JPH05271649A - Multicolor photochromic composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which can develop any desired color on exposure to ultraviolet rays of a suitably selected wavelength or intensity by using specified diarylethene compounds. CONSTITUTION:The objective composition comprises at least two diarylethene compounds selected from among compounds of formulas I-III, wherein Ar<1> to Ar<5> are each a group of formula IV or V and Ar<6> is a group of formula VI R<1>, R<4>, R<9> and R<10> are each alkyl; R<2> and R<3> are each R<1>, alkoxyl, aryl or cyano; and R<5> to R<8> and R<11> to R<14> are each H, R<2> or acyl).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photochromic composition capable of multicolor display applicable to various displays, ornaments, advertisement displays and the like.

[0002]

2. Description of the Related Art In recent years, reversible hue changes by light irradiation have been used for recording, memory materials, copying materials, light control materials, printing photoconductors, laser photoconductors, masking materials, photometers, or display materials. Compounds having various photochromic properties have been proposed.

For example, compounds such as benzospiropyrans, naphthoxazines, fulgides, diazo compounds and diarylethenes have been proposed as the photochromic compounds.

By the way, in order to apply the color change of the photochromic compound to a display, a decorative article, a toy, etc., it is preferable that there are various color changes. Therefore, the photochromic compounds having various structures can be used alone or in combination. It is proposed to bring out the color of.

However, in these methods, the color change is generally limited to a specific two colors, and it is not possible to change a large number of colors with the same material, and there is no photochromic material capable of multicolor display. The current situation.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and its object is to:
Another object of the present invention is to provide a photochromic composition capable of exhibiting a large number of colors, including intermediate colors, by changing the wavelength and intensity of irradiation light.

[0007]

[Means for Solving the Problems] The above-mentioned object is to achieve the following three compounds represented by the following general formulas (7), (8) and (9):
It is achieved by a multicolor photochromic composition composed of a diarylethene compound selected from at least two compound groups.

[0008]

[Chemical 7]

[0009]

[Chemical 8]

[0010]

[Chemical 9]

However, in the formula, Ar ¹ , Ar ² , Ar ³ and Ar
⁴ and Ar ⁵

[Chemical 10] , Or

[Chemical 11] And Ar ⁶ is

[Chemical 12] Represents.

R ¹ , R ⁴ , R ⁹ and R ¹⁰ are alkyl groups, R ² and R ³ are alkyl groups, alkoxy groups,
An aryl group or a cyano group is added to R ^{5 to} R ⁸ and R ^{11 to} R ^14.
Represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an acyl group or a cyano group.

The diarylethene compound represented by Chemical formula 7 used in the present invention can be produced as follows. That is,

[Chemical 13] Octafluoro-2-butene represented by

[Chemical 14] Lithiothiophene represented by or

[Chemical 15] Is reacted with lithiobenzothiophene.

The diarylethene compound represented by Chemical formula 8 used in the present invention can be produced as follows. That is,

[Chemical 16] And a perfluoroalkene compound represented by
Alternatively, it is reacted with an aryl lithiation compound represented by Chemical formula 15.

The diarylethene compound represented by Chemical formula 9 used in the present invention can be produced as follows. That is, the perfluoroalkene compound represented by the chemical formula 16 and the aryl lithiated compound represented by the chemical formula 14 or 15 and

[Chemical 17] Is reacted with lithioindole represented by.

All of the diarylethene compounds used in the present invention are colorless unless they are irradiated with ultraviolet light. However, the compounds represented by the general formula 7 are a group of compounds having a high coloring intensity at ultraviolet light of 300 nm or less, As an example,
2,3-bis- (2-methyl-3-benzothienyl)-
When 1,1,1,4,4,4-hexafluoro-2-butene is irradiated with ultraviolet light of 254 nm as shown in Chemical formula 18 below, it undergoes a ring closure reaction and is colored yellow. Then 400 nm
Irradiation with the above visible light causes a ring-opening reaction and returns to the original colorless state. Also, this compound hardly develops color under light of 300 nm or more.

[0017]

[Chemical 18]

The compound represented by the general formula 8 is 270 to 3
It is a group of compounds that are particularly likely to develop color with 30 nm UV light,
For example, as an example thereof, 1,2-bis- (2,4,5-trimethyl-3-thienyl) -3,
3,4,4,5,5-hexafluoropentene is 31
It is colored from colorless to red by irradiation with 3 nm ultraviolet light, and returns to its original colorlessness by irradiation with visible light.

[0019]

[Chemical 19]

The compounds of general formula 9 are 330-38.
It is a group of compounds that easily develop color with 0 nm ultraviolet light, and one example thereof is 1- (1,2-dimethyl-3-indolyl) -2- (2-methyl-3-benzothienyl)- 3,3,4,4,5,5-hexafluoropentene changes from colorless to blue-violet when irradiated with 365 nm ultraviolet light, and similarly returns to the original colorless color when irradiated with visible light.

[0021]

[Chemical 20]

Therefore, for example, the composition comprising the above-mentioned three kinds of diarylethene compounds has three kinds of peaks of absorbance and is colorless unless it is irradiated with ultraviolet light, but it is yellow-orange under the ultraviolet light of 254 nm. , 313nm ultraviolet light is red, 365nm ultraviolet light is blue-violet, 254nm and 31
3 nm UV light is orange, 254 nm and 365 nm UV light is gray blue, 313 nm and 365 nm UV light is purple,
In addition, three kinds of ultraviolet light of 254 nm, 313 nm, and 365 nm give a grayish purple color. Furthermore, by changing the irradiation intensity of each ultraviolet light, it is possible to obtain an arbitrary intermediate color.

The photochromic composition of the present invention may be composed of a diarylethene compound selected from at least two of the above-mentioned three kinds of compounds, and a plurality of compounds from the same group may be used. it can.

Since the coloring of the diarylethene compound constituting the photochromic composition of the present invention is not erased by heat, the colored state is maintained for several tens of minutes or more under normal illumination, and the durability against repeated decolorization is maintained. It is extremely suitable for various displays because it has excellent Further, if the light beam of ultraviolet light is narrowed down by a lens or the like, it is possible to display fine patterns and characters.

The photochromic composition of the present invention can be prepared from only two or more compounds selected from three diarylethene compounds, but can be mixed with other dyes or pigments. In particular, when used in combination with a white pigment such as titanium oxide, there is an advantage that white and any hue can be obtained. Also, it can be used by being dispersed in a resin such as an acrylic resin, vinyl chloride resin, polyester resin, polyamide resin, polyolefin resin or urethane resin.

The photochromic composition of the present invention can be used by coating it on the surface of a transparent or opaque material having a shape suitable for the purpose.
The coating method, the spin coating method, the dipping method, the casting method and the like can be mentioned.

The photochromic composition of the present invention may be dispersed in a resin and used as a film or sheet, or may be impregnated or printed on paper or cloth.

The three kinds of diarylethene compounds may be mixed in advance and used, or they may be sequentially laminated on the surface of the material. It is also possible to use by laminating films or sheets separately dispersed in a resin.

The light source to be colored is not particularly limited as long as it emits ultraviolet light having a wavelength to be individually colored. For example, a mercury lamp or a xenon lamp is preferably used, and if necessary, a specific wavelength is used. It may be combined with a filter or the like that transmits the ultraviolet light.

Not only for applications where the color change of the photochromic composition can be directly observed such as various displays and ornaments, for example, a transparent film having the photochromic composition dispersed therein can be used to change the color due to ultraviolet light using a projector or the like. It can also be projected.

[0031]

INDUSTRIAL APPLICABILITY As described above, the photochromic composition of the present invention can be colored in any color by appropriately selecting the wavelength and intensity of ultraviolet light, and can be used for various displays, advertising displays, ornaments, or It can be suitably used for toys and the like. Further, it is preferably used as a so-called wavelength multiplex recording medium as an optical recording material.

The present invention will be specifically described below with reference to examples.

[0033]

【Example】

Example 1 2 g, 1.5 g, and 1 g of the diarylethene compounds represented by the following structural formulas 21, 22, and 23, respectively, and 40 g of polystyrene resin were dissolved in 400 ml of toluene. Put a filter paper with a diameter of 18 cm into this solution, pull it up and air dry,
A sheet having the photochromic composition was prepared.

[0034]

[Chemical 21]

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23]

The front of each of the three high pressure mercury lamps has 254
nm, 313 nm, 365 nm interference filter is installed, and a diameter of about 1 cm is placed on the sheet using a quartz lens.
The beams are arranged so that they overlap. The intensity of ultraviolet light was adjusted by combining a neutral density filter.

Table 1 shows an example of the hue when each ultraviolet light is irradiated. By selecting the wavelength and intensity of the ultraviolet light, it is possible to color various colors even with one type of photochromic composition. did it.

[0039]

[Table 1]

[Brief description of drawings]

FIG. 1 shows respective absorption spectra of a diarylethene compound used in Example 1 when colored.

[Explanation of Codes] (A) ... Absorption spectrum of colored body of Chemical formula 21 (B) ... Absorption spectrum of colored body of Chemical formula 22 (C) ... Absorption spectrum of colored body of Chemical formula 23

Claims (1)

[Claims] 1. A multi-color photochromic composition comprising a diarylethene compound selected from at least two compound groups selected from the three compound groups represented by the following general formulas 1, 2, and 3. [Chemical 1] [Chemical 2] [Chemical 3] However, in the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ and Ar ⁵ are as follows. , Or And Ar ⁶ is Represents. R ¹ , R ⁴ , R ⁹ and R ¹⁰ are alkyl groups, R ² and R ³ are alkyl groups, alkoxy groups, aryl groups or cyano groups, and R ^{5 to} R ⁸ and R ^{11 to} R ^{14 are} Is
It represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an acyl group or a cyano group.