considering durability of photochromic action and the like, more preferable compounds include those in which R ¹⁶ is an alkyl group and X is a group> N—R. Further, as another preferable compound, the ring represented by Z is an adamantylidene group, and the ring represented by Y is 6 to 1 carbon atoms.
A heterocyclic group which may be substituted with an aryl group having 0 to 8 carbon atoms or an alkoxyaryl group having 7 to 14 carbon atoms (that is, an aryl group having 6 to 10 carbon atoms substituted with an alkoxyl group having 1 to 4 carbon atoms), particularly The compound which is a thiophene ring is mentioned.

The compound represented by the general formula (VIII) may be used alone or in a mixture of two or more kinds.

The compound represented by the general formula (VIII) is known and is described in, for example, JP-A-64-52778.

Either a spirooxazine compound (for example, the compound represented by the above general formula (VII)) or a fulgide compound and a fulgimide compound (for example, a compound represented by the general formula (VIII)) are preferably used in the present invention. However, the fulgide compound and the fulgimide compound are more preferable in view of the color development performance, the decolorization performance, the temperature dependence, and the like.

Further, the chromene compound preferably used in the present invention can be represented by, for example, the general formula (IX). Chromene compounds are generally orange to
It develops a yellow color. By mixing it with a spirooxazine compound, a fulgide compound or a fulgimide compound, an intermediate color such as gray or brown can be developed.

[0066]

[Chemical 10] (Wherein R ²⁰ , R ²¹ , R ²² , and R ²³ are independently
Each represents a hydrogen atom, an alkyl group, an aryl group, a substituted amino group, or a saturated heterocyclic group, or R ²² and R ²³ may be taken together to form a ring, and the ring represented by Y is It represents an aromatic ring or an unsaturated heterocycle, and one or more hydrogen atoms on either ring have 1 carbon atoms.
It may be substituted with an alkyl group having 20 to 20 or an alkoxyl group having 1 to 20 carbon atoms. ) In the general formula (IX), R ²⁰ , R ²¹ , R ²² , and R ²³
The alkyl group represented by is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a phenyl group,
An aryl group having 6 to 10 carbon atoms such as a tolyl group and a xylyl group. Further, the substituted amino group is preferably at least one hydrogen atom in the above-mentioned alkyl group or aryl group.
One is a substituted amino group. Further, the saturated heterocyclic group is a monovalent group derived from a 5- or 6-membered ring containing 1 to 2 nitrogen atom, oxygen atom or sulfur atom such as pyrrolidine, imidazolidine, piperidine, piperazine, and phorforin. Is mentioned.

In formula (IX), the ring formed by R ²² and R ²³ together is preferably a norbornylidene group or a bicyclo (3,3,1) 9-nonylidene group.

In the general formula (IX), preferable examples of the aromatic hydrocarbon group as the ring represented by Y are:
One benzene ring or two or three condensed rings thereof may be mentioned. Specific examples of this aromatic hydrocarbon include rings having 6 to 14 carbon atoms such as benzene ring, naphthalene ring, phenanthrene ring, and anthracene ring. Moreover, as a preferable example of the unsaturated heterocycle as a ring represented together with Y, a 5- to 7-membered ring containing 1 to 2 oxygen atoms, nitrogen atoms, or sulfur atoms, or a benzene ring Examples include condensed rings. Further, specific examples thereof include rings having 4 to 9 carbon atoms such as furan ring, benzofuran ring, pyridine ring, quinoline ring, isoquinoline ring, pyrrole ring, thiophene ring and benzothiophene ring.

One or more hydrogen atoms on these rings may be substituted, and examples of the substituent include a halogen atom; a methyl group, an ethyl group and the like having 1 to 1 carbon atoms.
An alkyl group having 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms such as methoxy group and ethoxy group; an aryl group having 6 to 10 carbon atoms such as phenyl group, tolyl group and xylyl group; amino group,
Nitro group; cyano group can be mentioned.

Among the compounds represented by the general formula (XI), more preferred compounds are those in which R ²⁰ and R ²¹ are both hydrogen atoms, and R ²² and R ²³ are the same or different and each have 1 to 4 carbon atoms. It is an alkyl group or a bicyclo (3,3,1) 9-nonylidene group or norbornylidene group formed together with these, and the ring represented by Y is an alkyl group having 1 to 20 carbon atoms or Examples thereof include a compound having a naphthalene ring which may be substituted with an alkoxyl group having 1 to 20 carbon atoms.

The compound represented by the general formula (XI) may be used alone or in combination of two or more.

The compound represented by the general formula (IX) is known and is described in, for example, JP-A-3-121188.

Other Ingredients The photochromic resin composition of the present invention may be mixed with an ultraviolet stabilizer, if necessary, to further improve the photochromic durability.

Preferred examples of the UV stabilizer include a hindered amine light stabilizer, a hindered phenol antioxidant, a phosphite antioxidant and a thioether antioxidant. In particular, it is preferable to use at least one of the hindered amine light stabilizer and the phosphite antioxidant in combination.

Specific examples thereof include hindered amine light stabilizers such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2).
2,6,6-Pentamethyl-4-piperidyl) sebacate, 1- [2- [3- (3,5-di-t-butyl-4-
Hydroxyphenyl) propionyloxy] ethyl]-
4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 8-benzyl-7,7,9,9
-Tetramethyl-3-octyl-1,3,8-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2,2,6 , 6-Tetramethyl-4-methacryloyloxy-piperazine, and 1,2,2,6,6-
Mention may be made of pentamethyl-4-methacryloyloxy-piperazine.

Still another preferred specific example is the following general formula (X)

[0077]

[Chemical 11] Where R ²⁴ , R ²⁵ , R ²⁶ , and R ²⁷ are all 2, 2,
A hindered amine light stabilizer which is a 6,6-tetramethyl-4-methacryloyloxy-piperidyl group, R ²⁴ ,
A hindered amine light stabilizer in which all of R ²⁵ , R ²⁶ , and R ²⁷ are 1,2,2,6,6-pentamethyl-4-methacryloyloxy-piperidyl group, R ²⁴ , R ²⁵ , R ²⁶ , R
^At least one of ²⁷ is a 2,2,6,6-tetramethyl-4-methacryloyloxy-piperidyl group and the other is a tridecyl group, a hindered amine light stabilizer, and R ²⁴ , R ²⁵ and R ^26. , At least one of R ²⁷ is 1,
A hindered amine light stabilizer that is a 2,2,6,6-pentamethyl-4-methacryloyloxy-piperidyl group and the other is a tridecyl group may be mentioned.

Further preferred specific examples include a hindered amine light stabilizer represented by the following general formula (XI).

[0079]

[Chemical 12] (In the above formula, n is an integer of 1 to 5, W represents a tetravalent group represented by the following formula (XII),

[0080]

[Chemical 13] R ²⁸ are the same or different, 2, 2, 6,6-tetramethyl-4-methacryloyloxy - represents a piperidyl group - piperidyl group or a 1, 2, 2,6,6-pentamethyl-4-methacryloyloxy.

Preferred examples of the above-mentioned phosphite type antioxidant include tridecyl phosphite, triphenyl phosphite, octyl diphenyl phosphite, decyl diphenyl phosphite, didecyl phenyl phosphite, tris (nonylphenyl) phosphite. , 4,
4′-isopropylidene-diphenol-alkyl phosphite (the number of carbon atoms of the alkyl group is 12 to 15), hydrogenated bisphenol-pentaerythritol phosphite polymer, hydrogenated bisphenol A / phosphite polymer, etc. Can be mentioned.

The mixing ratio of these ultraviolet stabilizers is preferably in the range of 0.001 to 2 parts by weight with respect to 100 parts by weight of the total of the lens main component monomer and the photochromic compound.

Photochromic resin and photochromic
Kicklens The photochromic resin according to the present invention is obtained by subjecting the above-described photochromic composition according to the present invention to the polymerization conditions of the polymerizable monomer (component (a) and other polymerizable monomers) in the composition. You can

The polymerization and curing method is not particularly limited and may be appropriately determined in consideration of the use of the photochromic resin. Further, the molding method may be similarly determined.

For example, when molding for a lens, an ultraviolet stabilizer, a polymerization initiator and the like are contained in two mirror-polished glass molds via a gasket made of ethylene-vinyl acetate copolymer or the like. The photochromic composition according to the present invention may be injected and molded by heat polymerization. Then, if necessary, it may be shaped into a lens by polishing.

Here, various radical polymerization initiators can be mentioned as the polymerization initiator preferably used in the case of curing in such a mode. Specific examples thereof include benzoyl per-oxide, t-butyl per-oxy-2-ethyl hexanoate, t-butyl per-oxypivalate,
t-butyl peroxyisobutyrate, t-butyl per-
Examples thereof include oxyneodecanoate, t-butylper-oxyisopropyl carbonate, lauroylperoxide, azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile). These may be used alone or in a mixture of two or more. Further, in order to further enhance the moldability of the resin composition, a polymerization degree adjusting agent may be added in addition to the polymerization initiator. Specific examples of the polymerization degree adjusting agent include normal dodecyl mercaptan, normal octyl mercaptan, thioglycerol, and α-methylstyrene dimer. However, since the thiol compound may accelerate the deterioration of the photochromic compound during polymerization and during repeated color development, α-methylstyrene dimer is particularly preferable. The ratio of these polymerization initiators and the degree of polymerization mixture that can be mixed and used is
The amount is about 0.001 to 5 parts by weight with respect to 100 parts by weight of the total amount of each lens main component monomer and the photochromic compound. Further, in the case of injecting a monomer into a mold for polymerization, an adhesion-imparting agent may be added in order to enhance the adhesion between the resin and the mold during polymerization and curing. Specific examples of the adhesion-imparting agent include glycidyl methacrylate and 2-hydroxyethyl methacrylate. The preferred mixing ratio of these adhesion promoters is 0.001 with respect to the polymerization monomer.
It is about 10 parts by weight.

The composition according to the present invention can be cured by combining light and heat in combination with a photo-curing type polymerization initiator in addition to the above-mentioned polymerization initiator.
In this case, if the light irradiation time is too long, the photochromic compound is deteriorated and the mechanical strength of the resin is apt to decrease. Therefore, it is preferable that the light irradiation is up to gelation of the resin and the complete curing is performed by using heat.

In the above, as the mold, not only glass but also glass and plastic plate, glass and metal plate, or a combination thereof can be used. Further, as the gasket, in addition to the thermoplastic resin as described above, an adhesive tape made of polyester may be used.

When the photochromic resin according to the present invention is used for purposes other than lenses, polymerization and molding can be performed in the same manner as above.

Since the photochromic resin according to the present invention is thin and lightweight and has excellent optical characteristics, it can be suitably used particularly for photochromic lens applications.

When used as a lens, it is preferable to provide an antireflection film in order to increase the light transmittance of the lens and prevent flicker due to surface reflection. Further, it is particularly preferable to provide a hard coat layer on the surface of the lens base material in order to improve the adhesion between the lens base material and the antireflection film and prevent the occurrence of scratches on the surface. As described above, the photochromic resin according to the present invention has an advantage that it has extremely good adhesion to the hard coat layer, although it has a structure having an aromatic ring.

Preferred examples of the hard coat layer include those obtained by coating and curing the coating composition containing the following (a) and (b) as the main components. (A) One or more silane compounds having at least one reactive group. (B) Metal fine particles such as silicon oxide, antimony oxide, zirconium oxide, titanium oxide, tin oxide, tantalum oxide, tungsten oxide, or aluminum oxide; titanium oxide, cerium oxide, zirconia oxide, silicon oxide,
And one or more metal fine particles selected from composite metal fine particles using two or more selected from iron oxide; and composite metal fine particles obtained by coating tin oxide fine particles with composite metal fine particles of tin oxide and tungsten oxide.

The component (b) is a component effective for adjusting the refractive index of the hard coat and increasing the hardness,
They can be used alone or as a mixture. Generally (b)
Although it is possible to form the hard coat layer only with the component (2), the film-forming property may be poor with only the component (B).
By using the component (a) together, a transparent and tough hard coat layer can be obtained. The component (a) can be used as it is, but it is preferably hydrolyzed and used since the water resistance and hardness of the film can be improved.

The thickness of the hard coat layer is usually 0.2 μm.
It is preferably about 10 μm, more preferably 1 μm to 3 μm.
It is about μm.

Further, according to a preferred embodiment of the present invention, it is preferable to provide a primer layer between the lens substrate and the hard coat layer. This primer layer has a function of improving the impact resistance of the lens after the surface treatment and further improving the adhesion between the lens base material and the hard coat layer. This primer layer can be obtained by applying the following coating composition and drying.
Specific examples of the coating composition for forming the primer layer include, for example, a primer composition containing at least one resin selected from urethane series, acrylic series, and epoxy series.

The coating of the hard coat layer and the primer layer is preferably carried out by diluting the raw material components into an appropriate solvent system such as alcohol system or water system and applying it by a general coating method such as dipping, spinning or spraying. Then, it can be performed by heating and curing. The curing can be performed by simply heating, but it is preferable to add an appropriate curing catalyst because it becomes possible to form a hard film in a shorter time. Examples of curing catalysts include perchlorates such as magnesium perchlorate and ammonium perchlorate, and chelate compounds such as aluminum acetylacetonate.

In the hard coat layer, the above components (a) and (b) alone can obtain sufficient coating performance, but the appearance and durability of the hard coat layer and other functions can be added. Therefore, it is possible to add other components.

For example, in order to improve the water resistance of the hard coat layer or impart dyeing properties, a polyhydric alcohol,
It is preferable to add a polycarboxylic acid, a polycarboxylic anhydride, or an epoxy compound. Examples of the polyhydric alcohol preferably used include, for example, difunctional alcohols such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol and alkanediol, and trifunctional alcohols such as glycerin and trimethylolpropane. Functional alcohol, polyvinyl alcohol, etc. are mentioned. Examples of the polycarboxylic acid include malonic acid, succinic acid, adipic acid, azelaic acid, maleic acid, o-phthalic acid, terephthalic acid, fumaric acid, itaconic acid and oxaloacetic acid. Examples of polycarboxylic acid anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, 1,2-dimethylmaleic anhydride, phthalic anhydride, hexahydrophthalic anhydride, and naphthalic anhydride. Also,
As the epoxy compound, a diglycidyl ether of a bifunctional alcohol such as (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, catechol, resorcinol, and alkanediol,
Alternatively, di- or triglycidyl ethers of trifunctional alcohols such as glycerin and trimethylolpropane may be mentioned. When these additives are added, it is possible to obtain a film having high hardness by adding a curing catalyst.

Further, in order to prevent deterioration of the hard coat layer due to ultraviolet rays, an ultraviolet absorber or an antioxidant.
It is preferable to add a light stabilizer. Preferred specific examples of the ultraviolet absorber, antioxidant, and light stabilizer include salicylic acid ester-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel complex salt-based, phenol-based, and hindered amine-based compounds.

Further, it is preferable to use a surface active agent and a flow control agent in order to eliminate coating defects such as scratched skin and cissing at the time of application. Above all, silicone-based or fluorine-based surfactants are effective.

In the photochromic lens, the optical performance can be further improved by providing an antireflection film on the surface of the hard coat layer. The antireflection film is a single-layer or multi-layer thin film made of an organic material or an inorganic material, and is not particularly limited as long as the reflectance is reduced.

Examples of the film forming method for forming the antireflection film made of an inorganic substance include a vacuum vapor deposition method, an ion plating method and a sputtering method. In the vacuum vapor deposition method, an ion beam assist method in which an ion beam is simultaneously irradiated during vapor deposition may be used. Specific examples of the inorganic material used include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, hafnium oxide, and magnesium fluoride. These inorganic substances can be used alone or as a mixture of two or more.

As a film forming method for forming an antireflection film made of an organic substance, a resin (for example, a natural polymer or a synthetic polymer) as a film component is dissolved in an organic solvent to obtain a solution having an appropriate fluidity. After that, a method of applying the same by a spin method or a dipping method, and then heating and curing the same can be mentioned. This solution can contain a metal oxide such as silicon oxide, titanium oxide, and zirconium oxide, and a fluorine-based compound.

From the viewpoint of surface hardness and prevention of interference fringes,
It is more preferable to provide a single-layer or multi-layer antireflection film made of an inorganic material.

[0105]

The present invention will be described in more detail by the following examples, but the present invention is not limited to these specific descriptions.

Abbreviations of the polymerizable monomers used in the following Examples and Comparative Examples are as follows.

Di (meth) acryloyl represented by the general formula (I)
Rate compound METX: p-bis (2-methacryloyloxyethylthio) xylylene MPTX: p-bis (3-methacryloyloxypropylthio) xylylene Other polymerizable monomer BZMA: benzyl methacrylate PHMA: phenyl methacrylate PHEMA: phenoxyethyl methacrylate BPE: 2,2'-bis [4- (methacryloyloxyethoxy) phenyl] propane BBPE: 2,2'-bis [(3,5-dibromo-4-)
Methacryloyloxyethoxy) phenyl] propane MMA: methyl methacrylate EMA: ethyl methacrylate IBM: isobornyl methacrylate DCPM: dicyclopentanyl methacrylate 4 EGM: tetraethylene glycol dimethacrylate 4PGM: tetrapropylene glycol dimethacrylate photochromic compound compound S -A: Spirooxazine compound represented by the following chemical formula (S-a) Compound F-a: Flugimide compound represented by the following chemical formula (F-a) Compound F-b: Represented by the following chemical formula (F-b) Flugimide compound Compound Ca: chromene compound represented by the following chemical formula (Ca) Compound Cb: chromene compound represented by the following chemical formula (Cb)

[0108]

Embedded image The coating composition and primer composition used for forming the hard coat layer were prepared by the following method.

Coating composition (a) γ-glycidoxypropyltrimethoxysilane 23
g, methanol-dispersed colloidal silica (Catalyst Chemical Co., Ltd.)
(Manufactured by trade name "OSCAL-1132") and 32 g of methyl cellosolve were well stirred, and 2 g of 0.05 N hydrochloric acid was added and stirred for 30 minutes. Furthermore, 0.03 g of a silicone-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name "L-7604") was added and stirred to prepare a coating composition.

Coating compositions (b), (c), and
And (d) The composition shown in Table 5 was prepared in the same manner as the coating composition (a).

Primer composition (a) 20 g of an acrylic-styrene copolymer emulsion (manufactured by Daicel Chemical Industries, trade name "Cevian A4710"), 17 g of water, 70 g of ethyl cellosolve, 15 g of N, N dimethylformamide were prepared for 30 minutes. It was stirred. Furthermore, a silicone-based surfactant (manufactured by Nippon Unicar Co., Ltd.,
0.03 g (trade name "L-7604") was added and stirred to prepare a primer composition.

Primer composition (b) A primer composition (manufactured by Nippon ARC Co., Ltd., trade name "Crystal Coat CP-607") was used.

Example 1 METX 45 g, PHEMA 25 g, MMA 12 g, I
BM12g, 4EGM6g, compound F-a0.06g,
Compound F-b 0.06 g, compound C-a 0.065 g,
0.2 g of hindered amine light stabilizer (trade name "LA-63" manufactured by Asahi Denka Co., Ltd.), 0.3 g of tridecyl phosphite, 1 g of α-methylstyrene dimer, 1 g of glycidyl methacrylate, and t- After mixing 1.0 g of butylperoxynedecanoate and stirring well at room temperature, the pressure was reduced to 50 mmHg and the mixture was degassed for 10 minutes. This composition was poured into a mirror-finished glass plate mold through a gasket made of ethylene-vinyl acetate copolymer, kept at 35 ° C for 10 hours, and gradually increased from 35 ° C to 100 ° C in 7 hours. Molded by warming and holding at 100 ° C. for 2 hours. The lens was released from the mold and heated at 100 ° C. for 2 hours for annealing treatment.

The lenses thus manufactured were evaluated by the following methods. The results were as shown in Table 3.

Evaluation Test Refractive Index : Measured with an Abbe refractometer at a D line of 589.3 nm.

Saturated water absorption rate : Using a disk-shaped flat plate having a thickness of 5 mm, the weight was increased by allowing the plate to stand in saturated steam of 100% at 70 ° C. for 3 days.

Heat resistance : Load of 10 g by TMA measuring machine
Tg was measured.

Ball drop test : When a steel ball was dropped from a height of 127 cm to the center of five lenses having a center thickness of 1.5 mm,
The average value of the weight of the steel ball with the lens broken or cracked was calculated.

Bending test : The elastic modulus was measured according to JIS K7203.

Lens shape: The curved state of the central part of the lens was visually observed and classified into the following ranks. A There is no curvature. (The difference between the curvature at the time of design and the curvature at the time of molding is 0 to 1%) B Slightly curved. (Difference 1-3%) C Slightly curved. (Difference 3-5%) D Curved. (Difference 5-10%) E Remarkably curved. (Difference 10-20%) F Cannot be used. (Difference 20% or more) Example 2 In addition to 100 g of the lens composition monomer shown in Table 1, 0.12 g of compound S-a, and 0.065 g of compound C-a, the same amount of UV stability as in Example 1 was obtained. Agent, polymerization initiator,
A lens was produced in the same manner as in Example 1 from the composition containing the polymerization degree adjusting agent and the adhesion-imparting agent.

The lens was subjected to the same evaluation test as in Example 1. The results are as shown in Table 3.

Examples 3 to 8 100 g of the lens composition monomer shown in Table 1 and the same amount of the photochromic compound, the ultraviolet stabilizer as in Example 1,
A lens was produced in the same manner as in Example 1 from a composition containing a polymerization initiator and a polymerization degree adjusting agent.

The same evaluation test as in Example 1 was conducted on these lenses. The results are as shown in Table 3.

Examples 9 to 10 In addition to 100 g of the lens composition monomer shown in Table 1, 0.12 g of compound S-a and 0.065 g of compound C-b, the same amount of UV stabilizer and polymerization as in Example 1 was used. Initiator,
A lens was produced in the same manner as in Example 1 from the composition containing the polymerization degree adjusting agent and the adhesion-imparting agent.

The lens was subjected to the same evaluation test as in Example 1. The results are as shown in Table 3.

Comparative Example 1 CR39 (diethylene glycol bisallyl carbonate) 100 g, compound F-a 0.06 g, compound F-b
0.06 g, compound C-a 0.065 g, and diisopropyl peroxydicarbonate 3 g were mixed and stirred well, and then poured into a mold similar to that in Example 1, and then 45 ° C.
Molding was carried out by holding at 10 ° C. for 10 hours, 60 ° C. for 3 hours, 80 ° C. for 3 hours, and 95 ° C. for 6 hours. The lens was taken out from the mold and heated at 120 ° C. for 1 hour to be annealed.

The lens thus manufactured was evaluated in the same manner as in Example 1. The results are as shown in Table 4.

Comparative Examples 2 to 5 100 g of the lens composition monomer shown in Table 2 and the same amount of the photochromic compound, the ultraviolet stabilizer as in Example 1,
A lens was produced in the same manner as in Example 1 from a composition containing a polymerization initiator and a polymerization degree adjusting agent.

The same evaluation test as in Example 1 was conducted on these lenses. The results are as shown in Table 4.

Example 11 The lens of Example 1 was dipped in the coating composition (a) and pulled up at a speed of 20 cm / min for coating. Then, the lens was heated at 130 ° C. for 1.5 hours to dry the coat layer and apply the hard coat layer.

Further, an antireflection film (a) was formed on the surface of the hard coat layer by a vacuum vapor deposition method. That is, Zr is formed in order from the side of the lens substrate made of photochromic resin.
O ₂ 0.13λ / SiO ₂ 0.06λ / ZrO ₂
An antireflection film composed of 0.25λ / SiO ₂ 0.25λ (however, design wavelength λ = 520 nm) was formed.

The following evaluation tests were conducted on the photochromic lens thus obtained. The results are as shown in Table 6.

Evaluation test Hard coat adhesion : In accordance with JIS K5400
The test was conducted by a cross-cut tape method, and the residual rate of the film was converted into points. That is, when the residual rate is 91 to 100%, 10 points are given, and when the residual rate is 81 to 90%, 9 points are given.

Photochromic coloring performance : 20 lenses
It was placed in a constant temperature bath kept at ℃, and light irradiation was performed at a distance of 15 using an artificial solar lighting (XC-100 manufactured by Celic Co., Ltd.).
cm to 5 minutes to develop color. The values of A5-A0 were determined by setting the absorbances at the wavelengths shown in Table 6 before and after color development as A0 and A5, respectively, and this was defined as the color density.

Incidentally, 595 nm is the maximum absorption wavelength of the compound Sa, and 580 nm is the compounds Fa and Fb.
Is the maximum absorption wavelength of the compound C-
It is the maximum absorption wavelength of a and Cb.

Photochromic durability : Fatigue life was measured with a xenon long life fade meter-FAL-25AX-HC (manufactured by Suga Test Instruments Co., Ltd.). Fatigue life T _1/2 is determined by the compounds S-a, F-a, F-b, and C-
The absorbance at each maximum absorption wavelength of a is the initial T
It was expressed as the time required to reduce the absorbance to 1/2 of 0.

However, the absorbances at T0 and T1 _{/ 2} are both values obtained by subtracting the absorbance of the unirradiated lens.

Examples 12 to 18 and Comparative Examples 6 to 10 On the lens surfaces obtained in Examples 2 to 8 and Comparative Examples 1 to 5, the same hard coat layer as in Example 11 or the hard coatings shown in Table 5 were used. A coating layer was applied, and an antireflection film (ii) similar to that of Example 11 or an antireflection film (ii) was applied by a vacuum vapor deposition method to obtain Examples 12 to 18 and Comparative Examples 6 to 10, respectively. However, here, the antireflection film (b) means SiO ₂ 0.06 λ / ZrO ₂ 0.13 λ / in order from the side of the lens substrate made of photochromic resin.
SiO ₂ 0.06λ / ZrO ₂ 0.25λ / SiO ₂
0.25λ (where λ = 520 nm).

Hard coat adhesion and photochromic color development performance of these lenses were evaluated in the same manner as in Example 11 above. The results are as shown in Table 6.

Example 19 The lens obtained in Example 9 was used as a primer composition (a).
And the composition was applied to the lens by pulling it up at a speed of 10 cm / min. Then, the lens was heated at 60 ° C. for 0.5 hour to form a primer layer. In addition to this lens,
The coating composition (a) shown in Table 5 was applied, and an antireflection film similar to that of Example 11 was applied to obtain a lens of Example 19.

The hard coat adhesion and photochromic color development of this lens were evaluated in the same manner as in Example 11. The results are as shown in Table 6.

Example 20 The lens obtained in Example 10 was dipped in the primer composition (b) and pulled up at a rate of 15 cm / min to apply the composition to the lens. It heated at 90 degreeC for 0.5 hour, and formed the primer layer. Further, the coating composition (a) shown in Table 5 was applied to this lens, and the antireflection film similar to that in Example 11 was applied to obtain a lens of Example 20.

Hard coat adhesion and photochromic color development of this lens were evaluated in the same manner as in Example 11. The results are as shown in Table 6.

[0144]

[Table 1]

[0145]

[Table 2]

[0146]

[Table 3]

[0147]

[Table 4]

[0148]

[Table 5] Abbreviations in the table GTS: γ-glycidoxypropyltrimethoxysilane GMDS: γ-glycidoxypropylmethyldiethoxysilane TMS: tetramethoxysilane Sn / W: tin oxide sol is coated with a composite sol of tin oxide and tungsten oxide Sol (methanol dispersion, solid content 20%) CS: Colloidal silica (methanol dispersion, solid content 3
0%) Ti / Ce: Composite sol of titanium oxide and cerium oxide (methanol dispersion, solid content 20%) DOX: 1,4-dioxane GDPE: glycerol cypolyglycidyl ether MeOH: methanol MeCe: methyl cellosolve IPA: isopropanol

[0149]

[Table 6]

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toru Saito 3-5 Yamato 3-chome, Suwa City, Nagano Seiko Epson Corporation (72) Inventor Toshiyuki Miyabayashi 3-chome Yamato 3-chome, Suwa City, Nagano Prefecture No. Seiko Epson Corporation (72) Inventor Takashi Kobayakawa 1-5-7 Furuichi, Shinnanyo-shi, Yamaguchi Prefecture

Claims (14)

[Claims] 1. A photochromic composition which is polymerized into a photochromic resin, comprising: (a) a compound represented by the general formula (I): (In the formula, two R ¹ 's each independently represent a hydrogen atom or a methyl group, two R ^2's and two R ³ 's each independently represent an alkylene group having 1 to 4 carbon atoms, X represents a halogen atom other than fluorine, two Y's each independently represent an oxygen atom or a sulfur atom, and m represents an integer of 0 to 4), and a di (meth) acrylate compound, A photochromic composition comprising (b) a photochromic compound in an amount effective to impart a photochromic function to the photochromic resin. 2. 100 parts by weight of di (meth) acrylate,
The photochromic composition according to claim 1, comprising 0.01 to 5 parts by weight of the photochromic compound. 3. A di (meth) acrylate compound represented by the general formula (I) is p-bis (2-methacryloyloxyethylthio) xylylene, p-bis (3-methacryloyloxypropylthio) xylylene, p-bis. The photochromic composition according to claim 1, which is at least one compound selected from the group consisting of (2-methacryloyloxyethylthioethyl) phenylene and p-bis (3-methacryloyloxypropylthioethyl) phenylene. 4. The photochromic composition according to claim 1, wherein the photochromic compound is at least one compound selected from spirooxazine compounds, fulgide compounds, fulgimide compounds and chromene compounds. 5. A spirooxazine compound represented by the following general formula (VI
The photochromic compound according to claim 4, wherein the fulgide compound or the fulgimide compound is a compound represented by the following general formula (VIII) and the chromene compound is a compound represented by the following general formula (IX). Composition. Embedded image (In the formula (VII), one of A and B represents N, the other represents CH, n is an integer of 4 to 6, and R ¹¹
Represents a hydrocarbon group or an alkoxycarbonylalkyl group, and R ¹² and R ¹³ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxyl group, a nitro group, a cyano group, a halogenoalkyl group, or an alkoxycarbonyl. Represents a group, R ¹⁴ and R ¹⁵ are independently
Each is a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxyl group. In the formula (VIII), the ring represented by Y represents an aromatic hydrocarbon group which may have a substituent or an unsaturated heterocyclic group which may have a substituent, and R ¹⁶ represents , An alkyl group, an aryl group, or a heterocyclic group, the ring represented by Z represents a norbornylidene group or an adamantylidene group, and X represents an oxygen atom, a group>
N-R ^{17, group> N-A 1 -B 1 -} (A 2) M- (B 2)
N-R ^18, group> N-A ³ -A ^4, represents a group -A ³ -R ¹⁹ or a group> N-R, wherein, R ¹⁷ represents a hydrogen atom, an alkyl group or an aryl group, A ¹ , A ² , and A ³ each independently represent an alkylene group, an alkylidene group, a cycloalkylene group, or an alkylcycloalkane-diyl group, and B ¹ and B ² are each independently —O. -, -C
(= O)-, -OC (= O)-, -OC (= O) O-,
Represents -C (= O) NH- or -NHC (= O)-, and m and n each independently represent 0 or 1, but when m is 0, n is also 0, R ¹⁸ represents an alkyl group, a naphthyl group or a naphthylalkyl group, A ⁴ represents a naphthyl group, R ¹⁹ represents a halogen atom, a cyano group or a nitro group, and R represents a cyanoalkyl group, a nitroalkyl group, Alternatively, it represents an alkoxycarbonylalkyl group. Also, formula (IX)
Wherein R ²⁰ , R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom, an alkyl group, an aryl group, a substituted amino group, or a saturated heterocyclic group, or R ²² and R ²³ are And the ring represented by Y represents an aromatic ring or an unsaturated heterocycle, and one or more hydrogen atoms on any of the rings have a carbon number of 1 to 1. 20 alkyl groups or 1 to 2 carbon atoms
It may be substituted with 0 alkoxyl group. ) 6. The method according to claim 1, further comprising a polymerizable monomer that gives a homopolymer having a refractive index of 1.55 or more.
5. The photochromic composition according to any one of 5 above. 7. A polymerizable monomer that gives a homopolymer having a refractive index of 1.55 or more is a mono (meth) acrylate compound represented by the following general formula (II) or the following general formula (III). The photochromic composition according to claim 6, which is a di (meth) acrylate compound represented by: Embedded image (In the formula (II), R ¹ has the same meaning as defined in the formula (I), and R ⁴ is a phenyl group, a benzyl group, or a 2-phenoxyethyl group, or hydrogen in the substituents thereof. It represents a group in which some of the atoms are replaced by halogen atoms other than fluorine.
In the formula (III), R ¹ has the same meaning as defined in the formula (I), two R ³⁰ 's each independently represent a hydrogen atom or a methyl group, and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a halogen atom except fluorine, and m and n each represent an integer of m + n = 0 to 10. ) 8. A mono (meth) acrylate compound represented by the general formula (II) is phenyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 1,3,5-tribromo. Phenyl (meth) acrylate, and 2- (1 ', 3', 5 '
A photochromic composition according to claim 7, which is selected from the group consisting of: -tribromophenyl) oxyethyl (meth) acrylate. 9. The di (meth) acrylate compound represented by the general formula (III) is 2,2′-bis [4- (methacryloyloxyethoxy) phenyl] propane or 2,2′-bis [4- (methacryloyloxyethoxy) phenyl] propane.
It is 2'-bis [(3,5-dibromo-4-methacryloyloxyethoxy) phenyl] propane.
The described photochromic composition. 10. The composition further comprises a polymerizable monomer that gives a homopolymer having a refractive index of less than 1.55.
10. The photochromic composition according to any one of items 9 to 9. 11. A polymerizable monomer which gives a homopolymer having a refractive index of less than 1.55 is a mono (meth) acrylate compound represented by the following general formula (IV) or general formula (V), or a general formula ( The photochromic composition according to claim 10, which is the di (meth) acrylate compound of VI). [Chemical 4] (In formula (IV), R ¹ has the same meaning as defined in formula (I),
⁹ represents an alkyl group having 1 to 4 carbon atoms. Also, the formula (V)
Wherein R ¹ has the same meaning as defined in formula (I), R ^1
10 represents an alicyclic hydrocarbon group having 5 to 16 carbon atoms. Also,
In formula (VI), R ¹ has the same meaning as defined in formula (I), R ^1
30 represents the same meaning as defined in the above formula (III), and n represents an integer of 1 to 10. ) 12. A photochromic resin comprising a polymer of the photochromic composition according to any one of claims 1 to 11. 13. A photochromic lens comprising the photochromic resin according to claim 12. 14. The photochromic lens according to claim 13, wherein a hard coat layer is provided on the lens surface.