JP2003128713A - Curable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition suitable as a coating material having excellent adhesivity to a substrate of an eyeglass lens, etc., and having good stability even by storing in a one-pack state. SOLUTION: The curable composition contains a photo-base generation compound e.g. an oxime derivative such as o-phenylacetylacetophenoxime and a carbamic acid derivative such as 2-oxy-1,2-diphenylethyl-N-cyclohexylcarbamate, a radically polymerizable monomer having epoxy group such as glycidyl methacrylate and a photochromic compound such as a chromene compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic curable composition suitable for use in spectacle lenses and coating agents for spectacle lenses.

[0002]

2. Description of the Related Art Photochromism is a reversible property in which when a compound is irradiated with light containing ultraviolet rays such as sunlight or light from a mercury lamp, the color of the compound rapidly changes, and when the irradiation of light is stopped and the compound is left in a dark place, the original color is restored. It is a function and has been applied to various purposes.

For example, photochromism is applied also in the field of spectacle lenses, and a plastic lens having photochromic properties can be obtained by curing a polymerizable monomer to which various photochromic compounds having the above properties are added. ing. Also, as a photochromic compound, a fulgimide compound, a spirooxazine compound, a chromene compound, and the like, which can be suitably used for such applications, have been found.

However, these photochromic compounds often have a problem that the color density is gradually decreased or the color tone is changed due to repeated color development, that is, they do not have sufficient durability. On the other hand, the present inventors have found that it is possible to improve durability by adding a radically polymerizable monomer having an epoxy group as a component of the polymerizable monomer, and have already proposed (special feature). Kaihei 5-306392).

On the other hand, a curable composition mainly containing a photochromic compound and a polymerizable monomer has been conventionally cured by thermal polymerization, but in recent years, curing by photopolymerization is mainly used for the purpose of shortening the production time. Is becoming. In the case of photopolymerization, a basic compound such as an amine compound is also used in combination with a compound (photocatalyst) that exhibits radical polymerization initiation ability by irradiation with ultraviolet light or visible light. By using the basic compound in combination, the photopolymerization initiation ability of the photocatalyst is amplified.

In addition to the above, in order to obtain a spectacle lens having a photochromic property, a method of coating the spectacle lens with a layer having a photochromic property (coating layer) is used, instead of compounding the photochromic compound in the lens itself. Proposed. Such methods have been proposed in US Pat. No. 5,914,174, WO01 / 02449, etc., but the coating agents described therein have insufficient adhesion between the base lens and the coating layer. It was

Generally, as a method for improving the adhesion of the coating layer, a method of polishing the surface such as sand brush, a method of etching the surface with an alkali treatment and giving an active group on the surface by hydrolysis, or plasma, Surface treatment such as a method of activating the surface of a substrate by corona discharge treatment is known. However, heat treatment for a long period of time is often required for adhesion using only these treatments, and it has not yet reached a practical level for lens applications requiring optical precision. Therefore, the present inventors have already proposed and found that a curable composition containing a silyl monomer and an amine compound has high adhesiveness as a method for improving the adhesiveness by using a mild condition for a short time. (Japanese Patent Application No. 2001-227374) As described above, blending a basic compound with a curable composition composed of a photochromic compound and a radical-polymerizable monomer has various advantages, and demands thereof are not small. However, as described above, in order to improve the durability of the photochromic compound, when a radical polymerizable monomer having an epoxy group is added, the following problems occur when the basic compound is added.

That is, since a basic compound generally serves as an epoxy group ring-opening / polymerization catalyst, if both components are stored in the same package, both components will react. Therefore, it must be stored at least separately in a package containing a basic compound and a package containing a radical-polymerizable monomer having an epoxy group and mixed immediately before use. There is a risk that it will be troublesome and that a mixing error will occur.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, to provide a photochromic compound with excellent durability, and to store it as a single solution. It is to provide a curable composition having excellent adhesion to a substrate.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that in addition to a photochromic compound and a radical polymerizable monomer having an epoxy group,
Although it is a neutral compound during storage, it has a high storage stability even when coexisted with a photochromic compound by blending a compound that decomposes by light irradiation to generate a basic substance,
In addition, they have found that the same effect as in the case of blending a basic compound is exhibited by irradiating appropriate light at the time of use, and the present invention has been completed.

That is, the present invention provides (A) a photobase generating compound,
A photochromic curable composition comprising (B) a radical polymerizable monomer containing a radical polymerizable monomer having an epoxy group, and (C) a photochromic compound.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The first component of the curable composition of the present invention is a photobase generating compound. The photobase generating compound is a compound which produces a basic compound upon irradiation with light, and the photobase generating compound used in the present invention is not particularly limited as long as it is a compound which produces a compound having a basic group upon irradiation with light. Not done. Incidentally, in the present invention, the photobase generating compound is not only a compound which directly produces a compound having a basic group such as an amine compound by light irradiation, but like an acyloxime, an imino compound is produced by light irradiation, and Also included are compounds that produce amine precursors upon irradiation with light, such as those that produce amine compounds upon hydrolysis. Examples of the photobase generating compound that can be preferably used include those represented by the following general formulas (1) to (4).

[0013]

[Chemical 1]

[Wherein R ¹ is a linear, branched or cyclic alkyl group (which may be substituted with an alkoxy group),
A substituted or unsubstituted aromatic hydrocarbon group or a radically polymerizable group, R ² is represented by the following formula (A)

[0015]

[Chemical 2]

A group represented by: or the following formula (B)

[0017]

[Chemical 3]

[In the formula, R ³ and R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group (which may be substituted with an aromatic ring), or a substituted or unsubstituted aromatic hydrocarbon. Represents a group, and n is 0 or 1. }, M is 0 or 1 and l is an integer of 0-10. ]

[0019]

[Chemical 4]

{In the formula, R ⁵ has the same meaning as R ² described in the above formula (1), R ⁶ is an alkylene group having 2 to 20 carbon atoms, and X is NH.
Alternatively, it represents an oxygen atom, and s is 0 or 1. }

[0021]

[Chemical 5]

{In the formula, R ⁷ has the same meaning as R ¹ described in the above formula (1), R ⁸ is an alkyl group having 1 to 10 carbon atoms, R ⁹ is an alkylene group having 2 to 10 carbon atoms, and Y is Y. Represents NH or an oxygen atom, u is an integer of 0 to 10, and v is 0 or 1. }

[0023]

[Chemical 6]

{In the formula, R ¹⁰ has the same meaning as R ¹ described in the above formula (1), and R ¹¹ and R ¹² are each independently a hydrogen atom and a carbon number of 1
~ 5 alkyl group or a substituted or unsubstituted aromatic hydrocarbon group, R ¹³ represents a substituted or unsubstituted aromatic hydrocarbon group, w is an integer of 0 to 10, x is 0 or 1 Is. In the general formula (1), R ¹ is a linear, branched or cyclic alkyl group (preferably having 1 carbon atom) which may be substituted with an alkoxy group (preferably an alkoxy group having 1 to 6 carbon atoms). -10 alkyl group), a substituted or unsubstituted aromatic hydrocarbon group having 6 to 14 carbon atoms,
Alternatively, it is a radically polymerizable group. The alkyl group is not particularly limited, but specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group. Group, 1-methylpentyl group, 1-ethylbutyl group, 2-
Examples include methylpentyl group, cyclohexyl group, octyl group, decyl group, methoxymethyl group, ethoxyethyl group, ethoxybutyl group and the like.

Specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthranyl group and the like, and the substituent of the aromatic hydrocarbon group is not particularly limited, and a methyl group, Alkyl group having 1 to 5 carbon atoms such as ethyl group, alkoxy group having 1 to 5 carbon atoms such as methoxy group and ethoxy group, acyl group having 2 to 5 carbon atoms such as acetyl group and propionyl group, fluorine atom, chlorine atom And other halogen atoms, cyano groups, nitro groups and the like. Further, the alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms and the acyl group having 2 to 5 carbon atoms may be further substituted with a halogen atom or the like.

Examples of the radically polymerizable group include vinyl group, allyl group, acryl group and methacryl group.

R ⁶ in the general formula (2) has 2 carbon atoms.
To 20 alkylene groups, specifically an ethylene group,
Examples include a trimethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group.

R ⁸ in the general formula (3) has 1 carbon atom.
10 represents an alkyl group, and the alkyl group may be linear or branched, and specifically, a methyl group, an ethyl group, n-
Propyl group, i-propyl group, n-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylpentyl group, octyl group, decyl group, etc. R ⁹ is an alkylene group having 2 to 10 carbon atoms, and specific examples thereof include an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group.

R ¹¹ and R ¹² in the general formula (4)
Are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group. As the alkyl group having 1 to 5 carbon atoms, a methyl group, an ethyl group,
Examples thereof include a propyl group and a butyl group, and specific examples of the substituted or unsubstituted aromatic hydrocarbon group are the same as those described for R ¹ in the general formula (1). R ¹³ is a substituted or unsubstituted aromatic hydrocarbon group, and the same ones as described for R ¹ in the above general formula (1) are specifically exemplified.

Further, R ² in these general formulas (1),
R ⁵ in the general formula (2) and R ⁷ in the general formula (3)
And when R ¹⁰ in the general formula (4) is a group represented by the above formula (B), R ³ and R ⁴ in the group are each independently a hydrogen atom, a linear or branched alkyl group, or a substituent. Alternatively, it is an unsubstituted aromatic hydrocarbon group.

The linear or branched alkyl group is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms, specifically, methyl group, ethyl group, n group.
-Propyl group, i-propyl group, n-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylpentyl group, n-octyl group, n -A decyl group etc. are illustrated. Further, the alkyl group is a phenyl group, a naphthyl group,
It may be substituted with an aromatic ring having 6 to 14 carbon atoms such as a tolyl group.

Specific examples of the substituted or unsubstituted aromatic hydrocarbon group are the same as those exemplified for R ¹ .

Among the photobase-generating compounds represented by the above general formula, there is no initial coloration, the compound can be suitably used for applications such as spectacle lenses, and the base generation efficiency is high. A photobase generating compound which is generated can be preferably used.

Specific examples of photobase generating compounds that can be preferably used include O-phenylcarbamoylacetophenone oxime, O-phenylcarbamoylbenzophenone oxime, O-phenylcarbamoyl-2-acetonaphthone oxime, and O-phenylcarbamoylfluorenone oxime. , O-phenylacetylacetophenone oxime, O-phenylacetylbenzophenone oxime, O
-Phenylacetyl-2-acetonaphthone oxime, O
-Phenylacetylfluorenone oxime, O-benzoylacetophenone oxime, O-benzoylbenzophenone oxime, O-benzoyl-2-acetonaphthone oxime, O-benzoylfluorenone oxime, O-
(Meth) acryloyl acetophenone oxime, O-
(Meth) acryloylbenzophenone oxime, O-
(Meth) acryloyl-2-acetonaphthone oxime,
O- (meth) acryloylfluorenone oxime, O-1
(Or 2) -naphthoylacetophenone oxime, O-
1 (or 2) -naphthoylbenzophenone oxime, O
-1 (or 2) -naphthoyl-2-acetonaphthone oxime, O-1 (or 2) -naphthoylfluorenone oxime, O-pivaloyl acetophenone oxime, O-pivaloyl benzophenone oxime, O-pivaloyl-2 −
Acetonaphthone oxime, O-pivaloyl fluorenone oxime, O, O'-glutaryl diacetophenone oxime, O, O'-glutaryl dibenzophenone oxime, O,
O'-glutaryl di (2-acetonaphthone oxime),
O, O'-glutaryl difluorenone oxime, O, O'-succinyl diacetophenone oxime, O, O'-succinyl dibenzophenone oxime, O, O'-succinyl di (2-acetonaphthone oxime), O, O ' -Succinyldifluorenone oxime, 2-oxy-1,2-diphenylethyl N-cyclohexyl carbamate, 2-oxy-1- (3,5-dimethoxyphenyl) -2- (4-
Methoxyphenyl) ethyl N-cyclohexyl carbamate, 1-methyl-1-phenylethyl N-cyclohexyl carbamate and the like can be mentioned.

These photobase generating compounds may be used alone or as a mixture of plural kinds.

The compounding amount of these photobase generating compounds is not particularly limited as long as the effect is exhibited, but preferably 0.1 to 20 with respect to 100 parts by mass of all radical-polymerizable monomers to be compounded. It is a mass part, More preferably, it is 0.5-10 mass parts. When the amount is 0.1 part by mass or more, the adhesion between the coating layer and the base material is particularly effective, and when the amount is 20 parts by mass or less, the resulting cured product does not discolor (yellow). It becomes easy to do.

The second component in the curable composition of the present invention is a radical polymerizable monomer containing a radical polymerizable monomer having an epoxy group. By blending a radical-polymerizable monomer having an epoxy group as the radical-polymerizable monomer, it is possible to suppress deterioration of the photochromic compound over time and easily obtain an excellent photochromic material with little color shift for a long period of time. Becomes Further, when the curable composition of the present invention is used as a coating material, it has the effect of improving the adhesion to the substrate.

The radical polymerizable monomer having an epoxy group is not particularly limited as long as it is a compound having at least one radical polymerizable unsaturated group and one epoxy group in the molecule, and known compounds can be used. However, a compound having a (meth) acryl group as a polymerizable unsaturated group is preferable in consideration of polymerizability, easiness of acquisition and synthesis, stability and the like.

Specific examples of such radically polymerizable monomers having an epoxy group include glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl methacrylate, bisphenol A-monoglycidyl ether-methacrylate, 4-glycidyloxy methacrylate, 3- (glycidyl-2-oxyethoxy)
2-Hydroxypropyl methacrylate, 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate, 3-glycidyloxy-2
-Hydroxypropyloxy) -2-hydroxypropyl acrylate, glycidyloxy polyethylene glycol methacrylate having an average molecular weight of 540, and the like.

The radical polymerizable monomer having an epoxy group may be a single type or a combination of a plurality of types.

When the curable composition of the present invention is used as a coating material, in addition to the radical polymerizable monomer having an epoxy group, a silanol group (≡Si-) is used as the radical polymerizable monomer. OH) or a radical-polymerizable monomer having a group that produces a silanol group by hydrolysis is preferably used in combination. By blending such a radically polymerizable monomer, it is possible to further improve the adhesiveness to the substrate, and further, to use a hard coating used to coat the photochromic coating layer if necessary. The adhesiveness with the coat layer can also be significantly improved.

Such a radical-polymerizable monomer has at least one silanol group (≡Si—OH) or a group capable of producing a silanol group by hydrolysis and one radical-polymerizable unsaturated group in the molecule. If it ’s a compound,
Known compounds can be used without any limitation.

Specific examples of the group capable of forming a silanol group by the hydrolysis include an alkoxysilyl group (≡Si—O—R; R is an alkyl group) and an aryloxysilyl group (≡Si—O—Ar; Ar is an optionally substituted aryl group), a halogenated silyl group (≡Si—X;
X is a halogen atom), a silyloxysilyl group (disiloxane bond; ≡Si-O-Si≡), and the like. Among these groups that generate a silanol group by hydrolysis,
Ease of production of silanol groups, ease of synthesis and storage,
It is preferably an alkoxysilyl group or a silyloxysilyl group from the viewpoint that the group eliminated from the silicon atom by the reaction has little influence on the physical properties of the cured product, and has 1 to 1 carbon atoms.
It is more preferably an alkoxysilyl group containing an alkoxyl group of 4 and most preferably a methoxysilyl group or an ethoxysilyl group.

As the polymerizable unsaturated group, a (meth) acrylic group is particularly preferable.

Specific examples of the radical-polymerizable monomer having such a silanol group or a group capable of producing a silanol group by hydrolysis include γ-methacryloyloxypropyltrimethoxysilane and γ-methacryloyloxypropyltriethoxysilane. , Γ-methacryloyloxypropylmethyldimethoxysilane, (3-acryloyloxypropyl) dimethylmethoxysilane, (3-
Acryloyloxypropyl) methyldimethoxysilane, (3-acryloyloxypropyl) trimethoxysilane, 3- (N-allylamino) propyltrimethoxysilane, allyldimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, 3-aminophenoxydimethyl Vinylsilane, 4-aminophenoxydimethylvinylsilane, 3- (3-aminopropoxy)-
3,3-dimethyl-1-propenyltrimethoxysilane, butenyltriethoxysilane, 2- (chloromethyl) allyltrimethoxysilane, diethoxyvinylsilane, 1,3-divinyltetraethoxydisiloxane, docosenyltriethoxysilane, O- (methacryloyloxyethyl) -N- (triethoxysilylpropyl) urethane, N- (3-methacryloyloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, methacryloyloxyethoxytrimethylsilane,
(Methacryloyloxymethyl) dimethylethoxysilane, methacryloyloxymethyltriethoxysilane,
Methacryloyloxymethyltrimethoxysilane, methacryloyloxypropyldimethylethoxysilane, methacryloyloxypropyldimethylmethoxysilane,
Methacryloyloxypropyltris (methoxyethoxy) silane, 7-octenyltrimethoxysilane, 1,
3-bis (methacryloyloxy) -2-trimethylsiloxypropane, tetrakis (2-methacryloyloxyethoxy) silane, trivinylethoxysilane, trivinylmethoxysilane, vinyldimethylethoxysilane, vinyldiphenylethoxysilane, vinylmethyldiacetoxysilane, Vinylmethyldiethoxysilane, vinylmethyldimethoxysilane, O- (vinyloxyethyl) -N- (triethoxysilylpropyl) urethane,
Vinyloxytrimethylsilane, vinylphenyldiethoxysilane, vinylphenylmethylmethoxysilane, vinyltriacetoxysilane, vinyltri-t-butoxysilane, vinyltriethoxysilane, vinyltriisopropenoxysilane, vinyltriisopropoxysilane, vinyltrimethoxy Silane vinyltriphenoxysilane,
Vinyl tris (2-methoxyethoxy) silane etc. can be mentioned.

The radical-polymerizable monomer having a silanol group or a group capable of forming a silanol group by hydrolysis may be a single type or a combination of a plurality of types.

Also, a radical-polymerizable monomer having an isocyanate group (--NCO) may be added in place of the radical-polymerizable monomer having the silanol group or a group capable of forming a silanol group by hydrolysis. The effect of can be obtained. The radical polymerizable monomer having an isocyanate group is not particularly limited, and known compounds can be used, specifically, 2-isocyanatoethoxymethacrylate, 4- (2-isocyanatoisopropyl). Examples include styrene and the like.

In the curable composition of the present invention, in order to improve the mechanical properties and photochromic properties of the resulting cured product, the radical polymerizable monomer having the above-mentioned epoxy group is used as the radical polymerizable monomer. Radical polymerizable monomers other than monomers and radical polymerizable monomers having silanol groups or groups that generate silanol groups by hydrolysis and radical polymerizable monomers having isocyanate groups (hereinafter referred to as other radicals It is preferable that a polymerizable monomer) is blended.

Other radical-polymerizable monomers may be appropriately selected and blended depending on the use of the curable composition and the physical properties to be obtained, and known compounds can be used without particular limitation.

A radical polymerizable monomer having a plurality of radically polymerizable unsaturated groups (hereinafter, referred to as other polyfunctional radically polymerizable monomer) in terms of excellent curability and mechanical properties after curing. ) Is preferably blended. Further, as the polymerizable unsaturated group, a compound having a (meth) acrylic group is preferable.

Specific examples of the other polyfunctional radically polymerizable monomers that can be preferably used as the compounding component of the curable composition of the present invention include trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, and tetramethylol. Methane trimethacrylate, tetramethylol methane triacrylate, trimethylol propane trimethacrylate, tetramethylol methane tetramethacrylate, tetramethylol methane tetraacrylate, trimethylol propane triethylene glycol trimethacrylate, trimethylol propane triethylene glycol triacrylate, ethoxylated penta Erythritol tetraacrylate, ethoxylated pentaerythritol tetramethacrylate, pentaerythritol Methacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, urethane oligomer tetraacrylate, urethane oligomer hexamethacrylate, urethane oligomer hexaacrylate, polyester oligomer hexaacrylate, polyester oligomer tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra Radical polymerizable monomers having 3 to 6 (meth) acrylic groups as polymerizable unsaturated groups such as acrylates;
Ethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, nonaethylene glycol dimethacrylate, nonapropylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate , Bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (3,5-dibromo-4-methacryloyloxyethoxyphenyl) propane, 1,4 butylene glycol tolylene dimethacrylate, 1,9 Nonylene glycol dimethacrylate, neopentylene glycol As a polymerizable unsaturated group such as dimethacrylate, 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether, 1,4-bis (methacryloylthiomethyl) benzene, a (meth) acryl group is 2 Examples thereof include a radically polymerizable monomer and the like.

Other polyfunctional radically polymerizable monomers having radically polymerizable unsaturated groups other than (meth) acrylic groups include diallyl phthalate, diallyl isophthalate, diallyl tartrate, diallyl succinate and diallyl fumarate. , Diallyl chlorendate, diallyl hexaphthalate, allyl diglycol carbonate and the like.

These polyfunctional radically polymerizable monomers may be used in combination with a plurality of different compounds.

Further, the curable composition of the present invention may optionally contain, as another radical-polymerizable monomer, a compound having only one radical-polymerizable unsaturated group (hereinafter referred to as other monofunctional radical-polymerized monomer). (Functional monomer) may be blended.

As such other monofunctional radically polymerizable monomer, known polymerizable monomers can be used without any limitation, and specifically, acrylic acid, methacrylic acid, maleic anhydride can be used. Acid, methyl methacrylate, butyl methacrylate, benzyl methacrylate, phenyl methacrylate, biphenyl methacrylate, 2-hydroxyethyl methacrylate, oleyl methacrylate, nerol methacrylate, geraniol methacrylate, linalool methacrylate, farnesol methacrylate, methylthioacrylate, benzylthioacrylate , Benzylthiomethacrylate, diethyl fumarate,
Examples thereof include diphenyl fumarate, styrene, chlorostyrene, methylstyrene, vinylnaphthalene, α-methylstyrene dimer, bromostyrene, divinylbenzene and vinylpyrrolidone. These other monofunctional radically polymerizable monomers may be used in combination of a plurality of types.

In the curable composition of the present invention,
The type and amount of each radically polymerizable monomer may be appropriately selected and blended as necessary, but from the viewpoint of the photochromic property of the cured product and the adhesion to the substrate, the radically polymerizable monomer having an epoxy group is used. In addition to the monomer, it is preferable to use a radical polymerizable monomer having a group capable of generating a silanol group by hydrolysis and a polyfunctional radical polymerizable monomer in combination.

The mixing ratio of the radical polymerizable monomer having an epoxy group is 1 to 50 parts by mass (preferably 1 to 20) in 100 parts by mass of all the polymerizable monomers to be mixed.
1 part to 50 parts by mass (preferably 1 to 20 parts by mass) of a radical-polymerizable monomer having a group that produces a silanol group by hydrolysis, and a polyfunctional radical-polymerizable monomer of 5 to 95 parts by mass. It is preferably 10 parts by mass (preferably 10 to 90 parts by mass).

As the photochromic compound used as the third component in the present invention, known photochromic compounds can be used without any limitation. For example, photochromic compounds such as fulgimide compounds, spirooxazine compounds, and chromene compounds are well known,
In the present invention, these photochromic compounds can be used.

Examples of the above-mentioned fulgimide compound, spirooxazine compound and chromene compound are, for example, JP-A-2-28154, JP-A-62-288830, WO94 / 22850, WO96 / 145.
The compounds described in the specification of No. 96 and the like can be preferably used.

The compounds newly found by the present inventors as compounds having excellent photochromic properties and being patent-pending (JP 2001-114775A, JP 2001-031670A, JP
2001-011067, JP 2001-011066, JP 2000-347346
No. 2000-344762, 2000-344761, 2000
-327676, JP 2000-327675, JP 2000-256347,
JP 2000-229976A, JP 2000-229975A, JP 2000-229A
974, JP 2000-229973, JP 2000-229972, JP 2
000-219687, JP 2000-219686 A, JP 2000-219685 A
No. 11-322739, No. 11-286484, No. 11
-279171, JP-A-10-298176, JP-A-09-218301,
JP 09-124645, JP 08-295690, JP 08-176
No. 139, JP-A 08-157467, etc.) can also be preferably used.

Among these photochromic compounds,
The chromene-based photochromic compound is particularly preferably used because the durability of the photochromic property is higher than that of other photochromic compounds, and the improvement of the coloring density and the fading speed of the photochromic property according to the present invention is particularly large as compared with other photochromic compounds. be able to. Further, among these chromene-based photochromic compounds, compounds having a molecular weight of 540 or more can be suitably used because the color density and the fading speed of the photochromic properties according to the present invention are particularly improved as compared with other chromene-based photochromic compounds.

Examples of the chromene compound that can be preferably used in the present invention include compounds represented by the following general formula (5).

[0063]

[Chemical 7]

{In the formula, R ¹⁴ and R ¹⁵ are each independently the following formula (6):

[0065]

[Chemical 8]

(In the formula, R ¹⁹ is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, and R ²⁰ is a hydrogen atom, an alkyl group, or a halogen atom. Yes, w is an integer of 1 to 3.)
A group represented by the following formula (7)

[0067]

[Chemical 9]

(In the formula, R ²¹ is a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted aromatic heterocyclic group, and w ′ is an integer of 1 to 3.) Or a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or an alkyl group, or R ¹⁴ and R ¹⁵ together form an aliphatic hydrocarbon ring or Constitutes an aromatic hydrocarbon ring, R
¹⁶ and R ¹⁷ are each independently a hydrogen atom, or an alkyl group, an alkoxy group, an aralkoxy group, an amino group, a substituted amino group, a cyano group, a substituted or unsubstituted aromatic hydrocarbon group, a halogen atom, an aralkyl group. , A hydroxy group, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom and the nitrogen atom and a pyran ring are bonded, or a condensation of an aromatic hydrocarbon ring or an aromatic heterocycle condensed to the heterocyclic group It is a substituent selected from the group consisting of heterocyclic groups and has the following formula (8)

[0069]

[Chemical 10]

The group represented by is an aromatic hydrocarbon group or an unsaturated heterocyclic group, and R ¹⁸ which is a substituent of the group.
Is a substituent having the same meaning as R ¹⁶ and R ¹⁷ (provided that R ¹⁸
Is a substituted or unsubstituted heterocyclic group or condensed heterocyclic group having a nitrogen atom as a hetero atom and the nitrogen atom and the pyran ring are bonded, the nitrogen atom is a group represented by the above formula (8). , And u is an integer of 0-6. } The above formula (6), the above formula (7) or the above R
The substituted or unsubstituted aromatic hydrocarbon group for ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is represented by the above general formula (1)
Specific examples are the same as those described as R ¹ in. Specific examples of the unsubstituted aromatic heterocyclic group include a pyridyl group, a furyl group, and the like, and when the substituent is substituted with a substituent, the same substituent as the above aromatic hydrocarbon group is used. It is illustrated.

The alkyl group represented by the above formula (6) or R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group or a propyl group. , Butyl group and the like are specifically exemplified, and the above formula (6) or the above R ¹⁶ and R
Specific examples of the halogen atom in ¹⁷ are a fluorine atom, a chlorine atom and a bromine atom.

The alkoxy group for R ¹⁶ and R ¹⁷ is preferably one having 1 to 10 carbon atoms, and a methoxy group,
Specific examples thereof include an ethoxy group and a butoxy group. Examples of the aralkoxy group include those having 6 to 14 carbon atoms such as phenyloxy group and naphthyloxy group, and examples of the aralkyl group include phenylmethyl group and 2-phenylethyl group. 7 carbons
20 is preferable. Examples of the substituted amino group for R ¹⁶ and R ¹⁷ include those substituted with an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group and a propyl group, and a dimethylamino group and a diethylamino group. .

Specific examples of the more preferred chromene compound of the present invention include the chromene compounds having the following structures.

[0074]

[Chemical 11]

[0075]

[Chemical 12]

[0076]

[Chemical 13]

[0077]

[Chemical 14]

[0078]

[Chemical 15]

[0079]

[Chemical 16]

As for the amount of the photochromic compound compounded in the curable composition of the present invention, the larger the amount, the higher the color density at the time of color formation, while the smaller the amount, the more uniformly dissolved in the radical polymerizable monomer, resulting in uneven color density. Since it is easy to eliminate the occurrence of, and is also advantageous in terms of cost, with respect to 100 parts by mass of all the radical-polymerizable monomers to be blended,
0.001 to 20 parts by mass, preferably 0.005 to 15
Parts by mass, more preferably 0.01 to 10 parts by mass.

The curable composition of the present invention further comprises a surfactant, an antioxidant and a radical scavenger for improving the durability of the photochromic compound, the color development rate, the color fading rate and the moldability. Additives such as agents, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, plasticizers and the like may be added.
As these additives to be added, known compounds are used without any limitation.

For example, as the surface active agent, any of nonionic surface active agents, anionic surface active agents and cationic surface active agents can be used, but it is preferable to use nonionic surface active agents because of their solubility in the polymerizable monomer. Specific examples of the nonionic surfactant that can be preferably used include sorbitan fatty acid ester, glycerin fatty acid ester, decaglycerin fatty acid ester, propylene glycol / pentaerythritol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbit fatty acid ester. ,
Polyoxyethylene glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene phytosterol / phytostanol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene castor oil /
Examples thereof include hydrogenated castor oil, polyoxyethylene lanolin / lanolin alcohol / beeswax derivative, polyoxyethylene alkylamine / fatty acid amide, polyoxyethylene alkylphenyl formaldehyde condensate, and single chain polyoxyethylene alkyl ether. Two or more kinds of surfactants may be mixed and used. The addition amount of the surfactant is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass in total of all the radical-polymerizable monomers.

Further, as antioxidants, radical scavengers, ultraviolet stabilizers, and ultraviolet absorbers, hindered amine light stabilizers, hindered phenol antioxidants, phenolic radical scavengers, sulfur antioxidants, benzotriazoles A system compound, a benzophenone system compound, etc. can be used conveniently. These antioxidants, radical scavengers, UV stabilizers, and UV absorbers may be used as a mixture of two or more kinds. Further, in using these non-polymerizable compounds, a surfactant and an antioxidant, a radical scavenger, an ultraviolet stabilizer and an ultraviolet absorber may be used in combination.
The addition amount of these antioxidants, radical scavengers, UV stabilizers, and UV absorbers is in the range of 0.001 to 20 parts by mass based on 100 parts by mass of all radical-polymerizable monomers. preferable.

The curable composition of the present invention is particularly suitable for use as a photochromic coating material, which is a material that is applied and cured on the surface of an optical material such as an eyeglass lens to form a film having photochromic properties.

As a method for applying the curable composition of the present invention to the surface of a lens, a known method such as spin coating or dip spin coating can be used without limitation. Then, an optical material exhibiting photochromic properties can be obtained by curing by a known method.

The method for curing the curable composition of the present invention is not particularly limited, and a known polymerization method depending on the kind of the monomer used can be adopted. However, whichever method is used, light irradiation (preferably ultraviolet irradiation) is performed in order to decompose the photobase generating compound contained in the composition. Irradiation with light may be performed before or after curing the curable composition, or the light used for curing may be used. When used as a spectacle lens and a coating material for the spectacle lens, each component to be added to the curable composition of the present invention has no absorption in the visible region in order to make the obtained spectacle lens colorless and transparent. Is preferred. Therefore, it is preferable to use ultraviolet light (in particular, a wavelength of 400 nm to 250 nm) as the light for decomposing the photobase generating compound and the light for curing.

As the polymerization initiation means, use can be made of radical polymerization initiators such as various peroxides and azo compounds, photopolymerization initiators such as benzophenone derivatives and acetophenone derivatives, or a combination of both. it can.

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 and lauroyl peroxide. , Acetylperoxide and other diacyl peroxides; t-butylperoxy-2-ethylhexanoate, t-butylperoxydicarbonate, cumylperoxyneodecanate, t-butylperoxybenzoate and other peroxyesters; Percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and di-sec-butyloxy carbonate; 2,2 ′
-Azobisisobutyronitrile, 2,2'-azobis (4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) ) And other azo compounds.

The blending amount of the peroxide or azo compound is
It depends on the polymerization conditions, the type of the initiator, and the type and composition of the curable composition of the present invention and cannot be unconditionally limited, but generally, it is 0. It is preferably used in the range of 01 to 10 parts by mass.

Further, when carrying out photopolymerization using an active energy ray containing ultraviolet rays, the photopolymerization initiator is not particularly limited and known ones can be used without any limitation. Benzoin, benzoin methyl ether, benzoin butyl ether, benzophenol, aetophenone 4,4'-dichlorobenzophenone, diethoxyacetophenone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, benzylmethyl ketal, 1- (4-isopropylphenyl) -2
-Hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-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-benzyl-2-dimethylamino-1- (4-
Morpholinophenyl) -butanone-1 and the like.
These photopolymerization initiators are generally used in the range of 0.001 to 5 parts by mass based on 100 parts by mass of all radical-polymerizable monomers.

The thickness of the coating layer obtained as described above is not particularly limited, but a sufficient coloring density can be obtained even when the concentration of the photochromic compound is low, and the durability of the photochromic property is good. Is preferably relatively thick. On the other hand, however, the thicker the coating layer, the more the initial yellowness increases, so the thickness of the coating layer is preferably 10 to 100 μm, more preferably 20 to 50 μm. To obtain such a thick coating thickness, the viscosity of the curable composition at 25 ° C. is 20 to 500 cp, preferably 50.
˜300 cp, more preferably 60 to 200 cp, it can be easily achieved.

The spectacle lens coated with the photochromic layer thus obtained may be used as it is, but further, a hard coat layer is provided, antireflection treatment, antistatic treatment or the like is performed according to a known method. Is also preferable.

Further, it is of course possible to use the curable composition of the present invention alone as it is to cure it as an optical material such as an eyeglass lens, instead of using it as a coating material.

[0094]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

The abbreviations and names of the compounds used are shown below.・ Photobase generating compound oxime derivative 1

[0096]

[Chemical 17]

Oxime derivative 2

[0098]

[Chemical 18]

Oxime derivative 3

[0100]

[Chemical 19]

Oxime derivative 4

[0102]

[Chemical 20]

Oxime derivative 5

[0104]

[Chemical 21]

Carbamic acid derivative 1

[0106]

[Chemical formula 22]

Carbamic acid derivative 2

[0108]

[Chemical formula 23]

Radical polymerizable monomer GMA: glycidyl methacrylate TMPT: trimethylolpropane trimethacrylate EB1830 (manufactured by Daicel UCB): molecular weight 4
Polyfunctional polyester acrylate of 5000 to 55000 9 GDA: Polyethylene glycol diacrylate of average molecular weight 532 BPE oligo: 2,2-bis (4- of average molecular weight 776)
Acryloyloxy polyethylene glycol phenyl)
Propane BPE: 2,2-bis (4-methacryloyloxyethoxyphenyl) propane TMSiMA: γ-methacryloyloxypropyltrimethoxysilane / photochromic compound chromene 1

[0110]

[Chemical formula 24]

Photoinitiator CGI184: 1-hydroxycyclohexyl phenyl ketone CGI403: bis (2,6-dimethoxybenzoyl-
2,4,4-Trimethyl-pentylphosphine oxide amine compound MDEA: N-methyldiethanolamine DBU: 1,8-diazabicyclo [5,4,0] -7-
Undecene Example 1 TMPT 20 parts by mass, BPE oligo 40 parts by mass, EB1830:
3 parts by mass of chromene 1 and 5 parts by mass of oxime derivative 1 were added to a polymerizable monomer mixture consisting of 15 parts by mass, 15 parts by mass of 9GDA, and 10 parts by mass of GMA (hereinafter, the polymerizable monomer of composition A). And mixed well.

This mixed solution was heated and stirred at 40 ° C. in the dark,
An accelerated test of storage stability was performed. When the suspension did not occur after 12 hours, it was evaluated as ◯, and when it did occur, as ×,
The results are shown in Table 1.

[0113]

[Table 1]

Example 2 Example 1 was repeated except that 5 parts by mass of the carbamic acid derivative 1 was blended in place of the oxime derivative 1 as the photobase generating compound.
The storage stability was evaluated in the same manner as in. The results are shown in Table 1.

Example 3 20 parts by weight of TMPT, 40 parts by weight of BPE, 30 parts by weight of 9GDA, and 10 parts by weight of GMA (3 parts by weight of chromene 1) were added to a polymerizable monomer mixture (hereinafter, polymerizable monomer of composition B). 5 parts by mass of the oxime derivative 2 was added and mixed sufficiently, and the storage stability was evaluated in the same manner as in Example 1 using this. The results are shown in Table 1.

Example 4 Example 3 was repeated except that 5 parts by mass of carbamic acid derivative 2 was blended in place of oxime derivative 2 as the photobase generating compound.
A mixed solution was prepared in the same manner as above, and the storage stability was evaluated.
The results are shown in Table 1.

Comparative Examples 1 to 3 The amine compounds shown in Table 3 were used in place of the photobase generating compound.
The storage stability was evaluated in the same manner as in Example 1 using parts by mass. The composition of the polymerizable monomer used, the amine compound, and the evaluation results are shown in Table 1.

Example 5 5 parts by mass of a silyl monomer, TMSiMA, 3 parts by mass of chromene 1 as a photochromic compound, and 5 parts by mass of oxime derivative 1 as a photobase generating compound, were added to the polymerizable monomer of the composition A. , CGI as a polymerization initiator
0.4 parts by mass of 184 and 0.1 parts by mass of CGI403 were added and mixed sufficiently to obtain a solution. The storage stability of this solution was evaluated in the same manner as in Example 1.

Approximately 2 g of this solution was applied to a surface of a plastic lens (CR39) having a thickness of 2 mm using a spin coater 1H-DX2 manufactured by MIKASA and the rotation speed was 50 r.
Spin coating was performed under the conditions of 40 seconds for pm → 200 rpm for 2 seconds → 400 rpm for 1 second. Then, the coating film was cured by irradiation in a nitrogen gas atmosphere for 3 minutes using an electrodeless lamp with an output of 120 / cm. Then, it was further heated at 120 ° C. for 2 hours. The plastic lens used was subjected to atmospheric pressure plasma treatment using ST-7000 manufactured by Keyence Corporation before coating, washed with water, and then dried to have its surface modified.

A lens having the obtained photochromic coating layer was used as a sample, and a xenon lamp L-2480 (300 W) SHL-100 manufactured by Hamamatsu Photonics was placed on the sample 20 through an aeromas filter (manufactured by Corning).
C. ± .1 ° C., beam intensity on polymer surface 365 nm = 2.
4 mW / cm ² , 245 nm = 24 μW / cm ² 12
The sample was irradiated for 0 seconds to develop a color, and the photochromic property of the sample was measured. Each photochromic property was evaluated by the following method, and the results are shown in Table 2.

Maximum absorption wavelength (λmax): Co., Ltd.
It is the maximum absorption wavelength after color development determined by a spectrophotometer manufactured by Otsuka Electronics Co., Ltd. (instantaneous multi-channel photo detector MCPD1000). The maximum absorption wavelength is related to the color tone during color development.

Color density {ε (120) −ε
(0)}: The difference between the absorbance {ε (120)} after 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 property.

Discoloration speed [t1 / 2 (min.)]: 12
When the light irradiation is stopped after 0 seconds of light irradiation, the absorbance of the sample at the maximum wavelength is {ε (120) −ε (0)}.
The time required to drop to 1/2. It can be said that the shorter the time, the better the photochromic property.

Adhesion test: 100 mm 1 mm × 1 mm squares were formed on the surface of the sample with a cutter knife having a sharp tip.
After individual pieces are attached, a commercially available cellophane tape is attached, and then, when there is no peeling due to the peeling state of the coat film when quickly peeled off, those that are not peeled at all are indicated as ○, those that are partially peeled off are indicated as △, and those that were all peeled off are indicated as ×. did.

Coloring Degree (YI): The color difference was measured with a color difference meter (SM-4 type) manufactured by Suga Test Instruments Co., Ltd., and the coloring degree was indicated by a YI value.

[0126]

[Table 2]

The photobase generating compounds and polymerizable monomer mixtures used in Examples 6 to 19 and Comparative Examples 4 to 6 are shown in Table 4.
A curable composition was prepared in the same manner as in Example 5 except that the above was changed, and a photochromic cured product was obtained using this, and the physical properties thereof were evaluated. The results are shown in Table 2.

As is clear from the results of the above Examples and Comparative Examples, the curable composition of the present invention containing a photobase generating compound in place of the amine compound has good storage stability even when stored as a single solution. Showed sex. Further, it showed the same adhesion to the substrate as when the amine compound was used (Comparative Example 6).

On the other hand, the curable composition containing neither the amine compound nor the photobase generating compound showed no adhesiveness to the substrate.

[0130]

By using the photobase generating compound as a constituent of the curable composition of the present invention, it becomes possible to obtain various physical properties equivalent to those obtained when an amine compound is used.
Moreover, unlike the case where an amine compound is used, it is possible to obtain excellent storage stability even when stored in one solution.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G02C 7/10 C09D 5/00 Z // C09D 5/00 G02B 1/10 Z F term (reference) 2H006 BE02 BE05 2H048 DA01 DA04 DA09 DA24 2K009 BB11 CC33 CC47 DD02 DD05 DD06 EE01 4J011 PA35 PA43 PA44 PB40 PC02 PC08 QA02 QA03 QA08 QA09 QA12 QA13 QA23 QA24 QA25 FA61 QA37 QA34 Q46 QA37 QA37 QA37 QA37 QA37 QA37 QA37 QA37 QA37 QA37 QA37 QA37 QA37 QA38 GA07 JA56 JA73 JB18 JB23 JB30 JB39 NA12 PA17

Claims (2)

[Claims] 1. A photochromic compound comprising (A) a photobase generating compound (B) a radically polymerizable monomer containing a radically polymerizable monomer having an epoxy group (C) a photochromic compound. Curable composition. 2. A photochromic optical material obtained by coating at least one surface of a substrate with the cured product of the photochromic curable composition according to claim 1.