JP2013035877A - Photochromic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photochromic composition which is produced by combining an indeno[2,1-f]naphtho[1,2-b]pyran compound having a skeleton represented by formula (1) with a specific UV absorber and can offer a photochromic spectacle lens excellent in repetition durability by improving durability of the pyran compound.SOLUTION: This photochromic composition includes: 100 pts.mass of the indeno[2,1-f]naphtho[1,2-b]pyran compound having the basic skeleton represented by formula (1); and 1-300 pts.mass of the UV absorber which has the maximum absorption wavelength in the range of 280-330 nm, in the longest wavelength region.

Description

  The present invention relates to a photochromic composition excellent in repeated durability.

  Photochromism is a reversible action that quickly changes color when a compound is irradiated with light containing ultraviolet light, such as sunlight or light from a mercury lamp, and returns to its original color when light is turned off and placed in a dark place. It is applied to various uses. As photochromic compounds having such properties, fulgimide compounds, spirooxazine compounds, chromene compounds and the like have been found. These compounds can be made into an optical article having photochromic properties by compounding with a plastic. Therefore, many studies have been made on the compounding of the above compound and plastic.

  Photochromism is also applied in the field of spectacle lenses. Photochromic eyeglass lenses that use photochromic compounds function as sunglasses by rapidly coloring the lens outdoors when exposed to light containing ultraviolet rays such as sunlight, and fading indoors where there is no such light irradiation. It functions as normal transparent glasses, and its demand has increased in recent years.

  As for photochromic eyeglass lenses, those made of plastic are particularly preferred from the viewpoint of lightness and safety. Generally, the photochromic property is imparted to such plastic lenses by combining the above photochromic compound and plastic. It is done by. As a compounding method, the surface of a lens having no photochromic property is impregnated with a photochromic compound (hereinafter referred to as impregnation method), or the photochromic compound is dissolved in a polymerizable monomer and directly polymerized. A method of obtaining a photochromic lens (hereinafter referred to as a kneading method), and a method of coating a surface of a lens with a photochromic compound dissolved in a polymerizable monomer (hereinafter referred to as a coating method) are known. ing.

  About these photochromic compounds and plastic optical articles having photochromic properties containing them, from the viewpoint of their function, (I) the degree of coloring in the visible light region before irradiation with ultraviolet rays (hereinafter referred to as initial coloring) is low. (II) The degree of coloration (hereinafter referred to as color density) when irradiated with ultraviolet rays is high, and (III) the speed (hereinafter referred to as fading speed) from when the irradiation of ultraviolet rays is stopped until it returns to the original state. Fast, (IV) good repetitive durability of this reversible action, (V) high storage stability, (VI) easy to mold as an optical article, and (VII) high mechanical strength as an optical article are required. ing.

  As a chromene compound having excellent characteristics, a compound having indeno [2,1-f] naphtho [1,2-b] pyran as a basic skeleton (hereinafter referred to as indeno [2,1-f] naphtho [1,2-b] ] (Also referred to as a pyran compound) is known (see Patent Documents 1 to 4). Since these compounds have excellent photochromic properties, they are widely used in current photochromic eyeglass lenses.

International Publication No. 96/014596 Pamphlet International Publication No. 01/019813 Pamphlet International Publication No. 01/060811 Pamphlet International Publication No. 05/028465 Pamphlet

  However, even in photochromic eyeglass lenses using these compounds, the repeated durability is still not sufficient, and there is room for further improvement. Specifically, when it is used for a long period of time, a decrease in color density (decrease in residual rate) and a yellowing of the lens, which are considered to be caused by decomposition of the compound, are observed.

  Although the previous patent document describes that various additives are added to the indeno [2,1-f] naphtho [1,2-b] pyran compound, there is no disclosure about improvement of repeated durability. Absent.

  Accordingly, an object of the present invention is to provide a photochromic composition capable of providing a photochromic eyeglass lens excellent in repeated durability.

  The present inventor has intensively studied on this problem. As a result, repeated durability can be improved without lowering the color density by combining a specific ultraviolet absorber with the indeno [2,1-f] naphtho [1,2-b] pyran compound. As a result, the present invention has been completed.

  That is, the present invention relates to an ultraviolet absorber in which the maximum absorption wavelength in the longest wavelength region is in the range of 280 to 330 nm with respect to 100 parts by mass of the indeno [2,1-f] naphtho [1,2-b] pyran compound. 1 to 300 parts by mass of a photochromic composition.

  The present invention also relates to a photochromic polymerization curable composition comprising 0.01 to 20 parts by mass of the photochromic composition with respect to 100 parts by mass of the polymerizable monomer, and a photochromic cured product obtained by polymerizing and curing the photochromic composition. It is.

  ADVANTAGE OF THE INVENTION According to this invention, the photochromic composition which gives the photochromic spectacle lens excellent in repetition durability can be obtained.

  The present invention will be described in detail below.

  The present invention relates to 1 ultraviolet absorber having a maximum absorption wavelength in the longest wavelength range of 280 to 330 nm with respect to 100 parts by mass of the indeno [2,1-f] naphtho [1,2-b] pyran compound. It is a photochromic composition formed by blending ~ 300 parts by mass.

  In addition, the present invention provides a photochromic polymerization curable composition comprising 100 parts by mass of a polymerizable monomer and 0.01 to 20 parts by mass of the photochromic composition, and photochromic curing obtained by polymerizing and curing the photochromic composition. Is the body.

  The indeno [2,1-f] naphtho [1,2-b] pyran compound used in the present invention has the following formula (1):

It is a compound which has the basic skeleton represented by these.

  More specifically, for example, an indeno [2,1-f] naphtho [1,2-b] pyran compound represented by the following formula (4) can be given.

(Group R ⁶ )
In the formula (4), each R ⁶ independently includes a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a nitrogen atom, and the nitrogen atom is directly bonded to a carbon atom of the benzene ring. Heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, aralkyl group, aryl group, aryloxy group, two R ⁶ adjacent to each other An alkylenedioxy group having 1 to 8 carbon atoms to be formed is represented.

  The alkyl group is not particularly limited, but an alkyl group having 1 to 6 carbon atoms is preferable. Examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and the like. Can do.

  The haloalkyl group is not particularly limited, but a haloalkyl group having 1 to 6 carbon atoms substituted with a fluorine atom, a chlorine atom, or a bromine atom is preferable. Examples of suitable haloalkyl groups include trifluoromethyl group, pentafluoroethyl group, chloromethyl group, 2-chloroethyl group, bromomethyl group and the like.

  The cycloalkyl group is not particularly limited, but a cycloalkyl group having 3 to 8 carbon atoms is preferable. Examples of suitable cycloalkyl groups include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

  The alkoxy group is not particularly limited, but an alkoxy group having 1 to 6 carbon atoms is preferable. Examples of suitable alkoxy groups include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and the like.

The amino group is not limited to a primary amino group, and may be a secondary amino group or a tertiary amino group having a substituent. Examples of the substituent of the amino group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and 4 carbon atoms. ˜12 heteroaryl groups and the like. These alkyl group, alkoxy group and cycloalkyl group are the same groups as those described for R ⁶ above. Examples of the aryl group include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of the heteroaryl group include thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, and benzopyrrolinyl group. Examples of suitable amino groups include amino groups, methylamino groups, dimethylamino groups, ethylamino groups, diethylamino groups, phenylamino groups, diphenylamino groups, and the like.

  The heterocyclic group including the nitrogen atom and directly bonded to the carbon atom of the benzene ring is not particularly limited, and examples thereof are morpholino group, piperidino group, pyrrolidinyl group, piperazino group, N-methylpiperazino. Group, indolinyl group and the like. Furthermore, the heterocyclic group may have an alkyl group having 1 to 6 carbon atoms as a substituent, and specific examples of the substituent include an alkyl group such as a methyl group. Preferred examples of the heterocyclic group having a substituent include 2,6-dimethylmorpholino group, 2,6-dimethylpiperidino group, 2,2,6,6-tetramethylpiperidino group and the like. Is mentioned.

  The alkylcarbonyl group is not particularly limited, and preferred examples include an acetyl group and an ethylcarbonyl group.

  The alkoxycarbonyl group is not particularly limited, and preferred examples include a methoxycarbonyl group and an ethoxycarbonyl group.

  The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The aralkyl group is not particularly limited, but an aralkyl group having 7 to 11 carbon atoms is preferable. Examples of suitable aralkyl groups include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, naphthylmethyl group and the like.

  The aryl group is not particularly limited, but an aryl group having 6 to 14 carbon atoms is preferable. Specific examples of suitable aryl groups include phenyl, 1-naphthyl and 2-naphthyl groups.

  The aryloxy group is not particularly limited, but an aryloxy group having 6 to 14 carbon atoms is preferable. Examples of suitable aryloxy groups include phenoxy group, 1-naphthoxy group, 2-naphthoxy group and the like.

  The aralkyl group, aryl group, and aryloxy group are 1 to 13 hydrogen atoms such as benzene or naphthalene ring, particularly preferably 1 to 4 hydrogen atoms are the hydroxyl group, alkyl group, haloalkyl group, A cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group containing a nitrogen atom and the nitrogen atom being bonded to a carbon atom of the benzene ring, a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group May be substituted with a halogen atom.

Further, the alkylenedioxy group formed by combining two R ⁶ adjacent to each other is not particularly limited, but an alkylenedioxy group having 1 to 8 carbon atoms is preferable. Examples of suitable alkylenedioxy groups include methylenedioxy groups and ethylenedioxy groups.

Note that p is an integer of 0 to 4, and when p is 2 or more, R ⁶ may be the same as or different from each other.

(Group R ⁷ )
In the formula (4), each R ⁷ independently includes a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a nitrogen atom, and the nitrogen atom is directly bonded to a carbon atom of the benzene ring. It represents a heterocyclic group, a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aryl group, or an aryloxy group. As these groups, the same groups as those described above for R ⁶ are used.

In addition, q is an integer of 0 to 4, and when q is 2 or more, R ⁷ may be the same or different from each other.

(Groups R ⁸ and R ⁹ )
In the formula (4), R ⁸ and R ⁹ each independently include a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a nitrogen atom, and the nitrogen atom is indene It represents a heterocyclic group, cyano group, nitro group, formyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, halogen atom, aralkyl group, aryl group or aryloxy group directly bonded to a ring carbon atom. As these groups, the same groups as those described above for R ⁶ are used. And R ⁸ and R ⁹ together form an aliphatic ring having a carbon number of 3 to 20 including the carbon atom of the indene ring, together with the carbon atom of the indene ring, the aliphatic ring A condensed polycyclic ring condensed with an aromatic ring or an aromatic heterocyclic ring, a heterocyclic ring having 3 to 20 atoms including the carbon atom of the indene ring, or an aromatic ring or It may be a group that forms a condensed polycycle in which an aromatic heterocycle is condensed. Preferred examples include the following. In the ring shown below, the lowermost carbon atom represented by Z corresponds to the carbon atom to which the group R ⁸ and the group R ⁹ are bonded.

(Groups R ¹⁰ and R ¹¹ )
In the formula (4), R ¹⁰ and R ¹¹ each independently represent a group represented by the following formula (5), a group represented by the following formula (6), an aryl group, a heteroaryl group, or an alkyl group. .

R ¹² in the formula (5) is an aryl group or a heteroaryl group. Here, the same aryl group as the group already described as R ⁶ is applied.

  The heteroaryl group is not particularly limited, but a heteroaryl group having 4 to 12 carbon atoms is preferable. Examples of suitable heteroaryl groups include thienyl group, furyl group, pyrrolinyl group, pyridyl group, benzothienyl group, benzofuranyl group, benzopyrrolinyl group and the like.

  The heteroaryl group has 1 to 7 hydrogen atoms, particularly preferably 1 to 4 hydrogen atoms in the group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon It may be substituted with a cycloalkyl group of several 3 to 8 or a halogen atom.

R ¹³ is a hydrogen atom, an alkyl group, or a halogen atom. As the alkyl group and the halogen atom, the same groups as those already described as R ⁶ are applied.

  m is an integer of 1 to 3, but m is preferably 1 from the viewpoint of obtaining raw materials.

  Examples of suitable groups among the groups represented by the formula (5) include phenyl-ethylenyl group, (4- (N, N-dimethylamino) phenyl) -ethenyl group, (4-morpholinophenyl) -ethenyl group. , (4-piperidinophenyl) -ethenyl group, (4-methoxyphenyl) -ethenyl group, (2-methoxyphenyl) -ethenyl group, phenyl-1-methylethenyl group, (4-methoxyphenyl) -1-methylethenyl Group, phenyl-1-fluoroethenyl group, (4- (N, N-dimethylamino) phenyl) -1-fluoroethenyl group, 2-thienyl-ethenyl group, 2-furyl-ethenyl group, 2- (N -Methyl) pyrrolinyl-ethenyl group, 2-benzothienyl-ethenyl group, 2-benzofuranyl-ethenyl group, 2- (N-methyl) indolyl-ethenyl group It can be mentioned.

In the formula (6), R ¹⁴ is the same aryl group or heteroaryl group as the R ¹² . Moreover, n is an integer of 1 to 3, but n is preferably 1 from the viewpoint of easy availability of raw materials.

  Examples of suitable groups among the groups represented by the formula (6) include phenyl-ethynyl group, (4- (N, N-dimethylamino) phenyl) -ethynyl group, and (4-morpholinophenyl) -ethynyl group. (4-piperidinophenyl) -ethynyl group, (4-methoxyphenyl) -ethynyl group, (4-methylphenyl) -ethynyl group, (2-methoxyphenyl) -ethynyl group, 2-thienyl-ethynyl group, Examples include 2-furyl-ethynyl group, 2- (N-methyl) pyrrolinyl-ethynyl group, 2-benzothienyl-ethynyl group, 2-benzofuranyl-ethynyl group, 2- (N-methyl) indolyl-ethynyl group, and the like. it can.

The same groups as those already described as R ¹² and R ¹⁴ are applied to the aryl group, heteroaryl group, and alkyl group of R ¹⁰ and R ¹¹ .
R ¹⁰ and R ¹¹ can also be bonded to each other to form an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.

  The aliphatic hydrocarbon ring is not particularly limited, and specific examples of suitable rings include an adamantane ring, a bicyclononane ring, and a norbornane ring.

  In addition, the aromatic hydrocarbon ring is not particularly limited, and preferred examples of the ring include a fluorene ring.

In particular, in order to exhibit excellent photochromic properties in the groups of R ¹⁰ and R ¹¹ , it is preferable that at least one, preferably both groups are aryl groups or heteroaryl groups. Furthermore, it is particularly preferable that at least one of R ¹⁰ and R ¹¹ , preferably both groups, is any group shown in the following (i) to (iv).

(I) an aryl group having an alkyl group or an alkoxy group as a substituent, or a heteroaryl group,
(Ii) an aryl group having an amino group as a substituent, or a heteroaryl group,
(Iii) an aryl group having a nitrogen atom as a heteroatom and a heterocyclic group to which the nitrogen atom and an aryl group or a heteroaryl group are bonded as a substituent, or a heteroaryl group;
(Iv) an aryl group having a condensed heterocyclic group obtained by condensing an aromatic hydrocarbon ring or an aromatic heterocyclic ring to the heterocyclic group in the above (iii), or a heteroaryl group;
In addition, in the aryl group in said (i)-(iv), the position which a substituent substitutes is not specifically limited, The total number is also not specifically limited. However, in order to exhibit excellent photochromic properties, the substitution position is preferably the 3-position or the 4-position when the aryl group is a phenyl group. Moreover, it is preferable that the number of the substituents in that case is 1-2. Examples of such a suitable aryl group include 4-methylphenyl group, 4-methoxyphenyl group, 3,4-dimethoxyphenyl group, 4-n-propoxyphenyl group, 4- (N, N-dimethylamino) phenyl. Group, 4- (N, N-diethylamino) phenyl group, 4- (N, N-diphenylamino) phenyl group, 4-morpholinophenyl group, 4-piperidinophenyl group, 3- (N, N-dimethylamino) ) Phenyl group, 4- (2,6-dimethylpiperidino) phenyl group and the like.

  Moreover, in the heteroaryl group in the above (i) to (iv), the position where the substituent is substituted is not particularly limited, and the total number is not particularly limited, but the number is preferably 1. Specific examples of suitable heteroaryl groups include 4-methoxythienyl group, 4- (N, N-dimethylamino) thienyl group, 4-methylfuryl group, 4- (N, N-diethylamino) furyl. Groups, 4- (N, N-diphenylamino) thienyl group, 4-morpholinopyrrolinyl group, 6-piperidinobenzothienyl group, 6- (N, N-dimethylamino) benzofuranyl group and the like.

(Preferred photochromic compound)
Of the above-mentioned photochromic compounds, examples of suitable compounds include chromene compounds of the following formula.

  The indeno [2,1-f] naphtho [1,2-b] pyran compound of the present invention may be used alone or in combination of two or more for the purpose of color tone adjustment. In addition, photochromic compounds having a structure other than indeno [2,1-f] naphtho [1,2-b] pyran may be appropriately mixed and used as long as the effect is not impaired.

  In the present invention, the above-mentioned indeno [2,1-f] naphtho [1,2-b] pyran compound is combined with an ultraviolet absorber having a maximum absorption wavelength in the longest wavelength range of 280 to 330 nm. It is characterized by. Thereby, the photochromic hardened body excellent in repeated durability can be obtained without impairing the color density. UV absorbers having a maximum absorption wavelength in the longest wavelength range of less than 280 nm, for example, benzoate-based compounds represented by 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate The ultraviolet absorber does not show the effect of improving the durability repeatedly. On the other hand, an ultraviolet absorber having the longest maximum absorption wavelength exceeding 330 nm, for example, a benzotriazole type represented by 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole In the case of ultraviolet absorbers or triazine ultraviolet absorbers typified by tri (pn-hexyloxyphenyl) triazine, the effect of improving durability is obtained, but the color density is significantly lowered.

(UV absorber)
As the ultraviolet absorber having the maximum absorption wavelength in the longest wavelength range in the range of 280 to 330 nm, a cyanoacrylate ultraviolet absorber represented by the following formula (2) can be preferably used.

Here, R ¹ is an aryl group which may have a substituent, R ² is an organic group having 1 to 12 carbon atoms, and x is 1 or 2.

The number of carbon atoms of the aryl group represented by R ¹ is not particularly limited, but generally it is preferably 6 to 14 carbon atoms. Specific examples of such an aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

  The above aryl group may have a substituent. Examples of such substituents include alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group, and butyl group; methoxy group, ethoxy group, propoxy group, butoxy group, hexyloxy group, 2-ethylhexyloxy C1-C12 alkoxy groups, such as a group, an octyloxy group, and a dodecyloxy group; C1-C4 alkylene dioxy groups, such as a methylenedioxy group and an ethylenedioxy group, etc. can be mentioned.

In the present invention, specific examples of the aryl group that may have a substituent represented by R ¹ include a phenyl group, a methoxyphenyl group, a methylenedioxyphenyl group, a tolyl group, a xylyl group, and an anthryl group. And a phenanthryl group.

The organic group having 1 to 12 carbon atoms represented by R ² is preferably an alkyl group, specifically a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, A dodecyl group and the like are preferable. In particular, a methyl group, an ethyl group, a 2-ethylhexyl group and a dodecyl group are more preferable.

In the above formula (3), a preferable cyanoacrylate-based ultraviolet absorber in the present invention is that R ¹ is an aryl group having 6 to 14 carbon atoms, R ² is an alkyl group having 1 to 12 carbon atoms, and x is 2 is a compound.

  Specific examples of the cyanoacrylate-based UV absorber in the present invention include ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, ethyl-2- Cyano-3- (3 ′, 4′-methylenedioxyphenyl) -2-acrylate, 2′-ethylhexyl-2-cyano-3- (3 ″, 4 ″ -methylenedioxyphenyl) -2-acrylate, dodecyl -2-cyano-3- (3 ′, 4′-methylenedioxyphenyl) -2-acrylate, methyl-2-cyano-3,3-diphenyl acrylate, ethyl-2-cyano-3,3-ditolyl acrylate And ethyl-2-cyano-3,3-dinaphthyl acrylate. Of these, ethyl-2-cyano-3,3-diphenyl acrylate and methyl-2-cyano-3,3-diphenyl acrylate are preferable, and ethyl-2-cyano-3,3-diphenyl acrylate is most preferable.

  These cyanoacrylate ultraviolet absorbers may be used alone or in combination of two or more.

  Further, as another ultraviolet absorber having a maximum absorption wavelength in the longest wavelength region in the range of 280 to 330 nm, a benzophenone-based ultraviolet absorber represented by the following formula (3) can also be suitably used.

Here, R ^{3 to} R ⁵ are each independently a hydrogen atom, a hydroxyl group, an alkoxy group, or an aralkoxy group.

  Examples of the alkoxy group include alkoxy groups having 1 to 12 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a dodecyloxy group.

  An example of the aralkoxy group is a benzyloxy group.

  Specific examples of the benzophenone-based UV absorber in the present invention are 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-benzyloxy. Benzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-dodecyl And oxybenzophenone.

  These benzophenone-based ultraviolet absorbers may be used alone or in combination of two or more. Further, the cyanoacrylate ultraviolet absorber described above may be further mixed and used.

  In the present invention, with respect to 100 parts by mass of the indeno [2,1-f] naphtho [1,2-b] pyran compound, another ultraviolet ray having a maximum absorption wavelength in the longest wavelength range in the range of 280 to 330 nm. The absorbent is mixed in an amount of 1 to 300 parts by mass, preferably 3 to 100 parts by mass, and more preferably 5 to 50 parts by mass to obtain a photochromic composition. If the amount is less than 1 part by mass, the effect of improving the repeated durability is small. If the amount exceeds 300 parts by mass, the effect of improving the repeated durability is large, but the color density is insufficient.

  The photochromic composition of the present invention develops a good reversible photochromic effect in a polymer material by color development upon irradiation with sunlight or ultraviolet light, and quickly returns to a transparent state when the light is blocked. Therefore, the photochromic composition of the present invention can be made into a photochromic spectacle lens by uniformly dispersing in a polymer material (polymer solid matrix) exemplified below and molding it. The polymer solid matrix to be used is not particularly limited as long as the photochromic composition of the present invention is uniformly dispersed, and optically preferably, for example, polymethyl acrylate, polyethyl acrylate, polymethyl methacrylate, Mention may be made of thermoplastic resins such as polyethyl methacrylate, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylamide, poly (2-hydroxyethyl methacrylate), polydimethylsiloxane and polycarbonate.

  Further, the chromene compound of the present invention can be made into a photochromic curable composition by mixing with various polymerizable monomers before being made into a polymer, and can also be made into a photochromic composition by polymerizing and curing it. . That is, a cured product in which the photochromic composition is uniformly dispersed can be obtained by polymerizing and curing the photochromic composition of the present invention and the photochromic curable composition containing various polymerizable monomers. Examples of the polymerizable monomer include ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4- Polymethacrylic acid and polymethacrylic acid ester such as methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane, trimethylolpropane trimethacrylate, polyester acrylate, urethane acrylate Compound: diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxy succinate, Polyvalent allyl compounds such as allyl fumarate, diallyl chlorendate, diallyl hexaphthalate, diallyl carbonate, allyl diglycol carbonate, trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthio) Ethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene and other polyvalent thioacrylic acid and polyvalent thiomethacrylic acid ester compounds; glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl methacrylate, bisphenol A monoglycidyl ether Methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1- Acrylic acid ester compounds and methacrylic acid ester compounds such as isopropyloxy) -2-hydroxypropyl acrylate and 3-glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate; styrene, divinylbenzene, α-methylstyrene, α -A methyl styrene dimer etc. can be mentioned.

  Examples of a method for obtaining a photochromic eyeglass lens containing the photochromic composition of the present invention include a method in which a photocatalytic composition is dissolved in the above polymerizable monomer, and then a polymerization catalyst is added and polymerized by heat or light. It is done.

  When the photochromic curable composition is prepared by mixing the photochromic composition of the present invention and the above polymerizable monomer, the mixing ratio of the photochromic composition and the polymerizable monomer is the photochromic composition of the present invention. Is not particularly limited as long as it can be uniformly dissolved, but in order to make the photochromic performance of the resulting cured product practical, it is usually 0.001 to 20 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the polymerizable monomer. 0.01 to 5 parts by mass.

  In addition, when the main component is a bisphenol A and a monomer that does not contain a skeleton similar thereto, among the polymerizable monomers, the effect of improving the repeated durability of the present invention tends to be particularly large, which is particularly preferable. . At this time, the refractive index of the lens is about 1.48 to 1.52.

  In the photochromic composition of the present invention, various stabilizers such as antioxidants, ultraviolet stabilizers, dyes, pigments, anti-coloring agents, antistatic agents, and fluorescent dyes, and additives may be added as necessary. . For example, as the UV stabilizer, a hindered amine light stabilizer, a hindered phenol light stabilizer, a sulfur-based antioxidant, and the like can be suitably used. Although the usage-amount of a ultraviolet stabilizer is not specifically limited, Usually, 1-1000 mass parts with respect to 100 mass parts of photochromic compositions, Preferably it is chosen from the range of 10-300 mass parts.

  There is no restriction | limiting in particular as a method of polymerization hardening, A well-known method is employable. The polymerization means can be carried out by using polymerization initiators such as various peroxides and azo compounds, or by irradiation with ultraviolet rays, α rays, β rays, γ rays, etc., or in combination with both. A typical polymerization method is exemplified by injecting a polymerizable composition comprising a polymerization initiator, the photochromic composition of the present invention and a polymerizable monomer between molds held by an elastomer gasket or a spacer, and a heating furnace. Cast polymerization that is removed after polymerization in can be employed.

  Although it does not specifically limit as a polymerization initiator and a well-known thing can be used, When a typical thing is illustrated, benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, etc. Diallyl peroxide: t-butylperoxy-2-ethylhexanate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxybenzoate, t-butylperoxyisobutyrate, Peroxyesters such as 1,3,3-tetramethylbutylperoxy-2-ethylhexanate; percarbonates such as diisopropylperoxycarbonate and di-sec-butylperoxydicarbonate; azobisisobutyronitrile, etc. Azo compound And the like can be given. Among these, t-butyl peroxyneodecanate, t-butylperoxyneodecanate / t-butylperoxyisobutyrate, t-butylperoxyneodecanate / 1,1,3,3-tetramethylbutylper A combination of oxy-2-ethylhexanate is preferable in terms of polymerization efficiency and hardness of the cured product.

  As another method for obtaining a photochromic spectacle lens, after dissolving the photochromic composition in the above polymerizable monomer, a polymerization catalyst is added and applied to the surface of a lens made of a thermoplastic resin or a thermosetting resin. A method of obtaining a coated lens by polymerizing and curing a coating film with heat or light can be mentioned. In this case, it is particularly preferable to contain a photopolymerization initiator exemplified below. For example, as the photopolymerization initiator, benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, aethofenone 4,4′-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , Benzyl methyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-isopropylthiooxanthone, bis (2,6-dimethoxybenzoyl- 2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, 2- Njiru 2-dimethylamino-1- (4-morpholinophenyl) - butanone-1 and the like can be suitably used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. “Parts” in the examples are “parts by mass”. Below, the symbol of the compound used by an Example and a comparative example is demonstrated.

  1. Indeno [2,1-f] naphtho [1,2-b] pyran compounds

  2. Other photochromic compounds

3. Cyanoacrylate UV absorber Seesorb 501: Ethyl-2-cyano-3,3-diphenyl acrylate (maximum absorption wavelength in the longest wavelength region is 300 nm, manufactured by Cypro Kasei).
Seesorb 502: 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate (the longest wavelength, the maximum absorption wavelength is 300 nm, manufactured by Cypro Kasei).

4). Benzophenone-based UV absorber Adekastab 1413: 2-hydroxy-4-octyloxybenzophenone (maximum absorption wavelength in the longest wavelength range is 320 nm, manufactured by ADEKA).

5. Other UV absorbers SUMISORB 400: 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate (benzoate-based UV absorber; maximum absorption wavelength in the longest wavelength range) 255 nm, manufactured by Sumika Chemitex).
ADK STAB LA36: 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole (benzotriazole ultraviolet absorber; maximum absorption wavelength in the longest wavelength range is 355 nm, manufactured by ADEKA).

6). Polymerizable monomer 3PG: tripropylene glycol dimethacrylate.
4G: Tetraethylene glycol dimethacrylate.
A400: Polyethylene glycol diacrylate (average molecular weight 532).
THHA: urethane acrylate obtained by reacting trimethylhexamethylene diisocyanate with 2-hydroxyethyl acrylate.
EB-1830: Polyester oligomer hexaacrylate.
BPE-100N: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane.
BPE-500: 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane.
GMA: glycidyl methacrylate.
MS: α-methylstyrene.
MSD: α-methylstyrene dimer.

7). Polymerization initiator perbutyl ND: t-butyl peroxyneodecanate.
Perocta O: 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanate.
CGI1800: A mixture of 1-hydroxycyclohexyl phenyl ketone and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide (mass ratio 3: 1).

Example 1
A photochromic composition comprising 0.04 part of PC1 as an indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.01 part of Seasorb 501 as a cyanoacrylate ultraviolet absorber, 3 parts of 50 parts of 3PG. , 25 parts of THHA, 10 parts of TMPT, 13 parts of A400, and 100 parts of a polymerizable monomer consisting of 2 parts of MSD were added, and 1 part of perbutyl ND and 0.1 part of peroctaO were added and mixed well. This mixed solution 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 performed using an air furnace, gradually increasing the temperature from 30 ° C. to 90 ° C. over 18 hours, and maintaining at 90 ° C. for 2 hours. After completion of the polymerization, the polymer was removed from the mold glass mold.

The obtained photochromic cured product (thickness 2 mm) was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics was added to this at 20 ° C. ± 1 ° C. via an aeromass filter (manufactured by Corning). The polymer was irradiated with a beam intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² for 120 seconds to develop a color, and the photochromic properties of the cured product were measured. Each photochromic characteristic was evaluated by the following method.

  1) Maximum absorption wavelength (λmax): This is the maximum absorption wavelength after color development determined by a spectrophotometer (instant multichannel photodetector MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.

  2) Color density {ε (120) −ε (0)}: difference between the absorbance {ε (120)} after the light irradiation for 120 seconds and the above ε (0) at the maximum absorption wavelength. It can be said that the higher this value, the better the photochromic properties. Further, when the color was developed outdoors, the color tone was visually evaluated.

  3) Fading rate [t1 / 2 (sec.)]: When light irradiation is stopped after 120 seconds of light irradiation, the maximum absorbance of the sample is {ε (120) −ε (0)}. Time required to drop to 1/2. It can be said that the shorter this time is, the better the photochromic property is.

4) Repeated durability The following deterioration acceleration test was performed in order to evaluate the repeated durability of color development by light irradiation. That is, the obtained polymer (sample) was accelerated and deteriorated for 200 hours by a Xenon weather meter X25 manufactured by Suga Test Instruments Co., Ltd. Thereafter, the color density was evaluated before and after the test, and the color density before the test (A0) and the color density after the test (A200) were measured, and the residual ratio (%) = {(A200 / A0) × 100}. Was obtained and used as an index of repeated durability. The higher the residual rate, the higher the repetition durability. Moreover, the value of yellowing degree (DELTA) YI = YI (200) -YI (0) was calculated | required using the color difference meter (SM-4) by Suga Test Instruments Co., Ltd. The smaller the degree of yellowing, the higher the repetition durability.

  Furthermore, the characteristics of the substrate were evaluated by the following items. The obtained results are shown in Table 2.

  5) Refractive index: The refractive index at 20 ° C. was measured using a refractometer manufactured by Atago Co., Ltd. Bromonaphthalene or methylene iodide was used as the contact liquid, and the refractive index at the D line was measured.

  The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Example 2
Example 1 with the exception that 0.03 part of PC3 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.04 part of Seasorb 502 was used as the cyanoacrylate UV absorber. Similarly, a lens was prepared and evaluated. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Example 3
Example 1 except that 0.01 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.01 part of Adekastab 1413 was used as the benzophenone-based ultraviolet absorber. A lens was made and evaluated. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Example 4
As an indeno [2,1-f] naphtho [1,2-b] pyran compound, 0.02 part of PC2 and 0.01 part of PC3, as a photochromic compound, 0.02 part of PC4, a cyanoacrylate ultraviolet absorber As in Example 1, a lens was prepared and evaluated except that 0.01 part of Seesaw 501 was used. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Example 5
A lens was prepared and evaluated in the same manner as in Example 1 except that the polymerizable monomer was 50 parts of BPE-100N, 7 parts of TMPT, 30 parts of 4G, 3 parts of GMA, 8 parts of MS, and 2 parts of MSD. It was. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Example 6
As an indeno [2,1-f] naphtho [1,2-b] pyran compound, 0.04 part of PC1 and as a cyanoacrylate ultraviolet absorber, 0.005 part of Seesorb 501 and 0.005 part of Adeka Stub 1413 are combined. A lens was prepared and evaluated in the same manner as in Example 1 except that it was used. The composition is shown in Table 1, and the evaluation results are shown in Table 2.

Example 7
As an indeno [2,1-f] naphtho [1,2-b] pyran compound, a photochromic composition comprising 2 parts of PC1 and 0.5 part of Seesorb 501 as a cyanoacrylate ultraviolet absorber was added to 56 parts of BPE-500. , A400 11 parts, TMPT 11 parts, EB-1830 11 parts, GMA 11 parts, dissolved in 100 parts of polymerizable monomer, CGI1800 as photopolymerization initiator 0.3 parts by weight, stabilizer bis 5 parts by mass of (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] 3 parts by mass, 7 parts by mass of γ-methacryloyloxypropyltrimethoxysilane as a silane coupling agent, and N-methyldiene 3 parts by weight was added and mixed thoroughly Noruamin was photochromic curable composition.

Subsequently, about 2 g of the photochromic curable composition obtained by the above method was spun onto the surface of a lens substrate (CR39: allyl resin plastic lens; refractive index = 1.50) using a MIKASA spin coater 1H-DX2. Coated. The surface-coated lens was irradiated with a metal halide lamp having an output of 120 mW / cm ^{2 in} a nitrogen gas atmosphere for 3 minutes and cured (an optical article coated with a polymer film in which a chromene compound was dispersed (photochromic (Plastic lens) was produced (thickness of polymer film: 40 μm).

  The obtained lens was used as a sample, and the same evaluation as in Example 1 was performed. The composition is shown in Table 1, and the results are shown in Table 3.

Comparative Example 1
A lens was prepared in the same manner as in Example 1 except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and no ultraviolet absorber was used. And evaluated.

  The composition is shown in Table 1, and the evaluation results are shown in Table 4.

  Compared to Example 1, it can be seen that the repeated durability is inferior.

Comparative Example 2
A lens was prepared in the same manner as in Example 1 except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and no ultraviolet absorber was used. And evaluated.

  The composition is shown in Table 1, and the evaluation results are shown in Table 4.

  Compared to Example 5, it can be seen that the repetition durability is inferior.

  In addition, it turns out that the improvement effect of repetition durability by addition of a ultraviolet absorber is a little small compared with the system using the polymerizable monomer of Example 1 and Comparative Example 1.

Comparative Example 3
As in Example 1, except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound and 1 part of Seesorb 501 was used as the UV absorber. A lens was created and evaluated. The composition is shown in Table 1, and the evaluation results are shown in Table 4.

  It can be seen that when the amount of the ultraviolet absorber added to the indeno [2,1-f] naphtho [1,2-b] pyran compound is large, the color density is significantly lowered although the repetition durability is good.

Comparative Example 4
Implemented except that 0.04 part of PC1 was used as the indeno [2,1-f] naphtho [1,2-b] pyran compound, and 0.01 part of benzoate-based Sumisorb 400 was used as the UV absorber. A lens was prepared and evaluated in the same manner as in Example 1. The composition is shown in Table 1, and the evaluation results are shown in Table 4.

  It can be seen that when an ultraviolet absorber having a shortest maximum absorption wavelength in the longest wavelength region is as short as 255 nm, the repeated durability improvement effect is not observed.

Comparative Example 5
Except for using 0.04 part of PC1 as the indeno [2,1-f] naphtho [1,2-b] pyran compound and 0.01 part of benzotriazole-based ADK STAB L36 as the UV absorber, A lens was prepared and evaluated in the same manner as in Example 1. The composition is shown in Table 1, and the evaluation results are shown in Table 4.

  It can be seen that when a UV absorber having the longest maximum absorption wavelength of 355 nm is used, the color density is significantly reduced although the repetition durability is good.

Claims (7)

Following formula (1)

Ultraviolet rays having a maximum absorption wavelength in the longest wavelength range of 280 to 330 nm with respect to 100 parts by mass of an indeno [2,1-f] naphtho [1,2-b] pyran compound having a basic skeleton represented by A photochromic composition containing 1 to 300 parts by mass of an absorbent. An ultraviolet absorber having a maximum absorption wavelength in the longest wavelength range of 280 to 330 nm is represented by the following formula (2).

(In the formula, R ¹ is an aryl group which may have a substituent, R ² is an organic group having 1 to 12 carbon atoms, and x is 1 or 2.)
The photochromic composition of Claim 1 which is a cyanoacrylate type ultraviolet absorber represented by these. An ultraviolet absorber having a maximum absorption wavelength in the longest wavelength range in the range of 280 to 330 nm is represented by the following formula (3).

(In formula, R < ³ > -R < ⁵ > represents a hydrogen atom, a hydroxyl group, an alkoxy group, and an aralkoxy group each independently.)
The photochromic composition according to claim 1, which is a benzophenone ultraviolet absorber represented by the formula: Indeno [2,1-f] naphtho [1,2-b] pyran compounds are represented by the following formula (4):

{Where,
R ⁶ is a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group containing a nitrogen atom and directly binding the carbon atom of the benzene ring, a cyano group, a nitro group, A formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aryl group, or an aryloxy group,
p is an integer of 0 to 4, and when p is 2 or more, R ⁶ may be the same or different groups, and when p is 2 or more and R ⁶ is adjacent to each other Two adjacent R ⁶ groups may form an alkylenedioxy group together,
R ⁷ represents a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a heterocyclic group containing a nitrogen atom and the nitrogen atom directly bonded to a carbon atom of the benzene ring, a cyano group, a nitro group, A formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aryloxy group, or an aryl group,
q is an integer of 0 to 4, and when q is 2 or more, R ⁷ may be the same or different groups,
R ⁸ and R ⁹ each independently include a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, a cycloalkyl group, an alkoxy group, an amino group, a nitrogen atom, and the nitrogen atom is directly bonded to a carbon atom of the indene ring A heterocyclic group, a cyano group, a nitro group, a formyl group, a hydroxycarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, a halogen atom, an aralkyl group, an aryloxy group, or an aryl group,
R ⁸ and R ⁹ may be combined with each other to form a ring structure;
R ¹⁰ and R ¹¹ each independently represent the following formula (5)

(Where
R ¹² is an aryl group or a heteroaryl group,
R ¹³ is a hydrogen atom, an alkyl group, or a halogen atom,
m is an integer of 1-3. )
A group represented by formula (6):

(Where
R ¹⁴ is an aryl group or a heteroaryl group,
n is an integer of 1 to 3. )
A group represented by the above, an aryl group, a heteroaryl group, or an alkyl group,
R ¹⁰ and R ¹¹ may be combined with each other to form a ring structure. }
The photochromic composition in any one of Claims 1-3 which is a compound represented by these.   The photochromic polymerization curable composition which contains 0.01-20 mass parts of photochromic compositions in any one of Claims 1-4 with respect to 100 mass parts of polymerizable monomers.   A photochromic cured product obtained by polymerizing and curing the photochromic polymerization curable composition according to claim 5.   A photochromic molded article comprising 0.01 to 20 parts by mass of the photochromic composition according to any one of claims 1 to 4 with respect to 100 parts by mass of the polymer material, wherein the photochromic composition is dispersed in the polymer material. .