JP2755537B2 - Polymerizable 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 polymerizable composition to be used as a raw material for a photochromic molded article having excellent photochromic durability.

[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 light such as sunlight or light from a mercury lamp, the color changes rapidly, and light irradiation is performed. It is a reversible action that returns to the original color when it is stopped and placed in a dark place. A compound having this property is called a photochromic compound, and various compounds have been conventionally synthesized, but no special common skeleton is recognized in the structure thereof. For example, Japanese Patent Application Laid-Open No. 2-69471
JP, JP-A-3-11074 and JP-A-3-11074
Japanese Patent No. 11075 discloses a chromene compound having a chromene skeleton.
No. 4 discloses a fulgide compound having a fulgide skeleton or a fulgimide compound obtained by reacting the fulgide compound with an amine.

[0003]

These photochromic compounds exhibit excellent photochromic properties, but have a so-called photochromic durability in which the color density gradually decreases when color development and decoloration are repeated. There was a problem. In order to put photochromic compounds into practical use for applications such as sunglasses, it is necessary to improve the durability of photochromic properties.

[0004]

Means for Solving the Problems Accordingly, the present inventors have:
Intensive research was conducted to improve the durability of photochromic compounds. As a result, a photochromic compound and a basic nitrogen-containing compound having a polymerizable group were combined to form a composition, and a photochromic molded article obtained by polymerizing the composition was found to be a molded article that solved the above-described problems. I came to the proposal.

That is, the present invention provides a) a chromene compound,
At least one photochromic compound 10 selected from the group consisting of fulgide compounds and fulgimide compounds
0 parts by weight, and b) an amino group-containing or substituted amino group-containing compound having a polymerizable group.
It is a polymerizable composition comprising parts by weight.

[0006] One component of the polymerizable composition of the present invention is at least one photochromic compound selected from the group consisting of chromene compounds, fulgide compounds and fulgimide compounds. The chromene compound, the fulgide compound, and the fulgimide compound each have a chromene skeleton and a fulgide skeleton, and a known compound exhibiting photochromic properties can be used without any limitation. For example, JP-A-2-28154, JP-A-2-69471, JP-A-3-11074, and JP-A-3-11
Compounds known in, for example, JP-A No. 075 can be suitably used. The fulgide compound, fulgimide compound, and chromene compound that can be suitably used in the present invention can be represented by the following formulas (1) and (2) when represented by a general formula.

[0007]

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[However,

[0009]

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Is a divalent aromatic hydrocarbon group or a divalent saturated heterocyclic group, each of which may have a substituent;
₁ is a monovalent hydrocarbon group or a monovalent heterocyclic group which may have a substituent,

[0011]

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Is a norbornylidene group or an adamantylidene group, each of which may have a substituent;
Represents an oxygen atom, a group> N-R _2, group> N-A ₁ -B ₁ -
(A ₂ ) _m- (B ₂ ) _n -R ₃ , group> NA ₃ -A ₄ , or group> NA ₃ -R ₄ , wherein R ₂ is a hydrogen atom, an alkyl A ₁ , A ₂ and A ₃ are the same or different and are an alkylene group, an alkylidene group, a cycloalkylene group or an alkylcycloalkane-diyl group, and B ₁ and B ₂ are the same or different ,

[0013]

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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 each of which may have a substituent, A ₄ is a naphthyl group which may have a substituent, and R ₄ is a halogen atom, a cyano group. Group or a nitro group. )]

[0015]

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Wherein R ₁ , R ₂ , R ₃ and R ₄ are the same or different hydrogen atoms, hydrocarbon groups, substituted amino groups or saturated heterocyclic groups, and R ₃ and R ₄ are taken together May form a ring,

[0017]

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Is an optionally substituted aromatic hydrocarbon group or unsaturated heterocyclic group. Among the photochromic compounds represented by the above formulas, considering the durability of the photochromic action and the like, among the fulgide compounds or fulgimide compounds, the general formula (1)
In R ₁ is an alkyl group, X is> N-R (R is a cyanoalkyl group, a nitro group, an alkoxycarbonylalkyl group.), And

[0019]

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Is an adamantylidene group,

[0021]

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Is preferably an optionally substituted heterocyclic group, particularly a compound having a thiophene ring.

In the chromene compound, R ₁ and R ₂ in the general formula (2) are both hydrogen atoms,
₃ and R ₄ are each an alkyl group or, together, a bicyclo [3.3.1] 9-nonylidene group or a norbornylidene group;

[0024]

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Is preferably a compound which is an optionally substituted naphthalene ring.

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

Flugimide compound: 1) N-cyanomethyl-6,7-dihydro-4-methyl-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.1.
^13.7 ] decane) 2) N-cyanomethyl-6,7-dihydro-2- (p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^3.7] decane) 3) N-cyanomethyl-6,7-dihydro - 4- methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^3.7] decane) 4) 6,7-dihydro -N- methoxycarbonyl methylspiro ( 5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^3.7]
Decane) 5) 6,7-dihydro-4-methyl-2-methoxycarbonylmethyl-spiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3.
1.1 ^3.7 ] 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) 4'-methylspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [f] chromene] 4) 3'-methylspiro [norbornane- 2,2- [2
H] benzo [f] chromene 5) 2,2-dimethyl-7-octoxy [2H] benzo [f] chromene The other component of the polymerizable composition of the present invention is a basic nitrogen-containing compound having a polymerizable group. It is. Adding a basic nitrogen-containing compound having no polymerizable group is also effective in improving the durability of photochromic properties.However, when it is mixed with a monomer and then polymerized to form a molded product, problems such as bleed out occur. Is not preferred. Further, when an attempt is made to add a large amount of a basic nitrogen-containing compound having no polymerizable group, a problem such as polymerization of the monomer occurs. However, in the case of a basic nitrogen-containing compound having a polymerizable group, elution due to bleed-out can be prevented since the basic nitrogen-containing compound is fixed to the matrix. Also, by using it as a component of the matrix, a larger amount can be added than when a compound having no polymerizable group is added. Such a basic nitrogen-containing compound is a compound having a polymerizable group and a basic nitrogen-containing group in one molecule. As the polymerizable group, a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, or the like is preferable, and as the nitrogen-containing group showing basicity, an amino group, an imino group, or an alkyl group, an alkoxy group, Preferred are a substituted amino group, a substituted imino group and the like substituted by an alkyl group, a phenyl group and the like.

The basic nitrogen-containing compound having a polymerizable group which can be suitably used as described above is represented by the following general formula.

[0029]

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(Where R ¹⁰ is a hydrogen atom or a methyl group, R ¹¹ and R ¹² are a hydrogen atom or an alkyl group or an alkoxyalkyl group, R ¹³ is an alkylene group, and n is 0 or In the above formula, the number of carbon atoms of the alkyl group, the alkylene group and the alkoxyalkyl group is not particularly limited, but usually, the carbon number of the alkyl group, the alkyl group and the alkylene group contained in the alkylene group and the alkoxyalkyl group. The number is preferably in the range of 1 to 10 from the viewpoint of polymerizability.

Specific examples of the basic nitrogen-containing compound having a polymerizable group that can be suitably used in the present invention include:
Among them, 2- (N-methylamino) ethyl acrylate, 2- (N-methylamino) ethyl methacrylate, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate , 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 3- (N, N-diethylamino) propyl acrylate, 3- (N, N-diethylamino) propyl methacrylate Compounds in which n is 1 in the above formula are preferred.

The mixing ratio of the photochromic compound and the basic nitrogen-containing compound having a polymerizable group is such that the basic nitrogen-containing compound having a polymerizable group is present in an amount of 0.01 to 10,000 parts by weight based on 100 parts by weight of the photochromic compound. Range. The amount of the basic nitrogen-containing compound having a polymerizable group is 0.
When the amount is less than 01 parts by weight, the effect of improving the photochromic repetition durability is hardly recognized, and
When the amount exceeds 0 parts by weight, it depends on the application, but when used for optical applications such as lenses, the optical and mechanical properties of the polymer obtained by polymerizing the polymerizable composition of the present invention are considered. Not preferred. In particular, from the viewpoint of the photochromic property of the polymerizable composition obtained, the amount of the basic nitrogen-containing compound having a polymerizable group is preferably in the range of 50 to 5,000 parts by weight.

In the polymerizable composition of the present invention, the durability of the photochromic compound can be sufficiently improved by simply mixing the above two components. Further, when producing a molded article by polymerizing the polymerizable composition of the present invention,
By using other polymerizable monomers in combination, a molded article having desired physical properties can be obtained. As such another polymerizable monomer, any one can be used as long as it can be copolymerized with the basic nitrogen-containing compound having a polymerizable group described above, but it is easy to control the polymerization and select the monomer. In particular, a monomer having a radical polymerizable functional group is preferable because it can be introduced into a polymer in an arbitrary state.

Examples of such a monomer include an acrylate monomer, a methacrylate monomer, a vinyl monomer and an allyl monomer. Specific examples thereof include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol bisglycidyl methacrylate, bisphenol A dimethacrylate, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, and 2,3-bis (3,5
-Dibromo-4-methacryloyloxyethoxyphenyl) propane and other polyacrylic acid and polymethacrylic acid ester monomers; diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diallyl tartrate, diallyl epoxysuccinate, diallyl hexaphthalate, diallyl carbonate, Polyvalent allyl monomers such as allyl diglycol carbonate and trimethylolpropane triallyl carbonate; 1,2-bis (methacryloylthio) ethane, bis (2-acryloylthioethyl) ether and 1,4-bis (methacryloylthiomethyl) benzene Thioacrylic acid and polythiomethacrylate monomers such as divinylbenzene; radically polymerizable polyfunctional monomers such as divinylbenzene; acrylic acid, methacrylic acid, maleic anhydride, Methyl acrylate, methyl methacrylate, benzyl methacrylate, glycidyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, diethyl fumarate, diphenyl fumarate, methyl thioacrylate, styrene, chlorostyrene, methyl styrene, vinyl naphthalene, bromostyrene , Acrylonitrile, methacrylonitrile, methyl vinyl ketone, butadiene, vinylidene chloride and the like. The above monomers can be used alone or in combination of two or more.

Preferred monomers from the viewpoint of imparting a high glass transition point include vinylcarbazole and N-substituted maleimide. When used as an optical material such as a lens, the monomer capable of improving the glass transition point is 1% of the total monomer when used as an optical material such as a lens.
Preferably, it is used in the range of 50 to 50% by weight.

The polymerization of the polymerizable composition of the present invention can be carried out by a known method. For example, various radical initiators, for example, peroxides such as benzoyl peroxide, pyrolytic radical initiators such as azo compounds such as azobisisobutyronitrile, and photolytic radical initiators such as benzophenone. It can be performed using: Furthermore, polymerization can be performed by irradiating ionizing radiation, for example, an electron beam or X-ray, without using a radical initiator.

The durability of the photochromic property can be further improved by adding an ultraviolet stabilizer to the polymerizable composition of the present invention. As the UV stabilizer, a known UV stabilizer added to various plastics can be used without any limitation.

In the present invention, considering the durability of the photochromic compound, among various ultraviolet stabilizers,
Singlet oxygen quenchers, hindered amine light stabilizers, hindered phenol antioxidants, and sulfur-based antioxidants are preferably used. More specific examples of these ultraviolet stabilizers include Sheasorb UV1084 and Sheasorb 334.
6, UV-Cek AM101, UV-Cek AM105 (Ferro Corporation), Irgas Tab 2002, Tinuvin 765, Tinuvin 144, Chimassorb 944, Tinuvin 622, Irganox 1010, Irganox 2
45 (all made by Ciba-Geigy), Rilex NBC
(Manufactured by DuPont), SANOL LS-744, SANOL L
S-1114, SANOL LS-26268 (all manufactured by Sankyo), Sumilizer GA-80, Sumilizer GM,
Sumilizer BBM-S, Sumilizer WX-R, Sumilizer S, Sumilizer BHT, Sumilizer TP-
D, Sumilizer TPL-R, Sumilizer TPS, Sumilizer MB (all manufactured by Sumitomo Chemical Co., Ltd.), Mark AO-
50, mark AO-20, mark AO-30, mark A
O-330, mark AO-23 (all manufactured by Asahi Denka Co., Ltd.),
Antioxidant HPM-12 (manufactured by SFP) and the like. Each of the above names is a trade name.

[0039]

According to the present invention, the durability of a photochromic compound can be improved by combining a photochromic compound with a basic nitrogen-containing compound having a polymerizable group. In addition, in the molded article obtained by polymerizing the polymerizable composition of the present invention, the basic nitrogen-containing compound having a polymerizable group, which is a component for improving the durability of the photochromic compound, is polymerized. It does not bleed out to the body surface and does not deteriorate the surface properties of the molded body.

Therefore, the polymerizable composition of the present invention can be applied to a wide range of fields, for example, various recording memory materials, copying materials, photoreceptors for printing, recording materials for cathode ray tubes, recording materials for lasers, and photosensitive materials for laser instead of silver photosensitive materials. It can be used as various recording materials such as materials. In addition, the polymerizable composition of the present invention can be used as a material for photochromic lens materials, optical filter materials, display materials, light meters, decorations, and the like.

[0041]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. “Parts” in the examples is “parts by weight”.

Flugimide compound (1): 1) N-cyanomethyl-6,7-dihydro-4-methyl-phenylspiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3 1.1.
1 ^3.7] decane) fulgimide compound (2): 2) N-cyanomethyl-6,7-dihydro-2-(p-
Methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^3.7] decane) fulgimide compound (3): 3) N-cyanomethyl - 6,7-dihydro-4-methylspiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^3.7] decane) fulgimide compound (4): 4) 6, 7-dihydro -N- methoxycarbonylmethyl - spiro (5,6-benzo [b] thiophene-dicarboximide -7,2- tricyclo [3.3.1.1 ^3.7]
Decane) Flugimide compound (5): 5) 6,7-dihydro-4-methyl-2-methoxycarbonylmethyl-spiro (5,6-benzo [b] thiophendicarboximide-7,2-tricyclo [3.3 .
1.1 ^3.7 ] decane) Chromene compound (1): 1) Spiro [norbornane-2,2 '-[2H] benzo [h] chromene] Chromene compound (2): 2) Spiro [bicyclo [3.3.1] Nonan-9,2 '
-[2H] benzo [f] chromene] Chromene compound (3): 3) 4'-Methylspiro [bicyclo [3.3.1] nonane-9,2 '-[2H] benzo [f] chromene] Chromene compound ( 4): 4) 3'-methylspiro [norbornane-2,2- [2
H] Benzo [f] chromene] Chromene compound (5): 5) 2,2-dimethyl-7-octoxy [2H] benzo [f] chromene Examples 1 to 7 Flugimide compound (1) in 100 parts of methyl methacrylate. 2 parts and 0.2 part of a basic nitrogen-containing compound having a polymerizable group shown in Table 1 were added, and 1 part of perbutyl ND as a radical polymerization initiator was further added and mixed well. This mixed solution was poured into a mold composed of a glass plate and a gasket composed of an ethylene-vinyl acetate copolymer, and cast polymerization was performed. The polymerization was carried out in an air oven at 30
The temperature was gradually increased from 18 ° C. to 90 ° C. over 18 hours, and kept at 90 ° C. for 2 hours. After completion of the polymerization, the mold was taken out of the air furnace, and allowed to cool, and then a polymer having a thickness of 2 mm was removed from the glass of the mold. The obtained molded product is used as a xenon long life fade meter FA manufactured by Suga Test Instruments Co., Ltd.
The fatigue life was measured by L-15AX-HC.

The fatigue life (T _1/2 ) was represented by the time required for the absorbance at the maximum absorption wavelength based on the fulgimide compound to fall to half of the initial (T ₀ ) absorbance. However, the absorbance at T ₀ and T _1/2 is a value obtained by subtracting the absorbance of the unirradiated molded article at the maximum absorption wavelength based on the fulgimide compound, and the absorbance at T ₀ was measured 60 seconds after light irradiation. . As the evaluation of bleed-out, the surface of the obtained molded article was wiped with acetone, and did not become cloudy, and no bleed-out was observed. The results are shown in Table 1.

[0044]

Comparative Example 1 The procedure of Example 1 was repeated, except that the basic nitrogen-containing compound having a polymerizable group was not used.
The results are shown in Table 1.

[0046]

[0047]

[Table 1]

[0048]

Examples 8 to 14 The procedure of Example 1 was repeated, except that the basic nitrogen-containing compound having a polymerizable group shown in Table 2 was used. No bleed-out was observed. The results are shown in Table 2.

[0050]

[0051]

[0052]

[Table 2]

Examples 15 to 19 The same procedures as in Example 3 were carried out except that the mixing ratio of the basic nitrogen-containing compound having a polymerizable group was changed. No bleed-out was observed.
The results are shown in Table 3.

[0054]

[Table 3]

Examples 20 to 24 The same procedures as in Example 10 were carried out except that the mixing ratio of the basic nitrogen-containing compound having a polymerizable group was changed. No bleed-out was observed. The results are shown in Table 4.

[0056]

[Table 4]

Examples 25 to 28 The procedures were performed in the same manner as in Example 3 except that the flugimide compound in Example 3 was changed to the compound shown in Table 5. No bleed-out was observed. Table 5 shows the results
It was shown to.

[0058]

[Table 5]

Examples 29 to 32 The same procedures as in Example 10 were carried out except that the chromene compound in Example 10 was changed to the compounds shown in Table 6. No bleed-out was observed. The results are shown in Table 6.

[0060]

[Table 6]

Claims (1)

(57) [Claims] 1. a) 100 parts by weight of at least one photochromic compound selected from the group consisting of a chromene compound, a fulgide compound and a fulgimide compound; and b) a compound containing an amino group or a substituted amino group having a polymerizable group. 0.11 to 10000 parts by weight of a polymerizable composition.