JPH0632940A - Photochromic composition and device fitted therewith - Google Patents

Abstract

PURPOSE:To obtain a photochromic composition with which the monitoring of an ultraviolet radiation or the buildup of an ultraviolet radiation can be simply performed or measured by incorporating 4 specified compound which can easily liberate a color on exposure to an ultraviolet radiation in the composi tion. CONSTITUTION:This composition comprises a polymer containing a compound of formula I [wherein X is O or S; Y is O, S, NH or methylene; R1 is 1-6 C alkyl which may be substituted with phenyl, hydroxyl, alkoxyl, halogen, SO2, NH2, COOH or NO2 or phenyl which may be substituted with any of these substituents; R2 and R1' are each OH, NH2 or 1-6 C mono- or di-alkylamino; R3 and R3' are each H, 1-6 C alkyl provided that they together with one oxygen or sulfur atom may be combined with each other to form a ring; and R4 and R4' are each 1-6 C alkyl or halogen] (e.g. a compound of formula II or III). For example, by fitting a device with this composition and fitting its front face with a film which can absorb an ultraviolet radiation of a specified wavelength, the monitoring of an ultraviolet radiation or the buildup of an ultraviolet radiation can be simply performed or measured.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides an inexpensive, sensitive, and easily determinable instrument that can be used for monitoring and integrating the increase in ultraviolet rays due to the destruction of the ozone layer, which has recently been a problem. It is in.

2. Description of the Related Art Glasses which utilize silver halide and are colored in response to ultraviolet rays are used as an ultraviolet ray monitor as an extension of sunglasses and the like. However, the principle of this reaction is a reversible reaction in which silver halide liberates silver by light in the glass solid and the glass is colored, and only reflects the UV intensity at the time of measurement. . Moreover, this reaction is very slow, and the degree of coloring cannot change in real time due to the intensity of ultraviolet rays. It is also brittle because it uses glass, and has a large specific gravity. Since it uses a reversible reaction, it can be used repeatedly, but this is a drawback. That is, regarding the influence of ultraviolet rays on living things, the intensity of the ultraviolet rays and how long the ultraviolet rays last, so-called history, has a greater meaning than only the intensity at the present time. In this respect, reversible reactions are inappropriate. It is also expensive.

SUMMARY OF THE INVENTION It has been desired to develop an inexpensive and easy-to-see instrument that can count the intensity and duration of ultraviolet rays by utilizing an irreversible reaction.

Means for Solving the Problems

[Chemical 2] (In the formula, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, an —NH— group or a methylene group, and R ₁ represents an alkyl group having ₁ to 6 carbon atoms or a substituted alkyl group (phenyl group as a substituent group). , Hydroxy, alkoxy, halogen, sulfonyl, amino, carbonyl, nitro, each group), phenyl, substituted phenyl (the same as the above), R ₂ R ₂ ′ may be the same or different, and a hydroxyl group , Amino, and a mono- or dialkylamino group having 1 to 6 carbon atoms, R ₃ R ₃ ′ may be the same or different, and represent hydrogen, alkyl having 1 to 6 carbon atoms, or R ₃ R ₃ ′. May share one atom (oxygen or sulfur) to form a ring, R ₄ R ₄ ′ may be the same or different, and an alkyl group having 1 to 6 carbon atoms,
Indicates a halogen group. It was discovered that a compound having) easily liberates a dye in a polymer by ultraviolet rays, and this is an irreversible reaction. By combining this with various polymers or ultraviolet absorbers, a very convenient ultraviolet The present invention was completed when it was found that monitoring or ultraviolet accumulation can be measured. It is presumed that the basis of the present invention is the following reaction.

[Chemical 3] In this reaction, coloring occurs when the group represented by the formula is eliminated, but the energy of ultraviolet rays that is most efficiently eliminated depends on the type of the group to be eliminated. In other words, it is a great feature of the present invention that various kinds of ultraviolet rays can be separately measured depending on the kind of the group. The present invention can be achieved, for example, as follows. The heat-meltable polymer is heated and dissolved, and the compound represented by the above general formula is added and dissolved therein, and the mixture is uniformly stirred when heated. The solution is poured onto an aluminum plate having a temperature slightly lower than the melting temperature of the polymer, and then the temperature is lowered to form a film. As a method of incorporating a compound into a polymer, a thermoplastic polymer as described above may be dissolved by heating and mixed, but in the case of a crosslinked polymer or a polymer which is decomposed by heat, polymerization is performed. It can also be achieved by mixing at that time and molding into a film by the same method as is usually performed. The concentration to be contained in the polymer varies depending on the type of the polymer due to compatibility with the polymer, but 0.0001% to 10%
The film is cut into an appropriate shape and size, and set in a container as shown in the following figure to prepare the device of the present invention. The container shown here does not need to be particular in shape or size, as long as it is easy to see the colored result, and it may be equipped with pins and chains for attaching to the body, rubber bands, adhesive layers, etc. . FIG. 1 shows an elevation view and a plan view. The lengths shown in the figure indicate the thickness of the shape or the range of the length. The cover is a transparent quartz glass or transparent plastic plate that prevents liquid and dust, and the absorption layer is a layer that absorbs light other than ultraviolet rays to be detected, and a substance that selectively absorbs light that should be absorbed by glass or polymer. It is a plate-shaped product in which is dispersed. The color sample layer is printed with a dye of a certain density so that you can see how much the color is colored.Even if a symbol or character such as caution or danger is displayed here. Anything is acceptable as long as it is good and the design is easy to understand. The coloring layer is a layer containing the compound of the present invention. The support layer is generally made of a light plastic container, but the material and shape are not particularly limited.

FIG. 1 uses the prepared one with the side A as a table. The film surface of this product is colored when left outside the room where the ultraviolet rays are strong, and it is colored in proportion to the exposure time of the intensity of the ultraviolet rays. The shape of the device including the container may be any as long as the film is colored by ultraviolet rays and can be easily seen. It is also convenient if a color sample is installed so that the degree of coloration can be compared immediately. As specific examples of the compound represented by the general formula (hereinafter referred to as compound) used in the present invention, any of the compounds represented by the following formulas can be used.

[Chemical 4] The compounds shown in Table 1 can be synthesized by the following synthetic method. That is, methylene blue is dissolved in water, hydrosulfite is added to the methylene blue for reduction, and chloroform is added to extract the leuco base of methylene blue.
Methyl isocyanate, ethyl isocyanate,
Alkyl isocyanates such as hexamethylene diisocyanate, substituted alkyl isocyanates, or phenyl isocyanate, tolylene diisocyanate, xylylene diisocyanate are reacted, and then the other or excess isocyanate is reacted with alcohols, amines. A compound of the general formula where X is oxygen and Y is -NH- can be synthesized by reacting with a group of compounds. In addition, for those which are originally leuco bases such as bind shedler's green leuco base, the above isocyanates may be reacted in the solvent as they are. If a compound having a thioisocyanate group is reacted instead of the isocyanates, the target compound in which X is a sulfur atom and Y is —NH— is obtained, and chloroformic acid esters or chlorothioformate esters are used as isocyanates. If reacted instead of nates, X is oxygen and Y
The desired compound is obtained in which is oxygen or sulfur. Further, by reacting an acid anhydride or an acid chloride instead of the isocyanate, a target compound in which X is oxygen and Y is an alkylene group can be synthesized. As the type of the polymer containing the compound used in the present invention, any polymer that can give a transparent film can be used. Examples thereof include polystyrene and copolymers containing it as a main component, polyacrylic acid esters and copolymers containing it as a main component, polyethylene and copolymers containing it as a main component, polypropylene and its main component. Component copolymer, polybutadiene and copolymers containing it as a main component, polyvinyl halide and copolymers containing it as a main component, polyvinyl alcohol and copolymers containing it as a main component,
Examples include polyamides, polyesters, polycarbonates, polyurethanes, and polyethers. The compound used in the present invention absorbs even a very weak ultraviolet ray to develop a color, but if it is left as it is, the color develops immediately and only a small amount of ultraviolet ray can be measured. In order to be able to measure a large amount of ultraviolet rays, the front surface of this film may be covered with a transparent film that absorbs a certain amount of ultraviolet rays, and a polymer that absorbs ultraviolet rays from the beginning is mixed. It doesn't matter. Further, it is possible to modify into a device in which the influence of the ultraviolet ray of the wavelength is eliminated on the front surface of the film that develops the color of the film that absorbs the ultraviolet ray of the specific wavelength and the sensitivity to the ultraviolet ray of other wavelength is increased. For example, ultraviolet rays from the sun that affect the human body generally cause sunburn when classified into ultraviolet rays A (wavelength 320-400n).
m), ultraviolet rays B (wavelength 290-320n, which are not normally absorbed by ozone but are considered to cause skin cancer)
m), there is ultraviolet C (wavelength 290 nm or less) that does not reach the ground. (Chemistry, Vol. 46, No. 11, p. 48, published by Kagaku Doujinsha) If these can be detected separately, it is good for preventing skin cancer, and it is also very useful for people who are naturally born with allergies to ultraviolet rays. In this way, polyesters (310 n for polyethylene terephthalate) are placed on the front surface and absorb specific ultraviolet rays.
It absorbs almost all ultraviolet rays of m or less), polystyrene (most of ultraviolet rays of 280 nm or less is absorbed), ordinary glass (most of ultraviolet rays of 290 nm or less is absorbed), and ultraviolet rays of a specific wavelength in the polymer. Such compounds may be dispersed. Examples of such compounds include rosolinic acid, astrazone orange G, acridine yellow G, acridine orange, acriflavine,
3.6-diaminoacridine, 4- (4-nitrophenylazo) resorcinol, 2- (5-bromo-2-pyridylazo) -5- (diethylamino) phenol and the like can be used. The amount of these substances used is preferably in the range of 0.0001% to 10% with respect to the polymer to be mixed. Further, the ferrocene derivative may be contained in the polymer at the same time in order to increase the sensitivity to ultraviolet rays.
As the ferrocene derivative, any of commercially available ferrocene compounds such as ferrocene, ferrocenecarboxylic acid and dimethylaminoferrocene can be used. Since the product of the present invention having increased sensitivity develops color by exposure for a short time, it becomes a simple device for monitoring the intensity of ultraviolet rays at present. Next, examples will be shown.

【Example】

Example 1 Methylene blue tetrahydrate (manufactured by Wako Pure Chemical Industries for vital staining) 3
9 g was dissolved in 10 liters of water, and 25 g of sodium hydrosulfite (Wako Pure Chemical Industries, Ltd. reagent grade 1) was added and the reaction was carried out at room temperature for 1 hour. To this, 5 liters of chloroform (special grade manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred. The methylene blue leuco base is extracted in the chloroform layer. The chloroform layer was separated using a separating funnel, and 10 ml of triethylamine (the same) and 28 of methyl chloroformate (the same) were added to this.
g was added and reacted at room temperature for 18 hours. Methanol 1
After adding 00 ml and keeping at room temperature for 3 hours, the reaction solution was packed with silica gel and had a diameter of 8 cm and a length of 1
The solution was passed through a 50 m glass column (equilibrated with chloroform), and the fractions eluted with a mixed solvent of chloroform and methanol 20: 1 were collected and concentrated to give methanol 1.
The crystals were recrystallized from liter and dried under reduced pressure to obtain 12.6 g of 10-N-methoxycarbonyl-3.7-bis (dimethylamino) -phenothiazine (abbreviated as MOCP). The melting point of this product was 132-134 ° C. Example 2 39 g of methylene blue tetrahydrate (described above) was reduced with sodium hydrosulfite in the same manner as in Example 1, and the leuco base of methylene blue was similarly extracted into the chloroform layer. The chloroform layer was separated with a separating funnel, 33 g of phenyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, the reaction was carried out at room temperature for one day and night, and then 500 ml of methanol was further added and reacted at room temperature for 8 hours. The reaction solution was similarly purified with a glass column filled with the above silica gel,
The fraction was concentrated, recrystallized from methanol, dried under reduced pressure, and concentrated to 10
-N-phenylaminocarbonyl-3.7-bis (dimethylamino) -phenothiazine (abbreviated as PACP) 24.
3 g was obtained. The melting point of this product was 143-145 ° C. Example 3 Bind Shedler's Green Leuco Base (manufactured by Dojindo)
2.55 g of chloroform was dissolved in 500 ml of chloroform, to which methylthioisocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and reacted at room temperature for 2 days, and the reaction solution was passed through a silica gel column for purification in the same manner as above. Methanol 200
Recrystallized in milliliters. It was dried under reduced pressure to obtain 1.37 g of N-methylaminothiocarbonyl-bis (4-dimethylaminophenyl) amine (abbreviated as MATA). The melting point of this product was 180-182 ° C. Example 4 Instead of the phenyl isocyanate of Example 2, (1)
Acetic anhydride (the same), (2) methyl chlorothioformate (manufactured by Aldrich Chemical Company), (3) methyl isocyanate (manufactured by Wako Pure Chemical Industries), (4) methyl thioisocyanate (manufactured by Aldrich Chemical Company),
(5) m-xylylene diisocyanate (manufactured by Wako Pure Chemical Industries), (6) hexamethylene diisocyanate (the same),
(7) p-Tolylene diisocyanate (the same) and (8) ethyl isocyanate acetate (manufactured by Aldrich Chemical Company) were reacted and purified in the same manner to obtain compounds as shown in Table 1.

[Table 1] Example 5 Basic blue 3 was used in place of methylene blue in Example 1, acetic anhydride was reacted in place of phenyl isocyanate, and purification was carried out in the same manner as in Example 1 to obtain 10-N-methylcarbonyl-3.7-. 9.2 g of bis (diethylamino) -phenoxazine was obtained. Example 6 10 g of polystyrene was melted in a metal container heated to 110 ° C., 0.1 g of MOCP was added and dissolved therein, and the film was uniformly thinly spread on an aluminum plate and cooled to form a film. This film was cut into an appropriate size and attached to a container as shown in FIG. 2 below to prepare an ultraviolet film badge.

FIG. 2 Example 7 An ultraviolet irradiation device that emits ultraviolet rays having a wavelength of 254 nm to the film badge prepared in Example 6 (HP manufactured by ATTO Co., Ltd., HP
When exposed for 30 minutes under a lamp of (-6 LC) for 30 minutes, it was colored dark blue. Take out the blue-colored film near the center from the container and measure it with a spectrophotometer at 666 nm.
The absorbance at 0.98 was measured and found to be 0.938. When the thickness of the film was measured separately, it was 0.11 mm, and the absorbance per cm of the thickness of this film was calculated to be 85.27. In order to confirm the quantitativeness of the amount of ultraviolet rays, an experiment similar to this was performed with an exposure time of 0 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes.
The absorbance was 2.
It became 5, 16.3, 31.0, 43.6, and 57.7. When this was graphed, linearity was obtained as shown in FIG.

FIG. 3 Example 8 10 g of polystyrene was melted in a metal container heated to 110 ° C., 0.1 g of PACP was added and dissolved therein, spread evenly and thinly on an aluminum plate, and cooled to form a film. This film was cut into an appropriate size and attached to a container shown in the figure below to prepare an ultraviolet film badge. Example 9 An ultraviolet irradiation device (HP manufactured by Ato Co., Ltd., which emits ultraviolet rays having a wavelength of 254 nm, is applied to the film badge prepared in Example 8.
When exposed for 30 minutes under a lamp of (-6 LC) for 30 minutes, it was colored dark blue. The blue discolored film was taken out from the container, and the absorbance at 666 nm was measured with a spectrophotometer to find that it was 1.478. When the thickness of the film was measured separately, it was 0.13 mm, and the absorbance per cm of the thickness of this film was calculated to be 113.7. In order to confirm the quantitativeness of the amount of ultraviolet rays, the same experiment was carried out by changing the exposure time to 0 minutes, 5 minutes, 10 minutes, 15 minutes and 20 minutes, and the absorbances were 0.6 and 19.
5, 38.2, 56.8, and 76.1. This graph is shown in FIG. Example 10 10 g of polystyrene was melted in a metal container heated to 110 ° C., 0.1 g of MATA was added and dissolved therein, and uniformly spread thinly on an aluminum plate and cooled to form a film. This film was cut into an appropriate size and attached to a container shown in the figure below to prepare an ultraviolet film badge. Example 11 The film badge prepared in Example 10 was measured at a wavelength of 366 nm.
UV irradiation device that emits the
30 cm from the P-6LC switch) lamp
When it was left to stand for 30 minutes under exposure, it was colored green. Remove the blue-colored film from the container and use a spectrophotometer to
When the absorbance at 20 nm was measured, it was 0.951. When the thickness of the film was measured separately, it was 0.15 mm, and the absorbance per 1 cm of the thickness of this film was 63.
Calculated as 5. In order to confirm the quantitativeness of the amount of ultraviolet rays, an experiment similar to this was performed with an exposure time of 0 minutes, 5 minutes, 10 minutes, 15 minutes.
The absorbance was 0.5, 11.8, 20.3, 31.3, and 42.7, respectively, after changing the time to 20 minutes. This graph is shown in FIG. Example 12 An ultraviolet irradiation device that emits ultraviolet rays having a wavelength of 366 nm to the film badge prepared in Example 8 (HP manufactured by ATTO Co., Ltd., HP
When exposed by being left for 30 minutes under a lamp (switching of -6LC), it was colored dark blue. Remove the blue-colored film from the container and use a spectrophotometer to
The absorbance at 66 nm was 1.126. The thickness of the film was 0.13 mm, and the absorbance per cm of the thickness of this film was calculated to be 73.6.
In order to confirm the quantitativeness of the amount of ultraviolet rays of this wavelength, the same experiment was conducted with exposure times of 0 minutes, 5 minutes, 10 minutes, 15 minutes, and 2 minutes.
When it was changed to 0 minutes, the absorbance was 0.
It became 6, 12.9, 25.0, 37.1, and 48.2. This graph is shown in FIG. Moreover, even when this device was left under a sodium lamp that does not emit ultraviolet rays, it was hardly colored. Although it doesn't feel like visible light like this, even in the high energy UV of 254 nm,
Even at an energy as low as 366 nm, a coloring degree correlated with the cumulative amount of the irradiated ultraviolet rays was obtained, which proves that the film of the present invention is useful. Example 13 The film badge prepared in Example 8 was used in fine weather in summer, for 1 hour from 11:00 am to noon when the ultraviolet rays were strong, directly exposed to the sun, placed in the shade at the same time, and subjected to a metal plate as a target. Although the film was placed right next to it with a light shield in between, when the color of the film was examined by changing the three kinds of irradiation conditions, the product was strongly colored, and the absorbance per 1 cm of thickness was 53.9. calculated. The product of 1 was slightly colored, the same absorbance was calculated to be 5.4, and the product of 1 was not colored at all. Example 14 290 nm on side A of the film badge prepared in Example 8
When a 1 mm thick polyethylene terephthalate film was covered so as to absorb the following ultraviolet rays and the same experiment as in Example 2 and Example 3 was carried out, the object to which 254 nm ultraviolet rays were applied was slightly colored, but 366 nm. The product applied to the sample became dark blue, and the absorbance was measured and calculated to be 10.2 and 78.3, respectively. The coloration at 254 nm was drastically reduced by a factor of 11 and the coloration at 366 nm was slightly reduced. Stayed in. Thus, the device can be made specifically sensitive to 366 nm UV light. Example 15 Melted polystyrene 10 as in Example 8
A measuring instrument was prepared using a film in which 0.1 g of PACP and 0.01 g of ferrocene were dissolved in g. This instrument was exposed to 254 nm UV light for 0 minutes, 30 seconds, 1 minute,
After changing the color to 1.5 minutes and 2 minutes, the blue discolored film was taken out from the container, and the absorbance at 666 nm was measured with a spectrophotometer. The absorbance per 1 cm of film thickness was 0.7, 17. It was 6, 32.6, 44.7, and 66.2. When the photosensitizer is mixed in this way, it becomes a very sensitive instrument and the measurement can be completed in a short time, so that it can be used as a monitor. Example 16 The compounds shown in the following table were sequentially mixed with a polymer film in the same manner as in Example 6 to prepare a film. When this was left to stand for 30 minutes under a lamp of an ultraviolet irradiation device (HP-6LC manufactured by Atto Co., Ltd.) which emits ultraviolet rays having wavelengths of 254 nm and 366 nm, it was exposed to light, but all were colored in blue. The blue-discolored film was taken out of the container, and the absorbance at 666 nm was measured with a spectrophotometer. The values were as shown in the table.

[Table 2] As described above, it has been found that the compounds shown here exhibit coloration with various sensitivities to ultraviolet rays, and they can be applied to the apparatus of the present invention, and can detect ultraviolet rays with various sensitivities.

[Brief description of drawings]

FIG. 1 is a plan view and a front view (partially sectional view) of the present invention.

FIG. 2 is a plan view and a front view (partially sectional view) of the present invention.

FIG. 3 is a graph of the results obtained in Examples 7, 9, 11, and 12.

Claims (2)

[Claims] 1. A general formula: (In the formula, X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom, a sulfur atom, a —NH— group or a methylene group, and R ₁ represents an alkyl group having ₁ to 6 carbon atoms, or a substituted alkyl group (as a substituent group). Phenyl, hydroxy, alkoxy, halogen,
Sulfonyl, amino, carboxy, nitro, each group), phenyl, substituted phenyl (the same as the above), R ₂ R ₂ ′ may be the same or different, and hydroxy, amino, carbon number 1- 6 mono- or di-alkylamino groups, R ₃ R ₃ ′ may be the same or different and represent hydrogen, alkyl having 1 to 6 carbon atoms, or R ₃ R ₃ ′ has one atom (oxygen or (Sulfur) may be shared to form a ring. R ₄ R ₄ ′ may be the same or different, and are an alkyl group having 1 to 6 carbon atoms,
Indicates a halogen group. ) Containing polymer molded products 2. A light quantity measuring instrument equipped with the polymer molded article according to claim 1.