JP3537476B2 - 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 comprising a spiropyran-based compound or a spirooxazine-based compound, a hindered amine compound and a specific organic phosphite compound having excellent light resistance. It is.

[0002]

2. Description of the Related Art A photochromic substance is a substance that repeats color development / decoloration or discoloration depending on the presence or absence of light irradiation or the difference in the wavelength of light. In recent years, optical recording materials, copying materials,
It is expected to be used in a wide range of applications such as printing photoreceptors, photosensitive materials for lasers, masking materials, light control materials for automobiles, aircraft, and construction materials, printing materials, toys, and cosmetics.

[0003] Spiropyran compounds and spirooxazine compounds are known as excellent photochromic materials because they are particularly excellent in color-forming sensitivity and color-forming density. However, these organic photochromic materials themselves have extremely low stability to light, and emit light intermittently due to repetition of color-decoloration,
Alternatively, there is a disadvantage that the light is continuously decomposed in a short period of time by light irradiation.

To solve this problem, for example, Japanese Patent Application Laid-Open
JP-A-241383 and JP-A-63-33490 propose to use a hindered amine compound in combination to improve the light fastness of a spirooxazine compound, and JP-A-3-66790 discloses piperidyl. It has been proposed to introduce light-stabilizing functional groups such as groups, antioxidant functional groups, singlet oxygen deactivating functional groups and triplet quenching functional groups into spirooxazine-based compounds, but still satisfactory performance Has not been obtained. Further, Japanese Patent Application Laid-Open
No. 2,340,084 discloses that, in addition to a hindered amine compound, a phosphite-based antioxidant and the like can be used in combination in order to improve the light resistance of the spirooxazine-based compound. When used in combination, the combined effect is extremely small.

Accordingly, an object of the present invention is to provide a photochromic composition which is remarkably excellent in light resistance and can withstand intermittent light irradiation or continuous light irradiation by a coloring-quenching cycle.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a hindered amine compound and a specific organic phosphite compound are added to a spiropyran compound or a spirooxazine compound in combination. It has been found that the photochromic composition thus obtained can achieve the above object, and has reached the present invention.

That is, the present invention provides at least one of a spiropyran compound or a spirooxazine compound, at least one hindered amine compound and a compound represented by the following general formula (I) or (I):
It is intended to provide a photochromic composition comprising at least one of the organic phosphite compounds represented by I).

[0008]

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Hereinafter, the photochromic composition of the present invention will be described in detail.

The spiropyran-based compound and spirooxazine-based compound used in the present invention are preferably compounds represented by the following general formula (III).

[0011]

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Accordingly, as the spiropyran-based compound, for example, 1 ′, 3 ′, 3′-trimethylspiro (2
H-1-benzopyran-2,2'-indoline),
1 ′, 3 ′, 3′-Trimethyl-6-nitrospiro (2
H-1-benzopyran-2,2'-indoline),
1 ′, 3 ′, 3′-trimethyl-6-hydroxyspiro (2H-1-benzopyran-2,2′-indoline),
1 ′, 3 ′, 3′-trimethyl-8-methoxyspiro (2H-1-benzopyran-2,2′-indoline),
5'-chloro-1 ', 3', 3'-trimethyl-6-nitrospiro (2H-1-benzopyran-2,2'-indoline), 6,8-dibromo-1 ', 3', 3'-trimethyl Spiro (2H-1-benzopyran-2,2'-indoline), 8-ethoxy-1 ', 3', 3 ', 4',
7'-pentamethylspiro (2H-1-benzopyran-
2,2′-indoline), 5′-chloro-1 ′, 3 ′,
3'-trimethyl-6,8-dinitrospiro (2H-1
-Benzopyran-2,2'-indoline), 1,3,3
-Triphenylspiro [indoline-2,3 '-(3
H) naphtho (2,1-b) pyran], 1- (2,3,
4,5,6-pentamethylbenzyl) -3,3-dimethylspiro [indoline-2,3 ′-(3H) naphtho (2,1-b) pyran], 1- (2-methoxy-5-nitrobenzyl) ) -3,3-Dimethylspiro [indoline-2,3 ′-(3H) naphtho (2,1-b) pyran],
1- (2-nitrobenzyl) -3,3-dimethylspiro [indoline-2,3 ′-(3H) naphtho (2,1-
b) Pyran], 1- (2-naphthylmethyl) -3,3-
Dimethyl spiro [indoline-2,3 '-(3H) naphtho (2,1-b) pyran] and the like.

The spirooxazine compounds include, for example, 1,3,3-trimethylspiro [indoline-2,3 '-(3H) naphtho (2,1-b) (1,
4) -oxazine], 5-methoxy-1,3,3-trimethylspiro [indoline-2,3 ′-(3H) naphtho (2,1-b) (1,4) -oxazine], 5-chloro- 1,3,3-trimethylspiro [indoline-2,
3 ′-(3H) naphtho (2,1-b) (1,4) -oxazine], 4,7-diethoxy-1,3,3-trimethylspiro [indoline-2,3 ′-(3H) naphtho ( 2,1-b) (1,4) -oxazine], 5-chloro-1-butyl-3,3-dimethylspiro [indoline-
2,3 '-(3H) naphtho (2,1-b) (1,4)-
Oxazine], 1,3,3,5-tetramethyl-9'-
Ethoxyspiro [indoline-2,3 '-(3H) naphtho (2,1-b) (1,4) -oxazine], 1-benzyl-3,3-dimethylspiro [indoline-2,3'
-(3H) naphtho (2,1-b) (1,4) -oxazine], 1- (4-methoxybenzyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) naphtho (2 , 1-b) (1,4) -oxazine], 1- (2-
Methylbenzyl) -3,3-dimethylspiro [indoline-2,3 ′-(3H) naphtho (2,1-b) (1,
4) -oxazine], 1- (3,5-dimethylbenzyl) -3,3-dimethylspiro [indoline-2,3 ′
-(3H) naphtho (2,1-b) (1,4) -oxazine], 1- (4-chlorobenzyl) -3,3-dimethylspiro [indoline-2,3 '-(3H) naphtho (2 ,
1-b) (1,4) -oxazine], 1- (4-bromobenzyl) -3,3-dimethylspiro [indoline-
2,3 '-(3H) naphtho (2,1-b) (1,4)-
Oxazine], 1- (2-fluorobenzyl) -3,3
-Dimethylspiro [indoline-2,3 '-(3H) naphtho (2,1-b) (1,4) -oxazine], 1,
3,5,6-tetramethyl-3-ethylspiro [indoline-2,3 '-(3H) pyrido (3,2-f) (1,
4) -oxazine] and 1,3,3,5,6-pentamethylspiro [indoline-2,3 ′-(3H) pyrido (3,2-f) (1,4) -oxazine]. .

The hindered amine compound used in the present invention is a compound having a 2,2,6,6-tetramethylpiperidyl group in the molecule. Examples of the hindered amine compound include 2,2,6,6 -Tetramethyl-
4-piperidyl benzoate, N- (2,2,6,6-
Tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6
-Tetramethyl-4-piperidyl- (3,5-ditert-butyl-4-hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2 2,6,6-pentamethyl-
4-piperidyl) sebacate, bis (1,2,2,6,
6-pentamethyl-4-piperidyl) -2-butyl-2
-(3,5-di-tert-butyl-4-hydroxybenzyl)
Malonate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, Tetra (1, 2,
2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2 2,6,6-pentamethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl- 4-piperidyloxycarbonyloxy) butylcarbonyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,
1-dimethyl-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy)
Butylcarbonyloxydiethyl] -2,4,8,10
-Tetraoxaspiro [5.5] undecane, 1,5
8,12-tetrakis [4,6-bis {N- (2,2,
6,6-tetramethyl-4-piperidyl) butylamino {-1,3,5-triazin-2-yl] -1,5.
8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino-4,6-dichloro -S-triazine / N, N '
-Bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine / And dibromoethane condensates.

The amount of the hindered amine compound used is
Usually, the amount is from 1 to 10,000 parts by weight, preferably from 5 to 5,000 parts by weight, per 100 parts by weight of the spiropyran-based compound or spirooxazine-based compound. When the amount is less than 1 part by weight, little effect is observed.
Even if it is used in excess of 0000 parts by weight, its effect is not increased, and there is a possibility that coloring may occur or adverse effects such as inhibition of the color-decoloring mechanism may be exerted.

In the organic phosphite compound represented by the general formula (I) or (II) used in the present invention, in the general formula (I), the alkyl group represented by R ₁ is Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, decyl, undecyl, dodecyl, Groups such as tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and methoxycarbonylethyl; and the alkylphenyl group includes a phenyl group substituted with 1 to 3 alkyl groups. . In the above general formula (II), R ₂ , R ₃
Examples of the alkyl group represented by R ₄ include the alkyl group represented by R ₁ , and examples of the alcohol that provides the alcohol residue represented by A include methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, n-pentanol,
Isopentanol, tert-pentanol, n-hexanol, tert-hexanol, n-heptanol, isoheptanol, tert-heptanol, n-
Octanol, 2-ethylhexanol, tert-octanol, n-nonyl alcohol, isononyl alcohol, tert-nonyl alcohol, n-decanol,
Monoalcohols such as isodecanol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3 , 9-bis [1,
1-dimethyl-2-hydroxyethyl) -2,4,8,
Glycols such as 10-tetraoxaspiro [5.5] undecane, and other triols such as triisopropanolamine and trimethylolpropane.

Accordingly, examples of the organic phosphite compound represented by the general formula (I) used in the present invention include, for example, compounds Nos. 1 to N of the following [Chemical Formula 4] to [Chemical Formula 9].
o.6 and the like.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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The above general formula (I) used in the present invention
As the organic phosphite compound represented by I),
For example, compounds Nos. 7 to N of the following [Chemical Formula 10] to [Chemical Formula 19]
o.16 and the like.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The amount of the organic phosphite compound to be used is generally 1 to 10000 parts by weight, preferably 5 to 5000 parts by weight, per 100 parts by weight of the spiropyran compound or the spirooxazine compound. When the amount is less than 1 part by weight, the effect is hardly observed, and when the amount is more than 10,000 parts by weight, the effect is not increased, and the coloring or the color-decoloring mechanism is inhibited. It is not preferable because it may adversely affect the operation.

The photochromic composition of the present invention may be used as a photochromic film by forming a film dispersed or dissolved in a suitable binder resin on a support, or coated as a fine powder on the support, or , Coated with resin and used as microcapsules.

As a specific method for forming the photochromic film, for example, the above spiropyran-based compound or spirooxazine-based compound, a hindered amine compound and an organic phosphite compound are dissolved in an appropriate solvent, and a binder resin is added thereto. Add and stir. This mixed solution is applied to a support by a casting method, a spin coating method, a dipping method, a spraying method or the like, and the solvent is dried to form a film.

Examples of the solvent include methanol,
Examples thereof include alcohols such as ethanol, esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl ethyl ketone, and aromatic hydrocarbons such as toluene.

Examples of the binder resin include poly (methyl meth) acrylate, polystyrene, polyvinyl acetate, polyvinyl butyral, cellulose acetate, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, polyacrylonitrile, urethane resin, and epoxy resin. Resins, phenol resins, phenoxy resins, polyesters and the like can be mentioned.

Examples of the substance serving as the support include:
Examples thereof include polymethyl (meth) acrylate, polyester, polyimide, cellulose acetate, polycarbonate, ordinary paper, baryta paper, glass, and metal.

Further, as a specific method for producing the above microcapsules, for example, the following methods and the like can be mentioned. That is, the above spiropyran-based compound or spirooxazine-based compound, a hindered amine compound and an organic phosphite compound are heated and melted to obtain an oil. This is put into a water or organic solvent containing a surfactant, a protective colloid, a pH adjuster, an electrolyte, etc., as required, together with the film-forming substance, and stirred and emulsified, and an interfacial polymerization method, an in-site polymerization method, Microcapsules are obtained by a known encapsulation method such as a coacervation method.

Examples of the film-forming resin include polyurea, polyamide, polyester, urethane resin, epoxy resin, urea resin, melamine resin, gelatin, ethyl cellulose, polythrene, polyvinyl acetate and the like.

The microcapsules obtained by the above-mentioned preparation method are dispersed uniformly in various ink vehicles or paint vehicles to form photochromic inks or photochromic paints, or are uniformly dispersed in plastics to form molded articles. And can be used in the same applications as other ordinary pigments.

The photochromic film or microcapsule contains a plasticizer, a phenolic antioxidant, a sulfuric antioxidant, an ultraviolet absorber, a singlet oxygen quencher, an infrared absorber, a fat, a wax, and the like. be able to.

Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, triethylene glycol diacetate, dioctyl adipate, ethylene glycol, propylene glycol, glycerin and the like.

Examples of the phenolic antioxidants include 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-p-cresol.
Diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, thiodiethylene glycol bis [(3,5-di-tert-butyl-
4-hydroxyphenyl) propionate], 1,6-
Hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butyl) Tributylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butylic acid]
Glycol ester, 4,4'-butylidenebis (6-
Tert-butyl-m-cresol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 2,2′-
Ethylidenebis (4-sec-butyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-
Tertiary butyl-4-methyl-6- (2-hydroxy-3-
Tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-
Hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-
(Hydroxybenzyl) isocyanurate, 1,3,5-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-
Tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate,
Tetrakis [methylene-3- (3,5-di-tert-butyl-
4-hydroxyphenyl) propionate] methane, 2
-Tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-−２ (3-tert-butyl Butyl-4-hydroxy-5-methylphenyl) propionyloxydiethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy) −5-
Methylphenyl) propionate].

Examples of the sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl and distearyl, and polyols such as pentaerythritol tetra (β-dodecylmercaptopropionate). Β-alkyl mercaptopropionates and the like.

As the above-mentioned ultraviolet absorber, for example, 2-
(2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-
3,5-di-tert-butylphenyl) benzotriazole,
2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-
Chlorobenzotriazole, 2- (2-hydroxy-
3,5-dicumylphenyl) benzotriazole, 2,
2- (2-hydroxyphenyl) benzotriazoles such as 2′-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxybenzophenones such as -hydroxy-4-octoxybenzophenone and 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone); phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl- 3 ',
5'-di-tert-butyl-4'-hydroxybenzoate,
Benzoates such as hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2'-
Substituted oxanilides such as ethoxy oxanilide and 2-ethoxy-4'-dodecyl oxanilide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-
And cyanoacrylates such as cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

The singlet oxygen quencher includes, for example,
[2,2′-thiobis {4- (1,1,3,3-tetramethylbutyl) phenolato} butylamine] nickel,
Nickel-bis [O-ethyl (3,5-di-tert-butyl-
4-hydroxybenzyl)] phosphonate, nickel-
Dibutyldithiocarbamate, bis [2,2'-thiobis-4- (1,1,3,3-tetramethylbutyl) phenolato] nickel, cobalt (II) -tris-di-n-
Butyldithiocarbamate, iron (II) -diisopropyldithiocarbamate, cobalt (II) -di-isopropyldithiocarbamate and the like.

The photochromic composition of the present invention includes, for example, a surfactant, an antifoaming agent, a crosslinking agent, a viscosity modifier, an antistatic agent, a flame retardant, a heat stabilizer, an antioxidant, an ultraviolet absorber, and an ultraviolet stabilizer. Agents, lubricants, antioxidants, pigments, dyes, fillers, plasticizers and the like can be added.

The photochromic composition of the present invention can be used as an optical recording material, a copying material, a printing photoreceptor, a photosensitive material for a laser, a masking material, a light control material for automobiles, aircraft, building materials, a printing material, a toy, a cosmetic, etc. Can be used for a wide range of applications.

[0052]

The present invention will be described in more detail with reference to the following examples. However, the invention is not limited by these examples.

Example 1 1,3,3-trimethylspiro [indoline-2,3 '
-(3H) naphtho (2,1-b) (1,4) -oxazine] 10 mg, 3,9-bis [1,1-dimethyl-2-
{Tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (HALS) 10 mg and 10 mg of the test compound shown in the following [Table 1] was added to 10 ml of toluene.
Dissolves in water and irradiates it with a mercury lamp at 74 ° C to accelerate deterioration, and develops color over time and yellowish color when decolorized (coloring)
Was evaluated. The results are shown in Table 1 below. In addition, both evaluations are performed visually, and the evaluation criteria are as follows.

[Evaluation Criteria] Chromogenic ◎ Equivalent to original ○ Slightly thinner than original △ considerably thinner than original × no color

[0055]

[Table 1]

Example 2 1 ', 3'3'-Trimethyl-6-nitrospiro (2H
-1-benzopyran-2,2'-indoline) 10 m
g, 10 mg of the test compound and 10 mg of compound No. 2 shown in Table 2 below were dissolved in 10 ml of toluene, and the same test as in Example 1 was conducted. The results are shown in Table 2 below.

[0057]

[Table 2]

As is clear from the results of Tables 1 and 2, when a hindered amine compound is used alone together with a spiropyran-based compound or a spirooxazine-based compound, its light resistance is improved to some extent. The effect is still insufficient, and the above-mentioned general formula (I) or (I
When the organic phosphite compound represented by the formula (I) is used alone, there is almost no effect of improving the light resistance. Further, when the hindered amine compound is used in combination with an organic phosphite compound other than the above, there is almost no difference as compared with the case where the hindered amine compound is used alone.

On the other hand, only in the case of the present invention in which a hindered amine light stabilizer and the above organic phosphite compound are used together with a spiropyran compound or a spirooxazine compound, a remarkable synergistic effect on the light resistance improving effect is obtained. It turns out that it shows.

[0060]

The photochromic composition of the present invention is remarkably excellent in light resistance and can withstand intermittent light irradiation or continuous light irradiation by a coloring-quenching cycle.

Continuation of the front page (56) References JP-A-62-234084 (JP, A) JP-A-5-287131 (JP, A) JP-A-3-217441 (JP, A) JP-A-6-172748 (JP) (A) JP-A-5-202235 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09K 9/02 C09K 15/04-15/32 C08K 5/49-5/5399

Claims (1)

(57) [Claims] At least one of a spiropyran-based compound or a spirooxazine-based compound, at least one of a hindered amine compound and at least one of an organic phosphite compound represented by the following general formula (I) or (II): A photochromic composition comprising one kind. Embedded image