JPH0723470B2 - Photochromic molded article and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention provides a photochromic layer having excellent light controllability, scratch resistance, abrasion resistance, heat resistance, dyeability, chemical resistance and light resistance. The present invention relates to a molded body having the same and a manufacturing method thereof.

[Prior Art] Many compounds having photochromic properties are already known (GH Brown. “PHOTOCHRONISM” Wiley
Interscience.New York (1971)).

Among them, spiropyran compounds are well known for their synthetic methods and properties.

On the other hand, Japanese Patent Publication Nos. 45-28892, 49-48631 and 55-36284 disclose synthesis methods and characteristics of spirooxazine compounds.

Application examples of the coating of these photochromic compounds are disclosed in JP-A-59-78271 and JP-A-59-7.
It is described in Japanese Patent No. 8272.

[Problems to be Solved by the Invention] A coating film obtained by the techniques described in JP-A-59-78271 and JP-A-59-78272 has photochromic properties and high surface hardness. However, the obtained coating film is a colored coating film which is already yellow or magenta before irradiation with light, and has a serious problem in appearance. Further, depending on the photochromic compound, the color developability due to light irradiation may disappear.

An object of the present invention is to significantly enhance the photochromic property, especially the coloring and decoloring rate, and to endure repeated use.

[Means for Solving Problems] In order to achieve the above object, the present invention is achieved by the following configurations.

That is, the first invention has the following configuration.

"A photochromic molding having a layer made of a cellulose derivative polymer containing a compound represented by the following general formula [I].

(Wherein R ¹ , R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group, or a halogen group,
1 selected from nitro group and alkali metal sulfonate base
R ² represents one or more kinds of substituents, and R ² represents one or more kinds of substituents selected from a halogen group, a nitro group, a cyano group, a (halogenated) alkyl group having 1 to 4 carbon atoms and an alkoxy group, and a , C and d are 0, 1 or 2 respectively, and b is 0.
An integer of ~ 5. ) And a second invention is the production of a photochromic molded article, characterized in that a uniform solution comprising the compound represented by the general formula [I] and a cellulose derivative polymer is applied to the surface of the molded article and then dried. Is the way.

Hereinafter, a specific configuration of the present invention will be described in detail.

In the general formula [I] used in the present invention, a spirooxazine compound having hydrogen, an alkyl group having 1 to 6 carbon atoms or an alkoxy group for R ¹ , R ³ and R ⁴ is preferable, particularly from the viewpoint of light resistance. Preferably has hydrogen, a methyl group or a methoxy group.

Further, R ¹ , R ³ and R ⁴ in the general formula [I] may be the same or different. Further, even when a, c and d are 2, it does not matter if R ¹ , R ³ and R ⁴ are the same or different. Further, as for R ² , when b is 2 or more, they may be the same or different.

A typical specific example of the compound represented by [I] is 1-benzyl-spiro [indolino-2,3 '-[3H] -naphtho [2,1-b] (1,4) oxazine]. 3,3
-Dimethyl derivative, 1- (4-methylbenzyl) -3,3
-Dimethyl derivative, 1- (4-methoxybenzyl) -3,
3-dimethyl derivative, 1- (4-chlorobenzyl) -3,3
-Dimethyl derivative, 1- (4-bromobenzyl) -3,3
-Dimethyl derivative, 1- (4-fluorobenzyl) -3,
3-dimethyl derivative, 1- (2-fluorobenzyl)-
3,3-Dimethyl derivative, 1- (3-fluorobenzyl)
-3,3-Dimethyl derivative, 1- (2,3-difluorobenzyl) -3,3-dimethyl derivative, 1- (2,4-difluorobenzyl) -3,3-dimethyl derivative, 1- (2,5 -Difluorobenzyl) -3,3-dimethyl derivative, 1- (2,6-difluorobenzyl) -3,3-dimethyl derivative, 1- (3,4-
Difluorobenzyl) -3,3-dimethyl derivative, 1-
(3,5-difluorobenzyl) -3,3-dimethyl derivative,
1- (2,3,4-trifluorobenzyl) -3,3-dimethyl derivative, 1- (2,3,5-trifluorobenzyl) -3,3-
Dimethyl derivative, 1- (2,3,6-trifluorobenzyl) -3,3-dimethyl derivative, 1- (2,4,5-trifluorobenzyl) -3,3-dimethyl derivative, 1- (2, 4,6-Trifluorobenzyl) -3,3-dimethyl derivative, 1-
(3,4,5-Trifluorobenzyl) -3,3-dimethyl derivative, 1- (2,3,4,5-tetrafluorobenzyl) -3,3-
Dimethyl derivative, 1- (2,3,5,6-tetrafluorobenzyl) -3,3-dimethyl derivative, 1- (2,4,5,6-tetrafluorobenzyl) -3,3-dimethyl derivative, 1 − (2,
3,4,5,6-Pentafluorobenzyl) -3,3-dimethyl derivative, 1- (4-cyanobenzyl) -3,3-dimethyl derivative, 1- (4-trifluoromethylbenzyl) -3,3
-Dimethyl derivative, 1- (4-nitrobenzyl) -3,3
-Dimethyl derivative, 1- (2,3-dimethylbenzyl)-
3,3-Dimethyl derivative, 1- (2,4-dimethylbenzyl)
-3,3-dimethyl derivative, 1- (2,5-dimethylbenzyl) -3,3-dimethyl derivative, 1- (2,6-dimethylbenzyl) -3,3-dimethyl derivative, 1- (3,5 -Dimethylbenzyl) -3,3-dimethyl derivative, 1- (2,3,4-trimethylbenzyl) -3,3-dimethyl derivative, 1- (2,3,5-
Trimethylbenzyl) -3,3-dimethyl derivative, 1-
(2,3,6-Trimethylbenzyl) -3,3-dimethyl derivative, 1- (2,4,5-trimethylbenzyl) -3,3-dimethyl derivative, 1- (2,4,6-trimethylbenzyl) −3,3−
Dimethyl derivative, 1- (3,4,5-trimethylbenzyl)
-3,3-Dimethyl derivative, 1- (2,3,4,5-tetramethylbenzyl) -3,3-dimethyl derivative, 1- (2,3,5,6-tetramethylbenzyl) -3,3 -Dimethyl derivative, 1-
In the (2,3,4,5,6-pentamethylbenzyl) -3,3-dimethyl derivative and these various derivatives, 5,6,
Methyl group, ethyl group, propyl group, butyl group, phenyl group, methoxy group, ethoxy group, chloro group, bromine at 7,8-position and / or 5 ', 6', 7 ', 8', 9'10'-position Examples thereof include spirooxazine compounds having one or more substituents selected from a group, a fluoro group, a nitro group, and an alkali metal sulfonate group. These photochromic compounds may be used alone or in combination of two or more.

The present invention comprises a photochromic compound comprising such a spirooxazine compound contained in a cellulose derivative polymer.
There is a method in which it is contained in the molded body by its molding step, such as injection molding or extrusion molding, or it is contained in only a specific layer portion by two-color molding or the like. As still another means, there is a method of applying what is contained as a coating material on the surface of various molded bodies. Further, it is also possible to form it by including it in a sandwich form in the middle of various molded bodies.

Regarding the means for incorporating the above photochromic compound, various known methods, for example, (a) a method of mixing a cellulose derivative polymer and a photochromic compound.

(B) There is a method of mixing the cellulose derivative polymer and the photochromic compound in a volatile dispersion medium and then evaporating the volatile dispersion medium.

Of the above, when the present invention is applied as a coating agent, the method of item (b) is preferable. In this case, the coating film is formed by evaporation of the volatile dispersion medium, but it may be cured by containing an appropriate curing agent during and / or after the formation of the coating film.

The cellulose derivative polymer of the present invention is a derivative of various celluloses, that is, fibrin polymers. Examples of such a cellulose derivative include cellulose esters in which a part or all of hydroxyl groups of cellulose are esterified, and similarly, a cellulose ether in which a part or all thereof is etherified.

Specific examples of cellulose esters include acetyl cellulose, cellulose propionate, cellulose butyrate, nitrocellulose, cellulose sulfate, and cellulose phosphate. Further, mixed esters such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose nitrate acetate can be cited as examples. Other esterified products include valeric acid, caproic acid, enanthic acid, caprylic acid,
There are reaction products such as lauric acid, myristic acid, palmitic acid and phthalic acid. On the other hand, specific examples of cellulose ethers include methyl cellulose, ethyl cellulose,
Examples thereof include benzyl cellulose, trityl cellulose, cyanethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, aminoethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl hydroxyethyl cellulose and the like. Furthermore, these mixed ethers can also be used.

The optimum degree of esterification and degree of etherification of these cellulose esters or cellulose ethers should be determined depending on the method of use, the photochromic compound used, and the like.

Such a cellulose derivative polymer can also be used by grafting onto a common acrylic polymer or the like.

Among the above cellulose derivative polymers, mixed esters are preferable from the viewpoint of the color development and decoloring rate, and among them, cellulose acetate propionate and cellulose acetate butyrate are particularly preferably used.

Of course, it is possible to use not only one kind of such a cellulose derivative polymer but also a mixture of two or more kinds. Furthermore, the molecular weight of the cellulose derivative polymer is not particularly limited as long as it can form a layer, but from the viewpoint of ease of handling, chemical resistance, etc., a number average molecular weight of 4000 to
100,000 are preferred.

The present invention is to obtain a photochromic molded article having a layer composed of a cellulose derivative polymer containing a photochromic compound, the shape of the molded article,
There is no limitation with respect to size, use, etc. Therefore, it is not particularly important which method is used as the above-mentioned means, but when it is used as a coating agent after being contained in a volatile dispersion medium, it has the following advantages.

That is, when it cannot be easily contained in the polymer forming the molded body, a wide range of base materials can be selected as the molded body, which is an effective means for imparting a photochromic effect to the base material.

The composition ratio of each component constituting the cellulose derivative polymer containing the photochromic compound in the present invention, the application, should be determined by the purpose, etc., the addition amount of the photochromic compound in terms of color density, the photochromic 0.001 to 20 parts by weight is preferable with respect to 100 parts by weight of the cellulose derivative polymer layer containing the compound, and 0.01 to 10 parts by weight is particularly preferable from the viewpoint of light resistance.

Drying of the coating material for photochromic coating applied on the surface of the molded body as a solution of the cellulose derivative polymer containing the photochromic compound can be achieved by heating and / or drying only the coating material. When the polymer layer is cross-linked, various curing agents can be used for the purpose of accelerating curing and curing at low temperature. As the curing agent, various melamine resins, urea resins, silane coupling agents, etc. are used.

When the present invention is used as a coating agent on a substrate, various coating methods can be applied for coating. Brush, brush, roller, etc., other roll coating, spray coating, flow coating, dipping coating,
Spin coating or the like can be applied.

As the molded body to be coated, various materials such as plastic, glass, ceramics, inorganic materials, metal, wood, ceramics, concrete and paper can be used. Various surface-treated products can also be applied.

Further, the thickness of the layer made of the cellulose derivative polymer containing the photochromic compound in the present invention varies depending on the purpose of use, but for spectacle lenses and the like,
In order to remarkably exhibit the photochromic property, it is desirable that the thickness is 0.01 μm or more, preferably 0.1 μm or more.

Although the layer containing the photochromic compound used in the present invention can be dried at room temperature, it is generally heated for the purpose of shortening the time. The heating temperature at that time can be used in a fairly wide range, and sufficiently good results can be obtained at room temperature to 200 ° C.

Further, in order to improve light resistance and fatigue resistance, various ultraviolet absorbers and / or ultraviolet stabilizers may be added. Particularly, the Ni-containing ultraviolet absorber is effective in improving fatigue resistance.

Further, various organic substances can be added for the purpose of controlling photochromic properties such as color developing property, color erasing property, and color forming species. Preferred examples of such organic substances include various epoxy resins, vinyl polymers, nylon resins,
Examples include melamine resin, butyral resin, and polyethylene oxide.

On the other hand, it is possible to add various fine particle inorganic oxides for the purpose of improving the physical properties of the cellulose derivative polymer, for example, improving hardness and imparting antistatic property, and dispersed in the form of fine particles from the viewpoint of transparency of the layer. Preferred examples thereof include colloidal silica.

When the present invention is applied as a coating agent, the photochromic coating composition can be diluted with various solvents and used. The solvent that can be used is not particularly limited, but from the viewpoint of volatility and safety, various lower alcohols, ketones, ethers, esters, aromatic hydrocarbons, (halogenated) hydrocarbons And formamide compounds, dimethylsulfoxide and the like.
Of course, these can be used as a mixed solvent of two or more kinds. Although it cannot be used alone, water can be used.

The molded product according to the present invention is preferably used not only for various optical lenses represented by spectacle lenses, but also for displays, window glasses, automotive windshields, laminated windows such as rear windows, side glasses, etc., as well as hard tools and manicures. It is applied.

[Examples] Examples will be given below to clarify the gist of the present invention, but the present invention is not limited to these examples.

Examples 1 to 3 and Comparative Examples 1 to 2 (1) Preparation of Photochromic Compound-Containing Cast Film Composition Cellulose derivative polymers shown in Table 1 were dissolved in methylene chloride at 10 weight percent. A photochromic compound was added to the polymer solution as 1- (3-methylbenzyl) -3,3 dimethylspiro [indolino-2,
3 '-[3H] naphtho [2,1-b] (1,4) -oxazine]
Was dissolved in a concentration of 0.06 weight percent to obtain a cast film composition. In addition, it carried out similarly about polymethylmethacrylate and polyvinyl butyral as a comparative example. For the latter, the solvent was changed to n-butyl alcohol.

(2) Preparation of cast film The composition of (1) above was volatilized with a solvent on a petri dish to obtain a transparent film.

(3) Test Results After the photochromic compound-containing film obtained in (2) above was irradiated with a chemical lamp as an excitation light source for color development, the irradiation was stopped and the color development state and decolorization speed at that time were visually observed.

The results are shown in Table 1. It was found that the one using the cellulose derivative polymer was excellent in that the color density was high and the decoloring speed was extremely fast.

The abbreviations in Table 1 indicate the following.

* 1 CAB: Cellulose acetate butyrate PMMA: Polymethylmethacrylate PVB: Polyvinyl butyral * 2 Judgment of color development condition 55% or less of the total light transmittance was considered good, and when it was lighter than this, it was considered bad.

[Effects of the Invention] The molded product obtained by the present invention has the following effects.

It has an ideal photochromic property of being colorless before irradiation with ultraviolet light and rapidly colored after irradiation.

The photochromic properties are hardly deteriorated even after long-term use.

The molded body has high surface hardness and photochromic properties.

The photochromic molded product has an extremely high rate of coloring and decoloring.

Claims (3)

[Claims] 1. A photochromic molded article having a layer made of a cellulose derivative polymer containing a compound represented by the following general formula [I]. (Wherein R ¹ , R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group, or a halogen group,
1 selected from nitro group and alkali metal sulfonate base
R ² represents one or more kinds of substituents, and R ² represents one or more kinds of substituents selected from a halogen group, a nitro group, a cyano group, a (halogenated) alkyl group having 1 to 4 carbon atoms and an alkoxy group, and a , C and d are 0, 1 or 2 respectively, and b is 0.
An integer of ~ 5. ) 2. The photochromic molded article according to claim 1, wherein the layer made of a cellulose derivative polymer containing the compound represented by the general formula [I] has a thickness of 0.01 μm or more. 3. A compound represented by the following general formula [I]:
A method for producing a photochromic molded article, which comprises applying a uniform solution of a cellulose derivative polymer to the surface of the molded article and then drying. (Wherein R ¹ , R ³ and R ⁴ are each an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkoxy group, or a halogen group,
1 selected from nitro group and alkali metal sulfonate base
R ² represents one or more kinds of substituents, and R ² represents one or more kinds of substituents selected from a halogen group, a nitro group, a cyano group, a (halogenated) alkyl group having 1 to 4 carbon atoms and an alkoxy group, and a , C and d are 0, 1 or 2 respectively, and b is 0.
An integer of ~ 5. )