JPH0465482A - Photochromic composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having excellent light resistance and coloring light sensitivity, capable of reversibly repeating coloring and discoloring for a long period of time, by dissolving or dispersing an organic photochromic compound and a specific tertiary amine compound into a polymer substance. CONSTITUTION:(A) An organic photochromic compound (e.g. compound shown by formula I) and (B) a tertiary amine compound (e.g. compound shown by formula III) shown by formula II [R10 to R13 are 1-4C alkyl or epoxyalkenyl; A is alkylene, phenylene, etc.) are dissolved or dispersed into (C) a polymer compound (e.g. polymethacrylic acid or polyvinyl acetate) to give the objective composition. The amount of the component B is preferably 0.5-2 pts. wt. component A based on 100 pts. wt. component A and that of the component B is 3-30 pts. wt.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a photochromic composition, and more particularly to a photochromic material that has excellent light resistance and can repeat reversibly coloring and discoloring over a long period of time.

Technical Background of the Invention Photochromism is a substance that develops color by irradiating it with excitation light such as ultraviolet light, and returns to its original decolorized state when the excitation light irradiation is stopped and it is left alone, or when it is irradiated with visible light or heated. It means the property of reversible color development and fading.

Photochromic compounds having such properties are used in window glasses of various buildings, sunglasses, etc., taking advantage of the property that the color density varies depending on the intensity and irradiation time of excitation light. Further, attempts have been made to apply photochromic materials to image forming materials for copying, various types of recording, and the like.

Photochromic compounds used in such photochromic materials are broadly classified into organic photochromic compounds and inorganic photochromic compounds.

By the way, many inorganic photochromic compounds are hard particles with a higher specific gravity than organic polymeric substances, and they are rarely dissolved and incorporated into organic polymeric substances. It is difficult to dissolve or disperse homogeneously. On the other hand, organic 7-otochromic compounds can be homogeneously mixed with organic polymeric substances to produce photochromic films with no uneven coloring or fading, or to form such photochromic layers on substrates with no uneven coloring. You can

However, when organic photochromic compounds are irradiated with excitation light for a long period of time, they deteriorate due to oxidation, etc.
Another problem is that it loses its ability to reversibly develop and fade color upon oxidation.

For this reason, in photochromic compositions containing organic photochromic compounds, hydroxybenzophenone, hydroxybenzotriazole, and derivatives thereof may be added to suppress deterioration of the organic photochromic compounds (U.S. Pat. No. 3,212,898). It has been proposed to add a hindered amine compound (US Pat. No. 3,488,290) or a nickel complex (Japanese Patent Application Laid-Open No. 5,817,3181). It has also been proposed to add a thioether compound (Japanese Unexamined Patent Publication No. 58113203) or a hindered phenol compound and a phosphite compound (US Pat. No. 3,488,290).

However, ultraviolet absorbers such as hydroxybenzophenone and hydroxybenzotriazole absorb the ultraviolet rays necessary to excite organic photochromic compounds and develop color, resulting in decreased photosensitivity and In some cases, there is a problem in that the photodeterioration of the organic photochromic compound is accelerated.

In addition, hindered amine light stabilizers (HALS) are 1
Although it is said to have the functions of a heavy oxygen quencher, a radical scavenger, and a hydroperoxide decomposer, the photochromic composition containing this hindered amine light stabilizer and an organic photochromic compound does not have sufficient light resistance. In order to repeatedly use photochromic materials many times, it is necessary to further improve the light resistance.

Further, a photochromic composition containing a nickel complex and an organic photochromic compound also has a problem in that it does not have sufficient light resistance and is colored even when not irradiated with light due to the nickel complex.

Furthermore, even when a hindered phenol compound, a phosphite compound, or a thioether compound is used in place of the hindered amine light stabilizer or nickel complex, the light resistance of the photochromic composition is still insufficient.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and aims to provide a photochromic composition that has excellent light resistance without substantially reducing photosensitivity. The purpose is

Summary of the Invention The photochromic composition according to the present invention comprises an organic photochromic compound and the following formula [■] (wherein R1 to R13 may be the same or different, each having a carbon number of 1 to 20 is an alkyl group or an epoxyalkenyl group, which may be substituted with a substituent containing N1s or O.

A may have N, S or 0 in between, and is an alkylene group, a phenylene group, or a heterocycle containing N1S or O, and the alkylene group, phenylene group, or heterocycle may be substituted. good. ) is characterized by the addition of a tertiary amine compound represented by:

Detailed Description of the Invention The photochromic material according to the present invention will be specifically described below.

In the photochromic composition of the present invention, (1) an organic photochromic compound and (2) a specific tertiary amine compound are dissolved or dispersed in (3) a polymeric substance.

As such an organic photochromic compound, a spiro compound represented by the following formula [11] is preferably used.

During the ceremony, i is an integer of 0 or 1.

X is -O- or -8-, Y is one selected from =CH-=CH and =N-.

z, z' and Z'' each may be present or absent and are a saturated ring or an unsaturated ring which may contain a hetero atom. Examples of such saturated rings include a cyclohexyl ring, a cyclopentyl ring, etc. Examples of the unsaturated ring include a benzene ring, a heterocycle containing N, S or O, and the like.

R, RSR, and R8 may be the same or different, and each represents a hydrogen atom, a halogen atom, a nitro group, an optionally substituted amino group, a hydroxyl group,
Oxycarbonyl group, carboxyl group, sulfonic acid group,
From carbamoyl group, carboxamide group, sulfamoyl group, sulfonamide group, sulfanyl group, sulfonyl group, cyano group, optionally substituted alkyl group, optionally substituted aryl group, alkoxy group, aryloxy group, acyl group It is one of the selected types.

R2-R5 and R9 may be the same or different, and each represents a hydrogen atom, an optionally substituted alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 18 carbon atoms, or a carbon It is a cycloalkyl group having 4 to 10 atoms.

Examples of the substituents for R1 to R9 above include a halogen atom, an alkoxy group having 1 to 2 carbon atoms, an amino group, a nitro group, a mono- or dialkylamino group having 1 to 36 carbon atoms, a hydroxyl group, a carboxyl group, Or an oxycarboxyl group having 20 or less carbon atoms, 20 carbon atoms
Examples include the following acyl groups, oxycarbonyl groups having 20 or less carbon atoms, carbamoyl groups having 20 or less carbon atoms, and sulfamoyl groups having 20 or less carbon atoms.

When such a spiro compound represented by formula [II] is used in combination with a specific tertiary amine compound as described below, light resistance in particular is significantly improved.

Examples of the spiro compound represented by formula [11] include the following spiropyran compounds, and examples of the spirooxazine compound include the following compounds.

(Hereinafter, blank space) [Thiopyran] In the above formula, R is specifically -OCH3, -CH
, -H, -CI, -No2, and the like.

The specific tertiary amine compound used together with the organic photochromic compound in the present invention has the following formula [1] which may be the same or different and is an alkyl group having 1 to 4 carbon atoms, NSS Alternatively, it may be substituted with a substituent containing 0, and specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, and a 2-hydroxyethyl group.

A is an alkylene group, a phenylene group, or a heterocycle containing N1S or O, which may have NSS or O interposed therebetween, and these groups are, for example, alkyl groups such as methyl group and ethyl group, methoxy It may be substituted with a group, an alkoxy group such as an ethoxy group, or a halogen atom such as CI or Br. Specific examples of such a bonding group A include 1,000 CH2→], CH-CH-0-CH2-CH,, -CH2-→■→C
H2+, CHlr-CH2CH2NHCHp CHrc)12=
etc.

Examples of such tertiary amine compounds include the following compounds.

H (CH3)-2N-C)12-CHC)12-N-(C
l(3) 2(CH31N-C11,, -CII2-C
-N-GCI(3) 2(CH+-N-C12-N(-
C2H5) 2 In addition, the polymeric substance (3) plays a role as a binder and has good compatibility with organic photochromic compounds and specific tertiary amine compounds,
Moreover, it is preferably optically transparent.

Examples of such polymeric substances include polymethyl methacrylate, polyvinyl acetate, polyvinyl butyral,
Examples include polyvinyl alcohol.

The organic photochromic compound (1) is usually 0.01 to 25 parts by weight per 100 parts by weight of the polymeric substance (3).
It is used in amounts of parts by weight, preferably from 0.5 to 2 parts by weight.

In addition, the tertiary amine compound (2) is a polymer substance (3)
It is usually used in an amount of 1,001 to 100 parts by weight, preferably 3 to 30 parts by weight, per 100 parts by weight.

In the photochromic composition according to the present invention, an appropriate amount of a crosslinking agent consisting of various compounds such as isocyanate, epoxy, amine, ethyleneimine, metal chelate, etc. is used as necessary depending on the type of polymeric substance (3).

Further, depending on the type of polymeric substance (3), an appropriate amount of a plasticizer may be used in combination.

Examples of such plasticizers include phosphoric acid ester derivatives such as trioctyl phosphate and triphenyl phosphate, adipic acid ester derivatives such as di≠dyladipate and dibutyl adipate, and sepatic acid ester derivatives such as dibutyl sebacate and dioctyl sebacate. , azelaic acid ester derivatives such as dioctyl azelate, dihexyl azelate, and dihexyl azelate, citric acid ester derivatives such as triethyl citrate and tributyl citrate, and glycolic acids such as methyl phthalyl ethylene glycolate and butylphthalyl butyl glycolate. Ester derivatives, trimellitic acid ester derivatives such as trioctyl trimellitate, phthalic acid ester derivatives such as dioctyl phthalate, ricinoleic acid ester derivatives such as methyl acetyl lysyllate, butylacetyl lysyllate, polypropylene adipate, polypropylene sebacate, etc. Examples include polyester derivatives, epoxy derivatives such as epoxybutyl stearate and epoxyoctyl stearate, and glycol derivatives such as polyethylene glycol and polypropylene glycol.

The photochromic composition according to the present invention can be made into an appropriate form of photochromic material, for example, by the following procedure.

(2) Dissolve the polymer substance (3) in a suitable solvent, then add and mix the photochromic compound (1), tertiary amine compound (2), and crosslinking agent, plasticizer, etc. as necessary to this solution. Then, the mixed solution is applied onto the surface of the substrate by a cast coating method, a spin coating method, or the like and dried. In this way, a photochromic material having a photochromic layer laminated on the surface of the substrate is manufactured.

A powdered photochromic material is produced by spraying and drying the mixed solution described in (1) and (2) using a method such as a spray drying method.

(2) While stirring a solvent in which the polymer substance (3) is insoluble or poorly soluble, drop the mixture described in (2) into the solvent to precipitate it, and then collect and dry the precipitate. A granular photochromic material is produced by this method.

After melting and kneading a photochromic composition consisting of multiple components obtained by removing the solvent from the liquid mixture described in (1) and (2), a film or a photochromic material in any three-dimensional shape is produced by performing injection or extrusion molding.

Examples of solvents used when preparing the mixed solution described in (2) include water, alcohols such as methanol and ethanol, ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone, and aromatic solvents such as benzene, toluene, and xylene. , ethers such as diethyl ether and tetrahydrofuran, esters such as methyl acetate and ethyl acetate, and mixed solvents of two or more of these.

Effects of the Invention In the present invention, since an organic photochromic compound and a specific tertiary amine compound are used in combination, the light resistance of the organic photochromic compound is improved by the tertiary amine compound, and the coloring light sensitivity is improved. hardly ever decreases. Therefore, according to the present invention, a photochromic composition having excellent coloring light sensitivity and light resistance is provided.

Next, the filter structure of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples as long as the gist thereof is not exceeded.

Example 1 0.1 g of spiroindolinophenantrooxazine, which exhibits an absorption maximum at 366 nm, was dissolved in 23.3 g of a 1:1 mixed solution of toluene and 2-propanol, and 9.8 g of polyvinyl butyral was added to this solution. (Denka Butyral #2000-L manufactured by Denki Kagaku Kogyo Co., Ltd.) and dissolved, tertiary amine compounds N, N, N',
N'-tetramethyl-1,6 diaminohexane at 0.
1 g was added and stirred to prepare a solution with a total amount of 33.4 g.

This solution was applied onto a 38 μm thick polyethylene terephthalate film using a doctor blade and dried at 80° C. for 3 minutes to obtain a photochromic laminate in which a 25 μm thick photochromic layer was formed on the film.

The obtained photochromic laminate was usually colorless and transparent, and when irradiated with ultraviolet light, it developed a uniform bluish-purple color. Further, this colored photochromic laminate was returned to its original colorless and transparent photochromic laminate by irradiation with visible light or heating.

By the way, spiroindolinophenanthrooxazine is ring-opened by ultraviolet light irradiation, takes on a merocyanine structure, and develops color. If the deterioration progresses at this time, the original spiroindolinophenanthrooxazine structure cannot be restored even if the ultraviolet light irradiation is stopped.

Therefore, the light resistance of this photochromic laminate was evaluated in the following manner.

366, a colorless and transparent photochromic laminate in its initial state
Absorbance A in nm (maximum absorption wavelength of spiroindolinophenanthrooxazine). Ultraviolet light manufactured by Shimabara Manufacturing Co., Ltd.
Measurement was performed using a visible self-recording spectrophotometer MP32000.

Next, the photochromic laminate was continuously irradiated with ultraviolet light for 50 hours and 100 hours using a carbon arc lamp using a fade meter CF-20S manufactured by the same company.
It was heated to 80° C. to return to a completely colorless and transparent state, and the absorbance A at 366 nrr of this colorless and transparent photochromic laminate was measured by the same means as described above.

From the absorbance A (l and A) thus measured, the light resistance in the photochromic laminate was evaluated using the following formula.

Light resistance (%) = (A / Ao) x 100 In addition, the light resistance is evaluated to be better as the numerical value determined by the above formula is larger.

The results are shown in Table 1.

Example 2 A photochromic laminate was produced in the same manner as in Example 1 except that the tertiary amine compound was replaced with N, N, N', N'-tetramethyl p-phenylenediamine.
Light resistance was evaluated in the same manner as above.

The results are shown in Table 1.

Example 3 Tertiary amine compound N, N, N', N',
A photochromic laminate was produced in the same manner as in Example 1 except that N'-pentamethyl-diethylenetriamine was used,
Light resistance was evaluated in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Example 1 A photochromic laminate was produced in the same manner as in Example 1 except that no tertiary amine compound was added, and the light resistance was evaluated in the same manner as in Example 1.

The results are shown in Table 1.

Comparative Examples 2 to 6 A tertiary amine compound was added to the hindered phenolic antioxidant Irga'nox 1010 (manufactured by Ciba Geigy Co., Ltd.), the phosphite antioxidant Mark 135A (manufactured by Adeka Argus Chemical Co., Ltd.), and the thioether oxidation agent. Inhibitor AO-503A (manufactured by Adeka Argus Chemical Co., Ltd.), nickel metal complex light stabilizer Cyasorp UV1
Photochromic laminates of Comparative Examples 2 to 6 were produced in the same manner as in Example 1, except that the hindered amine light stabilizer Sanol LS-770 (manufactured by Sankyo Co., Ltd.) was used. .

Thereafter, the photochromic laminates of Comparative Examples 2 to 6 were each irradiated with ultraviolet rays in the same manner as in Example 1.
Only the photochromic laminate of Comparative Example 5 developed color. However, this color density was lower than that of the photochromic laminate of Example 1.2.

Next, the absorbance AI of each of the photochromic laminates of Comparative Examples 2 to 6 was measured in the same manner as in Example 1, and the light resistance of each photochromic laminate was evaluated, and the results shown in Table 1 were obtained.

(Hereinafter, blank space) As is clear from the results in the table and above, the photochromic laminates of Comparative Examples 1 to 6 have both lower colored light sensitivity and light resistance than the 7-photochromic laminate of Example 1.2.

Here, since the photochromic laminates of Example 1.2 and Comparative Examples 1 to 6 have the same structure except for the photochromic composition, the photochromic composition of the present invention has improved light resistance of the conventional one. It is found that both the color development light sensitivity and light resistance are excellent compared to photochromic compositions.

*This laminate was colored green by the Ni complex even before it was irradiated with ultraviolet light.

Patent applicant Lintech Co., Ltd. Agent Patent attorney Shun Suzuki Part 4
゜Procedural amendment 1991

Claims (3)

[Claims] (1) Organic photochromic compound and the following formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_10 to R_13 may be the same or different, and have a carbon atom number of 1 to 20 alkyl groups,
It is an epoxyalkenyl group and may be substituted with a substituent containing N, S or O. A is an alkylene group, a phenylene group, or a heterocycle containing N, S, or O, and the alkylene group, phenylene group, or heterocycle is substituted. Good too. A photochromic composition characterized in that a tertiary amine compound represented by the following formula is dissolved or dispersed in a polymeric substance. (2) A photochromic film comprising the photochromic composition according to claim 1. (3) A photochromic laminate having a photochromic layer comprising the photochromic composition according to claim 1 on the surface of a substrate.