JP3124182B2 - Photochromic composition - Google Patents

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 more particularly to a photochromic composition having excellent storage stability of a polymer.

[0002]

2. Description of the Related Art Photochromism is a phenomenon that has attracted attention in recent years. When a compound is irradiated with light containing ultraviolet rays such as sunlight or light from a mercury lamp, the color changes rapidly, and the light irradiation is performed. It is a reversible action that returns to its original color when it is stopped and placed in a dark place. A compound having this property is called a photochromic compound, and compounds having various structures have been conventionally synthesized. However, these photochromic compounds have a disadvantage of poor reversible durability.

The present inventors have continued research on a series of photochromic compounds, succeeded in synthesizing novel fulgide compounds, oxazine compounds and chromene compounds, and found that the compounds have excellent photochromic action, and have already proposed them. (USP 4,882,438, USP
4,960,678, USP5,130,058, US
P5,106,998, JP-A-2-28154, JP-A-3-11074, JP-A-3-1339
No. 88, Japanese Patent Application No. 3-138052).

At that time, it was also proposed that these photochromic compounds can exhibit functions in a polymer matrix obtained by polymerizing various radically polymerizable monomers.

Further, JP-A-3-124790 proposes, as a means for improving the repetitive durability of the photochromic properties of these photochromic compounds, to blend a hindered phenol-based ultraviolet stabilizer or the like with the compounds. did.

[0006]

By the way, the radical polymerizable monomer used as a raw material monomer of the polymer matrix in which the photochromic compound is dispersed has a property that the monomer is partially polymerized before the curing step. 100ppm as a polymerization inhibitor to prevent
In an amount exceeding the amount represented by the following general formula (I) represented by hydroquinone monomethyl ether:

[0007]

Embedded image

(Wherein R ₁ is a hydroxyl group, a methyl group or a methoxy group).

However, when such a radical polymerizable monomer containing a phenolic compound is used as a raw material monomer of a polymer matrix in which a photochromic compound is dispersed as described above, the resulting photochromic resin can be stored for a long time. Was found to yellow. Of course, in order to prevent such yellowing, it is only necessary to mix this phenolic compound with the radically polymerizable monomer. This causes a problem of polymerization.

[0010] From the above, it has been desired to develop a photochromic composition that does not cause yellowing in a polymer during long-term storage and that can maintain good storage stability of a radically polymerizable monomer component used when uncured. Was.

[0011]

The present inventors have intensively studied in view of the above problems. As a result, the content of the polymerization inhibitor comprising the phenolic compound in the composition is suppressed to 15 ppm or less, and the above problem can be solved by adding the hindered phenolic compound to the composition. As a result, the present invention has been completed.

That is, the present invention comprises (A) 100 parts by weight of a radical polymerizable monomer, (B) 0.001 to 1 part by weight of a hindered phenol compound, and (C) 0.001 to 10 parts by weight of a photochromic compound. , The following general formula (I)

[0013]

Embedded image

(Wherein R ₁ is a hydroxyl group, a methyl group or a methoxy group), the content of the phenolic compound is 15 ppm or less and
The polymerizable monomer (A) has the following formula (II)

Embedded image (However, R ₁ Is a hydrogen atom or a methyl group;
_Two Is an alkylene group having 1 to 4 carbon atoms, or the following formula

Embedded image (Where k is an integer of 0 to 5)
And n is an integer of 1 to 20).
~ 90% by weight, the following formula (III)

Embedded image (However, R ₁ Is a hydrogen atom or a methyl group;
_Two Represents 1 carbon atom which may be substituted by a hydroxyl group
4 to 4 alkyl groups, which may be substituted with a halogen atom
Aryl groups having 6 to 10 carbon atoms, substituted with halogen atoms
Which may be an aralkyl group having 7 to 10 carbon atoms)
And / or the following formula (IV)

Embedded image (However, R ₁ and R ₄ are the same or different
A hydrogen atom or a methyl group, and R ₂ and R ₃ are
Substituted with the same or different hydroxyl groups
C1-C4 alkylene group, or

Embedded image And m and n are each 0 or 1.)
0.1 to 50% by weight of a compound represented by the formula
From 0.1 to 50% by weight of other monomers copolymerizable with the product.
This is a photochromic composition.

[0015] In the photochromic composition of the present invention, the as the radically polymerizable monomer (II), (III)
And a compound represented by (IV), for use in combination with other radical polymerizable monomer as the compound and copolymerizable
In, it is possible to obtain a dark color density and fast fading rate of the photochromic compound, Ru can be further improved reversible durability of photochromic action. In addition, a photochromic resin having practical physical properties, for example, good transparency, surface hardness, heat resistance, and the like can be obtained, which is suitable in the present invention. The above general formula (I
Two or more of the compounds represented by I), (III) and (IV) may be used in combination.

[0016]

[0017]

[0018]

[0019] In the above SL formula (II), the alkylene group having 1 to 4 carbon atoms represented by R ₂ include a methylene group, an ethylene group,
Examples thereof include a propylene group, a butylene group, a trimethylene group, and a tetramethylene group.

[0020]

[0021] In the above following general formula (III), the alkyl group of carbon atoms which may be have 1-4 substituted with a hydroxyl group represented by R ₂ include a methyl group, an ethyl group, a propyl group, butyl group, hydroxyethyl And an aryl group having 6 to 10 carbon atoms which may be substituted with a halogen atom includes a phenyl group, a naphthyl group, a chlorophenyl group, a bromophenyl group, a trichlorophenyl group, and a trichlorophenyl group. Examples thereof include a bromophenyl group.The aralkyl group having 7 to 10 carbon atoms which may be substituted with a halogen atom includes a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, a trichlorobenzyl group, Examples thereof include a tribromobenzyl group.

[0022]

[0023]

[0024]

The alkylene group represented R ² and R ³ in the above above formula (IV) include methylene group, ethylene group, propylene group, butylene group, trimethylene group, tetramethylene group,
Alternatively, a group in which these are substituted with a hydroxyl group can be exemplified.

Specific examples of the compounds represented by formulas (II), (III) and (IV) include methyl acrylate, methyl methacrylate, benzyl methacrylate, phenyl methacrylate, and n-butyl methacrylate. T-butyl tribromophenyl methacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 2-hydroxyethyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4 -Methacryloyloxyethoxyphenyl) propane and other acrylic acid and methacrylic acid ester compounds.

Glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate,
β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxybutyl methacrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate,
Examples thereof include methacrylate compounds such as 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl acrylate or acrylate compounds.

The other radical polymerizable monomer copolymerizable with these compounds is not particularly limited as long as it is copolymerizable with the monomer. Chlorostyrene, α-methylstyrene,
Examples thereof include aromatic vinyl compounds such as α-methylstyrene dimer, vinylnaphthalene, isopropenylnaphthalene, bromostyrene, and divinylbenzene.

In view of the physical properties such as the photochromic durability and the speed of decoloring of the resin obtained by polymerizing the mixture of the photochromic composition and the monomer of the present invention, the compound of the above formula (II) is 30 to 90 wt%, compound and / or compounds (IV) of the formula (III) is 0.
1-50% by weight and copolymerizable with these monomers
Other monomers , such as α-methylstyrene and α-methylstyrene dimer, are blended in the range of 0.1 to 50% by weight.

Next, as the photochromic compound which is the component (C) of the photochromic composition of the present invention, a compound exhibiting a photochromic action can be employed without any limitation. For example, photochromic compounds such as a fulgide compound and a chromene compound are well known, and these photochromic compounds can be used in the present invention. The above fulgide compounds and chromene compounds are described in USP 4,882,438, USP 4,960,
678, USP 5,130,058, USP 5,10
Known compounds such as 6,998 can be suitably used.

In the present invention, the fulgide compound has a particularly large effect of preventing the photochromic resin according to the present invention from yellowing during long-term storage at room temperature as compared with other photochromic compounds, and has a large effect of improving the photochromic durability. It can be suitably used for.
A fulgide compound that can be suitably used in the present invention can be represented by the following general formula (V) when represented by the general formula.

[0032]

Embedded image

[However,

[0034]

Embedded image

Is a divalent aromatic hydrocarbon group or a divalent unsaturated heterocyclic group which may have a substituent, and R ₁ is an alkyl group, an aryl group or a substituent. May be a cyclopropyl group or a monovalent heterocyclic group,

[0036]

Embedded image

Is a norbornylidene group or an adamantylidene group, X is an oxygen atom, a group> NR ₂ ,
> NA ₁ -B _1- (A ₂ ) _m- (B ₂ ) _n -R ₃ , group> NA
₃ -A ₄ , or the group> NA ₃ -R ₄ , wherein
R ₂ is a hydrogen atom, an alkyl group or an aryl group, A _1, A ₂ and A ₃ are identical or different alkylene group, an alkylidene group, a cycloalkylene group or an alkyl cycloalkane - diyl group, B ₁ And B ₂ are the same or different

[0038]

Embedded image

And m and n each independently represent 0 or 1. When m is 0, n is 0 and R ₃
Is an alkyl group, a naphthyl group or a naphthylalkyl group, A ₄ is a naphthyl group, and R ₄ is a halogen atom, a cyano group or a nitro group)] In the above formula (V),

[0040]

Embedded image

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

These substituents are not particularly restricted but include, for example, halogen atoms such as chlorine, bromine and iodine:
Alkyl groups having 1 to 4 carbon atoms such as methyl group and ethyl group: alkoxy groups having 1 to 4 carbon atoms such as methoxy group and ethoxy group: 6 to 6 carbon atoms such as phenyl group, tolyl group and xylyl group
10 aryl groups: C7-C14 alkoxyaryl groups (C6-C10 aryl groups substituted with C1-C4 alkoxy groups): amino groups: nitro groups: cyano groups, etc. Can be.

In the above formula (V), the alkyl group, the aryl group and the heterocyclic group represented by R ₁ have the above-mentioned carbon number of 1 to 1.
From an alkyl group of 4, an aryl group having 6 to 10 carbon atoms, and a 5- to 7-membered ring containing 1 to 2 oxygen, nitrogen, or sulfur atoms as ring constituent atoms or a condensed ring thereof with a benzene ring Derived monovalent groups can be mentioned.

[0044] In the above formula (V), an alkyl group, an aryl group represented by R ₂ is the same as the above-mentioned R _1. The alkylene group represented by A ₁ , A ₂ and A ₃ is preferably a group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and the alkylidene group is ethylidene. Group, a propylidene group, an isopropylidene group or the like having 2 to 4 carbon atoms, and a cycloalkylene group is preferably a cyclohexylene group, and an alkylcycloalkane-diyl group is a dimethylcyclohexane-diyl group. Is preferred.

In the above formula (V), the alkyl group represented by R ₃ is the same as the above R, and the naphthylalkyl group is
11 to 11 carbon atoms such as a naphthylmethyl group and a naphthylethyl group
It is preferably 14 groups.

Among the fulgide compounds represented by the above formula, considering the durability of the photochromic action, etc., R
₁ is an alkyl group and a cyclopropyl group, and X is> N
R is a cyanoalkyl group having 1 to 4 carbon atoms, a nitroalkyl group having 1 to 4 carbon atoms, or an alkoxycarbonylalkyl group having 3 to 9 carbon atoms (an alkoxy group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms) 1-4 alkylene groups),

[0047]

Embedded image

Is an adamantylidene group,

[0049]

Embedded image

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

When a photochromic compound is used for an eyeglass lens, a color tone such as gray or brown is preferred. However, such a color tone cannot be obtained by a single photochromic compound, so that two or more different photochromic compounds are mixed. Is adopted. The above-mentioned fulgide compound generally develops an orange-blue color, but by mixing a chromene compound which develops a yellow-orange color, an intermediate color such as gray or brown can be obtained. A chromene compound suitably used for obtaining an intermediate color by mixing with a fulgide compound can be represented by the following formula (VI).

[0052]

Embedded image

Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different hydrogen atoms, alkyl groups, aryl groups, substituted amino groups or saturated heterocyclic groups, and R ₃ and R ₄ are They may together form a ring,

[0054]

Embedded image

The group represented by is a divalent aromatic hydrocarbon group which may be substituted or a divalent unsaturated heterocyclic group.] In the above formula (VI), R ₁ , R ₂ , R _{As the} alkyl group and the aryl group represented by ₃ and R ₄ , the alkyl group and the aryl group described in the formula (V) can be adopted, and the substituted amino group is at least a hydrogen atom in the above-described alkyl group or aryl group. One of the substituted amino groups can be mentioned, and the saturated heterocyclic group includes a nitrogen atom, an oxygen atom, or a sulfur atom such as a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring. Examples thereof include a monovalent group derived from a 5- to 6-membered ring containing 1 or 2 atoms.

In the above formula (VI), the ring formed by R ₃ and R ₄ together forms a norbornylidene group, a bicyclo [3.3.1] 9-nonylidene group, a 2-bicyclo [3.
3.1] 9-nonelidene group and the like.

In the above formula (VI),

[0058]

Embedded image

The aromatic hydrocarbon group or unsaturated heterocyclic group represented by is the same as the group in the above formula (V), and the substituent of each group is not particularly limited. Halogen atom such as iodine: alkyl group having 1 to 20 carbon atoms such as methyl group and ethyl group: alkoxy group having 1 to 20 carbon atoms such as methoxy group and ethoxy group: carbon number such as phenyl group, tolyl group and xylyl group 6 to 10 aryl groups: amino groups: nitro groups: cyano groups and the like.

As the chromene compound, R ₁ and R ₂ are both hydrogen atoms, and R ₃ and R ₄ are the same or different alkyl groups having 1 to 4 carbon atoms,
The bicyclo formed by these together [3.3.
1] 9-nonylidene group, 2-bicyclo [3.3.1] 9
Nonenylidene or norbornylidene,

[0061]

Embedded image

A compound which is a group derived from a naphthalene ring which may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms can be suitably used.

The fulgide compound and the chromene compound which can be suitably used in the present invention include the following compounds.

Fulgide compound: 1) N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.
1.1] Decane) 2) N-cyanomethyl-6,7-dihydro-2- (p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 3) N-cyanomethyl-6,7-dihydro-4 -Methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 4) 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl- 2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 5) 6,7-dihydro-4-methyl-2- (p -Methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 6) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-3-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 7) N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-spiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.
1] Decane) Chromene compound: 1) Spiro [norbornane-2,2 '-[2H] benzo [h] chromene] 2) Spiro [bicyclo [3.3.1] nonane-9,2'
-[2H] benzo [f] chromene] 3) 7'-methoxyspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [f] chromene] 4) 7'-methoxyspiro [ Norbornane-2,2'-
[2H] benzo [f] chromene 5) 2,2-dimethyl-7-octoxy [2H] benzo [h] chromene 6) spiro [2-bicyclo (3.3.1) nonene-9,
2 '-(2H) benzo (h) chromene] 7) Spiro [2-bicyclo (3.3.1) nonene-9,
2 '-(2H) benzo (f) chromene] In the present invention, the blending amount of the photochromic compound with respect to 100 parts by weight of the radical polymerizable monomer is 0.001.
10 to 10 parts by weight, preferably 0.01 to 0.5 part by weight. In this range, the best photochromic performance is obtained.

As described above, the composition comprising the radical polymerizable monomer and the photochromic compound is usually blended as a polymerization inhibitor of the radical polymerizable monomer with the following general formula (I):

[0066]

Embedded image

(Wherein R ₁ is a hydroxyl group, a methyl group or a methoxy group). The phenolic compound causes a significant yellowing in the photochromic resin due to the action of the photochromic compound. Under these circumstances, the present invention is most characterized in that the content of the phenolic compound is suppressed to 15 ppm or less, and a hindered phenolic compound is blended instead. That is, the hindered phenol compound has a good polymerization inhibiting ability for the radically polymerizable monomer, and does not cause yellowing in a photochromic resin obtained by polymerizing the monomer. Good storage stability is imparted to the resin.

Known hindered phenol compounds can be used without any limitation.
It is preferable to use a compound represented by the following general formula (VII).

[0069]

Embedded image

[Where X is a methyl group, a hydroxyl group or a t-butyl group, m is an integer of 0 to 3,
A is a hydrogen atom, a methyl group or

[0071]

Embedded image

(Where R ₁ is an alkyl group having 1 to 20 carbon atoms, for example, an alkyl group having 13 carbon atoms).

[0073]

Embedded image

(Where R ₂ is hydrogen or C 1 -C 2)
0, for example, an alkyl group having 3 carbon atoms) and m is 2.

[0075]

Embedded image

Where m is 3

[0077]

Embedded image

Examples of the hindered phenol compound of the above formula (VII) include 2,6-di-tert-butylhydroxytoluene,
4-hydroxy-2-t-butylphenol, tri (4
-Hydroxy-3,5-di-tert-butylbenzyl) isocyanurate, 1,1-di (4-hydroxy-2-methyl-5-tert-butylphenyl) -3 (4-hydroxy-2
-Methyl-5-t-butylphenyl) butane, 1,1-
Di (4-hydroxy-2-methyl-5-t-butylphenyl) butane, tri (4-hydroxy-3,5-di-t-
Butylphenyl) propion sanoctadecanyl, pentaerythritol tetrakis [tri (4-hydroxy-
3,5-di-t-butylphenyl) propionate], β
-Thiodiglycol di [tri (4-hydroxy-3,5
-Di-t-butylphenyl) propionate], spiroglycol-di (4-hydroxy-3-methyl-5-tbutylphenyl) propionate, 1,3,5 tri (4-
Hydroxy-3,5-di-tert-butylbenzyl) -2,
4,6 trimethylbenzene and the like can be mentioned.

In the present invention, when the content of the hindered phenolic compound is too small, the ability of the radical polymerizable monomer to inhibit polymerization during storage of the composition is not sufficient, Inhibits polymerization at the time of curing, and a practical photochromic resin cannot be obtained. For this reason, in the present invention, the hindered phenolic compound is used in an amount of 0.001 to 1 part by weight, preferably 0.01 to 0.
1 part by weight is blended.

In the photochromic composition of the present invention, the photochromic resin causes yellowing, and the content of the photochromic resin is suppressed to 15 ppm or less.

[0081]

Embedded image

(Where R ₁ is a hydroxyl group, a methyl group or a methoxy group): (a) hydroquinone (b) hydroquinone monomethyl ether (c) catechol (d) And methylphenol. In the case of the present invention, if the content of these phenolic compounds is more than 15 ppm, a sufficient yellowing prevention effect cannot be obtained.

In the present invention, the photochromic composition comprising the above components may be blended by any procedure, not to mention the method of blending the components simultaneously. Preferably, a hindered phenol-based compound is previously blended with the radical polymerizable monomer to inhibit polymerization during storage of the radical polymerizable monomer before providing the composition of the present invention. When the composition of the present invention is desired, a photochromic compound is preferably added thereto to obtain the composition of the present invention.

The polymerization method for obtaining a polymer from the photochromic composition of the present invention is not particularly limited, and a known radical polymerization method can be employed. The polymerization initiation means can be performed by using a radical polymerization initiator such as various peroxides and azo compounds. Illustrating a typical polymerization method, between a mold held by an elastomer gasket or a spacer, a photochromic composition of the present invention containing a radical polymerization initiator is injected, polymerized in a heating furnace, and then removed. Polymerization can be employed.
Further, when obtaining a photochromic polymer also having polarization properties, between the mold that also holds the polarizing film with an elastomer gasket or spacer, the photochromic composition of the present invention containing a radical polymerization initiator, and further, if necessary. It is possible to adopt cast polymerization in which a radical polymerizable monomer is injected, polymerized in a heating furnace, and then removed.

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

The amount of the radical polymerization initiator used depends on the polymerization conditions, the type of the initiator and the composition of the above-mentioned monomer.
Although it is not necessarily limited, it is generally 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the radical polymerizable monomer in the photochromic composition. is there.

[0087] Among the polymerization conditions, particularly the temperature affects the properties of the obtained photochromic resin. The temperature condition is affected by the type and amount of the initiator and the type of the monomer, and thus cannot be unconditionally limited. Generally, the polymerization is started at a relatively low temperature, and the temperature is gradually increased. It is preferable to perform a so-called tapered two-stage polymerization in which the composition is cured at a high temperature at the time of completion. Since the polymerization time also varies depending on various factors like the temperature, it is preferable to determine an optimum time in advance according to these conditions, but in general, the conditions are selected so that the polymerization is completed in 2 to 40 hours. Is preferred.

Of course, in the polymerization, various stabilizers and additives such as a releasing agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, an anticolorant, an antistatic agent, a fluorescent dye, a dye, a pigment and a fragrance are used. It can be selected and used as needed.

In the photochromic composition of the present invention, the hindered phenol compound is a compound which also has an action as an ultraviolet stabilizer, but in the present invention, a mixture of an ultraviolet stabilizer other than the compound may be used. Is preferable because the durability of the photochromic compound can be further improved. In particular, fulgide compounds
Because the effect of durability improvement by UV stabilizer is great,
When the fulgide compound and the chromene compound as described above are used in combination, it is possible to favorably prevent the intermediate color of these compounds from changing over time.

As the ultraviolet stabilizer, a hindered amine light stabilizer and a sulfur-based antioxidant can be preferably used, and particularly, a hindered amine light stabilizer having a hindered amine structure in a molecule is preferable.

The compounding amount of the ultraviolet stabilizer is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 1 part by weight, based on 100 parts by weight of the radical polymerizable monomer.

Further, when a fulgide compound and a chromene compound are used in combination, by adding a phosphite compound, it is possible to further suppress the change over time of the mixed color of these compounds. Therefore, the use of both the above-mentioned ultraviolet stabilizer and phosphite compound in a system in which a fulgide compound and a chromene compound are used in combination is the most preferred embodiment in the present invention.

The compounding amount of the phosphite compound is 0.001 to 100 parts by weight of the radical polymerizable monomer.
It is preferably 10 parts by weight, more preferably 0.01 to 1 part by weight.

The photochromic resin obtained by the above method can be subjected to the following treatment depending on the use. That is, dyeing using a dye such as a disperse dye, a silane coupling agent, a hard coat agent mainly containing a sol such as silicon, zirconium, antimony, aluminum, tin, and tungsten, SiO 2, TiO, and ZrO
It is also possible to perform processing such as antireflection processing and antistatic processing by depositing a thin film of a metal oxide such as the above or applying a thin film of an organic polymer, and secondary processing.

[0095]

By polymerizing the photochromic composition of the present invention, a stable photochromic resin free from yellowing or the like can be obtained even when stored at room temperature or the like for a long period of time. The photochromic resin has a high coloring density, a high fading speed, excellent durability of photochromic action, excellent transparency and surface hardness. Further, the photochromic composition of the present invention has good storage stability before curing, and suppresses partial polymerization of the radically polymerizable monomer component during the storage.

Therefore, the photochromic composition of the present invention is extremely useful as a composition for providing a photochromic resin used as a material for an organic glass having photochromic properties, for example, a photochromic lens.

[0097]

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

The compounds used in the following examples are as follows.

Radical polymerizable monomers A: glycidyl methacrylate B: β-methylglycidyl methacrylate C: bisphenol A-monoglycidyl ether methacrylate D: triethylene glycol dimethacrylate E: tetraethylene glycol dimethacrylate F: 2-hydroxyethyl methacrylate G: benzyl methacrylate H: n-butyl methacrylate I: α-methylstyrene J: α-methylstyrene dimer K: methacrylate compound of 2,2-bis (4-methacryloyloxyethoxyphenyl) propane hindered phenol Compound A: 2,6-di-tert-butylhydroxytoluene B: tri (4-hydroxy-3,5-di-tert-butylbenzyl isocyanurate C: tri (4-hydroxy-3,5-di-tert-butyl) Ruphenyl) propionsanoctadecanyl fulgide compound: A: N-cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [ 3.3.
1.1] Decane) B: N-cyanomethyl-6,7-dihydro-2- (p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) C: N-cyanomethyl-6,7-dihydro-4 -Methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) D: 6,7-dihydro-N-methoxycarbonylmethyl-4-methyl- 2-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) E: 6,7-dihydro-4-methyl-2- (p -Methylphenyl) -N-nitromethylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) F: N-cyanomethyl- 6,7-dihydro-4-cyclopropyl-3-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) Chromene compound: A: Spiro [Norbornane-2,2 '-[2H] benzo [h] chromene] B: Spiro [bicyclo [3.3.1] nonane-9,2'
-[2H] benzo [f] chromene] C: 7'-methoxyspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [f] chromene] D: 7'-methoxyspiro [ Norbornane-2,2'-
[2H] benzo [f] chromene E: 2,2-dimethyl-7-octoxy [2H] benzo [h] chromene F: spiro [2-bicyclo [3.3.1] nonene-9,
2 '-[2H] benzo [f] chromene] Kutadecanyl Hindered amine light stabilizer A: MARK LA-63 (trade name: manufactured by Asahi Denka Co., Ltd.) 1,2,3,4-butanetetracarboxylic acid and 1, 2,2,6,6, -pentamethyl-4-piperidinol and β, β, β ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane ) Condensate with diethanol

[0100]

Embedded image

Phosphite compound A: HBP (trade name: manufactured by Johoku Chemical Co., Ltd.) Hydrogenated bisphenol A / phosphite polymer

[0102]

Embedded image

Examples 1 and 2 65 parts by weight of tetraethylene glycol dimethacrylate, 15 parts by weight of triethylene glycol dimethacrylate, 9 parts by weight of glycidyl methacrylate, 2 parts by weight of 2-hydroxyethyl methacrylate, 8 parts by weight of α-methylstyrene, α A mixture of 1 part by weight of methylstyrene dimer and 0.03 part by weight of 2,6-di-tert-butylhydroxytoluene (hereinafter also referred to as BHT) as a hindered phenol compound; A polymerizable monomer mixture was obtained. The mixed liquid of radical polymerizable monomers contained hydroquinone monomethyl ether (hereinafter, also referred to as MEHQ) at a concentration shown in Table 1.

Next, N-cyanomethyl-6,7 as a fulgide compound was added to the radical polymerizable monomer mixture.
0.2 parts by weight of -dihydro-2- (p-methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.1] decane) 0.05 parts by weight of spiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [f] chromene] as a chromene compound and 0.2 parts by weight of LA-63 as a hindered amine light stabilizer. 0.7 parts of HBP was added as a phosphite compound and mixed well. The obtained mixture was stored at room temperature and in a dark place for 3 months, and the stability during storage was evaluated as ○ when no gelation occurred, and as X when slight gelation was observed. The results are shown in Table 1.

Also, 0.5 part by weight of t-butylperoxy-2-ethylhexanate as a radical polymerization initiator was mixed well with the same mixture, and the resulting mixture was mixed with a glass plate and ethylene-acetic acid. It was poured into a mold composed of a gasket made of a vinyl copolymer and cast polymerization was performed. The polymerization was carried out using an air furnace at 30 ° C. to 90 ° C. for 18 hours, and the temperature was gradually increased and kept at 90 ° C. for 2 hours. After the polymerization is completed, remove the mold from the air furnace and allow it to cool.
The weight was removed from the glass mold.

The resulting photochromic resin (2 m thick)
The photochromic properties of m) were measured by the following method, and the results are shown in Table 1.

(1) Change in Yellowness The photochromic resin was stored at room temperature for 3 months in the absence of light, and the change in yellowness before and after storage was measured using a color difference meter manufactured by JEOL Ltd. YI was measured by a transmission method. The higher the YI value, the higher the degree of yellowing during storage at room temperature.

(2) Coloring density A xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics was used as a photochromic resin at 20 ° C. ± 1 through an aeromass filter (manufactured by Corning).
° C, beam intensity 365n on photochromic resin surface
m = 2.4 mW / cm ² , 245 nm = 24 μW / cm ²
Irradiate for 120 seconds to develop color, ε (120 seconds)-ε
(0 sec) was determined and defined as the color density. However, ε (60
S) is the absorbance of the photochromic resin at the maximum absorption wavelength after light irradiation for 60 seconds under the above conditions, and ε
(0 seconds) is the absorbance of the unirradiated resin at the maximum absorption wavelength at the time of light irradiation.

(3) Discoloration speed In the measurement of the color density, the light irradiation was stopped after irradiating for 120 seconds, and the absorbance of the photochromic resin was changed to ε.
The time (sec) required to decrease to (120 sec) -ε (0 sec) was measured.

(4) Durability Xenon fade meter FAC- manufactured by Suga Test Instruments Co., Ltd.
The fatigue life was measured by 25AX-HC. The fatigue life (T _1/2 ) is defined as the absorbance at the maximum absorption wavelength based on the photochromic compound, which is 初期 of the initial absorbance (T ₀ ).
It was expressed by the time required to decrease. Where T ₀ and T
The absorbance of _1/2 is a value obtained by subtracting the absorbance of the unirradiated resin at the maximum absorption wavelength.

In Comparative Example 1 and Example 1, the concentrations of hydroquinone monomethyl ether are shown in Table 1,
The operation was performed in exactly the same manner as in Example 1 except that 2,6-di-tert-butylhydroxytoluene was not blended. Table 1 shows the results
It was shown to.

Comparative Example 2 The procedure of Example 1 was repeated, except that the concentration of hydroquinone monomethyl ether was changed as shown in Table 1. The results are shown in Table 1.

[0113]

[Table 1]

Comparative Example 3 The same operation as in Comparative Example 1 was carried out except that the fulgide compound and the chromene compound were not used.
The change in the degree of yellowing was only 0.9. From this,
It has been found that the yellowing of the photochromic resin occurs remarkably due to the mutual action of hydroquinone monomethyl ether and the photochromic compound.

Examples 3 to 8 In Example 2, the composition of the radical polymerizable monomer is shown in Table 2.
Example 2 was carried out in the same manner as in Example 2 except that the above-described method was used. The results are shown in Table 2.

[0116]

[Table 2]

Examples 9 to 12 The same procedures as in Example 1 were carried out except that the types of the hindered phenol compounds were changed to those shown in Table 3. The results are shown in Table 3.

[0118]

[Table 3]

Examples 13 to 21 In Example 1, the fulgide compound 0.5 shown in Table 4 was used.
The procedure was carried out in exactly the same manner as in Example 1 except that 0.2 part by weight of the chromene compound was used in combination with 0.2 part by weight. The results are shown in Table 4.

[0120]

[Table 4]

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 9/02 C08K 3/00-13/08 C08L 1/00-101/16 C08F 2/44-2/50 C08F 20 / 00-20/40 C08F 120/00-120/40 C08F 220/00-220/40

Claims (1)

(57) [Claims] 1. A radical polymerizable monomer (A) 100 weight
Parts by weight (B) hindered phenolic compound 0.001 to 1
Parts by weight (C) Photochromic compound 0.001 to 10 parts by weight
And having the following general formula (I):(However, R₁Is hydroxyl, methyl or meth
Phenolic compound content of
ButFifteenbelow ppmAnd the above radical polymerizable monomer
The body (A) has the following formula (II) Embedded image(Where R ₁ Is a hydrogen atom or a methyl group;
_Two Is an alkylene group having 1 to 4 carbon atoms, or the following formula Embedded image(Where k is an integer of 0 to 5)
And n is an integer of 1 to 20).
９０90% by weight, the following formula (III) (However, R ₁ Is a hydrogen atom or a methyl group;
_Two Represents 1 carbon atom which may be substituted by a hydroxyl group
4 to 4 alkyl groups, which may be substituted with a halogen atom
Aryl groups having 6 to 10 carbon atoms, substituted with halogen atoms
Which may be an aralkyl group having 7 to 10 carbon atoms)
And / or the following formula (IV) Embedded image (However, R ₁ And R _Four Are the same or different
A hydrogen atom or a methyl group; _Two And R _Three Is it
Substituted with the same or different hydroxyl groups
C1-C4 alkylene group, or Embedded image And m and n are each 0 or 1.)
0.1 to 50% by weight of a compound represented by the formula
From 0.1 to 50% by weight of other monomers copolymerizable with the product.
ToPhotochromic composition.