JPH11344376A - Photochromic composition and ultraviolet sensor with photochromic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prolong a resistance lifetime and to reduce the size and cost by mixing a resin with a photochromic compound dissolved in a solvent, and curing their mixture in a suitable shape. SOLUTION: A photochromic compound (variable color dye) reacting with an ultraviolet ray or particularly an ultraviolet ray having a wavelength range to be measured is dissolved in a solvent such as, for example, a ketone and the like such as an acetone, methylethylketone or the like, alcohol and the like or other toluene or the like having good compatibility with the compound, further mixed with a resin, molded in a suitable shape or filled in a suitable container, dried, and cured. The photochromic compound contained in the resin exhibits luminescent characteristics substantially similar to the state dissolved in the solvent to the ultraviolet ray, and can hold the initial characteristics at least for half a year.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photochromic composition, a method for producing the same, and an ultraviolet sensor containing the photochromic composition.

[0002]

2. Description of the Related Art In recent years, the harmful effects of ultraviolet rays, including not only short-term adverse effects of ultraviolet rays such as severe sunburn, but also long-term effects such as carcinogenesis, have been increasingly recognized in recent years. . Even in daily life, for example, while walking, working outdoors, etc., it is exposed to ultraviolet light throughout the year. It is desired that a device that can easily detect ultraviolet light is incorporated in a product that is always portable, that the intensity of ultraviolet light can be easily measured, and that each individual can respond to ultraviolet light according to the result. In addition, there is a demand for accessories and jewelry that change color when irradiated with ultraviolet light.

In such an application, a device that obtains an electrical signal and displays it, such as a conventional ultraviolet detector even though it is small, has a portability, a price, a size, and the like. In many respects such as securing power supply, it is not practical. Therefore, there is a need for an ultraviolet sensor capable of easily visually determining the intensity and properties of ultraviolet light so as to respond to ultraviolet light according to the intensity of ultraviolet light.

As a substance that can be used for detecting ultraviolet light, a variable color dye (photochromic compound) that changes color in response to irradiation of ultraviolet light is known. An ultraviolet sensor using such a photochromic compound is disclosed in JP-A-6-3188 and JP-A-6-1299.
The technology described in JP-A-01 is known. JP-A-6-3188 discloses an ultraviolet sensor for identifying ultraviolet rays A and B, in which a film that absorbs ultraviolet rays in a specific frequency range and a thin film of a photochromic compound are formed on the surface of an article by a printing method. ing.

[0005] This sensor can be easily arranged on the surface of various products because of the printing method. However, since the matting agent is used and the color tone of the color is monotonous and is applied deeply, the sensor cannot be used for earrings. Decorative items, such as necklaces, where emphasis is placed on aesthetics, have drawbacks that are difficult to apply. In addition, such a sensor has a drawback that its life is short. Japanese Patent Application Laid-Open No. 6-129901 discloses a photosensor that detects a change in absorbance due to ultraviolet rays using a photodiode. According to this technique, what is output as a result of detecting the ultraviolet light is the current of the photodiode.

Also, Japanese Patent Application No. 9-2818 filed by the present inventors.
No. 37 describes an ultraviolet sensor in which a solution of a photochromic compound is sealed.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an ultraviolet sensor having a long resistance life. Another object of the present invention is to provide a small and inexpensive ultraviolet sensor useful in applications where aesthetics are important, such as necklaces and bracelets. Still another object of the present invention is to provide a necklace, which allows fine adjustment of sensitivity and detection area.
It is possible to provide a small and inexpensive ultraviolet sensor useful in an application field where aesthetics are important, such as a bracelet, a button, and an earring. Still another object is to provide an ultraviolet coloring material.

[0008]

SUMMARY OF THE INVENTION The present invention provides a cured photochromic composition comprising a solvent, a photochromic compound dissolved in the solvent, and a resin. Further, the present invention provides an ultraviolet sensor containing the above photochromic composition and curing the composition.

Further, the ultraviolet sensor according to the present invention comprises:
A photochromic compound, a solvent, a resin, and at least one chamber containing and curing at least one of the above photochromic compositions whose concentrations are substantially the same,
It comprises at least two electrodes provided in each of the small chambers, a power supply unit for applying a voltage to each small chamber through the electrodes, and a control unit for controlling the voltage applied to each small chamber. be able to. Further, the ultraviolet sensor according to the present invention is a photochromic compound, a solvent, a resin,
A plurality of small chambers containing and curing at least two kinds of the photochromic compositions different in at least one of their concentrations; at least two electrodes provided in each of the small chambers; And a power supply for supplying power to the control unit. The ultraviolet sensor of the present invention may have a filter that transmits ultraviolet light in a specific frequency range so as to respond only to ultraviolet light in a specific frequency range.

In the present invention, a photochromic composition containing a solvent, a photochromic compound dissolved in the solvent, and a resin can be diluted with the solvent to a concentration at which the composition can be applied to be used as an ultraviolet coloring material. The present invention further provides a method for producing a cured photochromic composition in which a photochromic compound is dissolved, a solvent in which the photochromic compound is dissolved is mixed into a curable resin, and the resin mixture is cured.

Since the photochromic composition of the present invention is considered to be mixed in a resin in a state where the photochromic compound is dissolved in a solvent, the photochromic composition exhibits almost the same emission characteristics as the state dissolved in the solvent. In the state of being dissolved in the solvent, the resistance life is about one and a half months, whereas when the photochromic compound dissolved in the solvent is mixed into the resin as in the present invention, the initial life is at least half a year. Light emission characteristics can be maintained.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A photochromic compound according to the present invention is obtained by dissolving a photochromic compound in a solvent, further mixing it into a resin, molding it into an appropriate shape or filling it into an appropriate container, and then drying and curing. And

The solvent for dissolving the photochromic compound is appropriately selected according to the compatibility with the photochromic compound and the desired color development. The compatibility of the photochromic compound with the solvent, the color development, the resistance of the container material to the solvent, and the like are well known, and those skilled in the art can easily make this choice. Examples of the solvent include ketones such as acetone and methyl ethyl ketone, alcohols such as ethanol, and toluene. As the mixing ratio of the photochromic compound in the photochromic composition, the mixing ratio of the photochromic compound to the total volume of the photochromic composition is 0.1%.
5-3% is preferred. The most visible color is 1
~ 2%.

As the photochromic compound, for example, various dyes commercially available from Japan Photosensitive Dye Laboratories can be used. In the present invention,
It is used in the form of a resin containing a photochromic compound dissolved in a solvent. Since the photochromic compound contained in the resin is considered to be in a form dissolved in a solvent, it is in a state close to the characteristics when present in the solvent,
It exhibits the same luminescence characteristics as ultraviolet light contained in a solvent.

The photochromic compound that can be used in the present invention is not particularly limited as long as it reacts with ultraviolet rays, particularly, ultraviolet rays in a wavelength range to be measured. 3′-dihydro-1 ′, 3 ′, 3′-trimethyl-6-nitrospiro [2H-1-benzopyran-2,2 ′-[2H] indole], 1 ′, 3′-dihydro-8-methoxy-1 '
3'3'-trimethyl-6-nitrospiro [2H-1-
Benzopyran-2,2 ′-[2H] indole], 1,
3-dihydro-1,3,3-trimethylspiro- [2H
-Indole-2,3 '-[3H] -naphtha [2,1-
b] [1,4] oxazine] and the like. These substances are shown in the following Chemical Formulas 1 to 3, respectively.
"SP-
1 "," SP-2 ", and" SP-99 ". These dyes are known to reversibly change color upon receipt of ultraviolet light radiation. Upon irradiation with ultraviolet light in methanol, SP-1 and SP-2 show red, and SP-99 shows pale green. Of the photochromic compounds listed above, SP-99 is most preferred in terms of durability.

[0016]

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[0017]

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[0018]

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The resin which can be used in the present invention is preferably a resin having good crystallinity. For example, a vinyl acetate resin, a modified styrene butadiene rubber (hereinafter referred to as "modified SB")
R "), an acrylic resin, a styrene resin, and the like. Among them, vinyl acetate and acrylic resin are preferred. These resins are cured in accordance with evaporation of the solvent, and exhibit a solid state having various flexibility.

In an application field in which aesthetics are important such as necklaces and bracelets, it is particularly preferable to use vinyl acetate or acrylic resin as the resin. In this case, the photochromic composition of the present invention in which a solvent in which a photochromic compound is dissolved and a resin are mixed into a frame of metal, plastic, glass, or the like may be formed into a desired form and size.

For example, as shown in FIG. 2, a photochromic composition before drying is poured into a metal frame 5, the surface is closed with a glass plate 6, and cured, whereby the inside of the metal frame 5 and the glass plate 6 are sealed. The photochromic composition 7 is formed. The photochromic composition thus created is
Since it has a jewel-like appearance, it can be used in application fields where aesthetics are important such as accessories.

The mixing ratio of the resin in the photochromic composition is 10 to 40%, preferably 15 to 30%, more preferably about 20%, based on the total volume of the photochromic composition. Further, the mixing ratio of the photochromic compound in the photochromic composition, 0.05 to the total volume of the photochromic composition,
3%, preferably 0.1-2%, more preferably 0.1%.
It is about 5 to 2%.

In the present invention, the irradiation intensity of ultraviolet rays can be detected by filling a small chamber with a photochromic compound, a solvent, a resin, and a photochromic composition having the same concentration or one or more different concentrations. An ultraviolet sensor can be provided. Instead of the photochromic compound, it is also possible to use a fluorescent substance.

FIG. 1 shows an example of the ultraviolet sensor of the present invention. The ultraviolet level meter 1 has a plurality of cells (small chambers) 2
Are arranged, and a pair of electrodes (not shown) are stored therein. Each cell 2 is hermetically filled with a photochromic composition using the same concentration, the same solvent, and the same resin.
V) is applied through the DC-DC boosting circuit 4. By changing the voltage applied to each cell 2, the sensitivity of each cell to ultraviolet light can be changed. Therefore, the intensity of ultraviolet light can be measured by reading up to which cell the color has been formed.

Various plastics including polypropylene, glass, etc. can be used as the material of the small chamber. In addition to consideration of factors such as strength and aesthetics, materials having resistance to selected solvents and resins are used. You need to choose. In addition, a small container made of a material having resistance to a solvent and a resin may include a plurality of small chambers.

The size and shape of the small chamber are not particularly limited, but a cube of about 2 mm to 2 cm or a rectangular parallelepiped or a cylinder having sides within the range, and a size of about 2 mm to 2 cm.
There is a sphere having a diameter of about a centimeter. When the small container has a configuration including a plurality of small chambers, the small container is configured by collecting two or more such small chambers. When there are two or more compartments, it is possible to not only determine the presence or absence of ultraviolet light, but also to know the degree of ultraviolet light intensity. Each compartment is preferably independent of the other compartments.

In the ultraviolet sensor of the present invention, by providing an electrode in the small chamber and applying a voltage thereto, the color development, the ultraviolet detection sensitivity, and the like can be easily changed. The voltage can be controlled manually by setting circuit parameters in advance or by using a microswitch, a volume, or the like. This voltage control unit includes a booster circuit, a step-down circuit, and the like. Therefore, when the ultraviolet sensor includes a plurality of small chambers, a level meter including a plurality of cells having different colors can be obtained by changing the voltage of each cell even if the coloring matter, the solvent, and the concentration are the same. In addition, when the conditions such as coloring matter are changed in each cell, by controlling the voltage, it is possible to change the intensity of ultraviolet light that causes discoloration of the cell, etc., so that one sensor has a wider measurement range. be able to.

It is also possible to use one of the electrode pairs for each small chamber as an electrode common to all or a plurality of small chambers.

As a power source, various batteries including a solar battery and a small button battery can be used. The voltage from such a battery can be boosted using an electronic circuit such as a DC-DC boost circuit and applied to the electrodes.
Since the electrodes flowing between the electrodes are weak even when the voltage is raised, a small capacity of the power supply is sufficient. For example, even a solar cell having a small light receiving surface can obtain necessary power.

The photochromic compound is usually 2
Since it responds to the ultraviolet frequency of 00 to 400 nm, by using a filter that absorbs ultraviolet light of a different frequency, for example, by using a filter that absorbs ultraviolet light B (wavelength of 320 to 290 nm), the ultraviolet light A (wavelength of 400
(Up to 320 nm), and an ultraviolet level meter that is mainly sensitive to ultraviolet rays B can be created using a filter that absorbs ultraviolet rays A. By combining these UV level meters, for example, UV A and UV B
And the intensity of different types of ultraviolet light can be measured independently.

In the present invention, a photochromic composition containing a solvent, a photochromic compound dissolved in the solvent, and a resin can be diluted with the solvent to a concentration at which coating can be performed, and used in an ultraviolet color-forming paint. This UV-coloring paint is applied by spraying or brushing, printing method,
Can be placed on the surface of various products such as paper and fabric,
The degree of dilution with the solvent at this time was determined by dissolving the solvent in which the photochromic compound was dissolved in an amount of 1 to 2% (by volume) to 70% of the total volume.
It is desirable that the content be 80% to 80% and the resin be 20% to 30%. In addition, since various colors can be colored by selecting a photochromic compound and a solvent, the present invention can be applied to accessories and clothes where beauty is important, such as clothing and the like.

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. (Example 1) As a photochromic compound, "SP-
Using "1", it was dissolved in toluene at a rate of 1% (volume). The dissolved toluene of SP-1 was added to a total volume of 70%.
%, And modified SBR so as to be 30% of the total volume, molded into an appropriate shape, and air-dried to obtain a photochromic composition. The absorbance at 240 to 400 nm of the obtained photochromic composition was measured. The composition exhibited a blue color due to ultraviolet radiation.

Example 2 Using "SP-99" as a photochromic compound, 2% (volume) in ethanol
At a rate of The ethanol in which SP-99 was dissolved was mixed to 70% of the total volume, and vinyl acetate was mixed to 30% of the total volume, molded into an appropriate shape, and air-dried to obtain a photochromic composition. The absorbance at 240 to 400 nm of the obtained photochromic composition was measured. The composition exhibited a blue (blue-green) color due to ultraviolet radiation. This composition was irradiated with a black light to repeatedly perform a color development test. The test is U
The measurement was performed with a cycle in which irradiation was performed at a V intensity of about 60 W / m ² for 10 seconds and then stopped for 20 seconds as one cycle. As a result, it was found that the composition maintained its color even after at least 20,000 cycles of irradiation, and had a long life.

Example 3 A photochromic compound "SP-1" was dissolved in acetone at a ratio of 1% (volume). Acetone in which SP-1 was dissolved was mixed so as to be 80% of the total volume, and vinyl acetate was mixed so as to be 20% of the total volume. The mixture was molded into an appropriate shape, and then naturally dried to obtain a photochromic composition. The absorbance at 240 to 400 nm of the obtained photochromic composition was measured. This composition exhibited a purple-red color due to ultraviolet radiation.

(Example 4) "SP-1" was used as a photochromic compound and dissolved in toluene at a ratio of 1% (volume). A mixture of 20% of acrylic resin and 80% of methyl ethyl ketone was mixed to 40% of the total volume, and toluene in which SP-1 was dissolved was mixed to 60% of the total volume,
After being formed into an appropriate shape, it was air-dried to obtain a photochromic composition. 2 of the obtained photochromic composition
The absorbance at 40-400 nm was measured. This composition is:
The ultraviolet radiation of 5~50W / m ^2, exhibited a red color, the emission of 50 W / m ² or more UV exhibited color purple.

Example 5 "SP-1" was dissolved as a photochromic compound in a solvent consisting of 80% toluene and 20% methyl ethyl ketone at a ratio of 1% (volume). SP-1 dissolved toluene was added to the total volume of 8
0% and an acrylic resin were mixed so as to be 20% of the total volume, molded into an appropriate shape, and then naturally dried to obtain a photochromic composition. The composition exhibited a blue color due to ultraviolet radiation.

(Example 6) 20% of acrylic resin, 30% of toluene, 30% of methyl ethyl ketone,
Ethanol was mixed to 20%, and further dissolved in the above mixture at a ratio of 2% (volume) using "SP-99" as a photochromic compound. After being formed into an appropriate shape, it was air-dried to obtain a photochromic composition. 240 to 40 of the obtained photochromic composition
The absorbance at 0 nm was measured. This composition develops blue (blue-green) color and is subjected to repeated color development tests as described in Example 2 above. As a result, it is found that the composition retains color even after at least 20,000 cycles of irradiation, and has a long life. It was found to have

As is clear from the results of Examples 1 to 6,
It was found that the photochromic composition obtained by dissolving the photochromic compound in a solvent and further mixing the resin with the resin developed a color in accordance with the emission characteristics of the compound when irradiated with ultraviolet light.

[0039]

According to the present invention, it is possible to obtain an ultraviolet sensor having a small size, excellent aesthetics, and a long durability life. Such an ultraviolet sensor can be easily incorporated into accessories, clothes, bags, shoes, and various other everyday items worn daily. Therefore, according to the intensity of the ultraviolet light indicated by the sensor of the present invention, to avoid the ultraviolet light,
Various means can be taken. The sensor of the present invention
It is useful not only for women who are interested in beauty but also as a supplementary means to prevent skin damage from ultraviolet rays, such as policemen and outdoor construction workers who are often exposed to the sun. Further, since the color tone of the photochromic compound of the present invention changes due to ultraviolet light, it can be incorporated into the above-mentioned everyday product not for the function as a sensor but for enjoying the color tone change outdoors.

Since the ultraviolet sensor of the present invention can detect even an ultraviolet ray having an intensity of about 5 W / m ^2, it can measure even a small amount of ultraviolet light entering a room and can be used as an indoor ultraviolet sensor. Furthermore, the ultraviolet sensor of the present invention has a measurement capability in the UVB to UVC range as UV characteristics, and can detect destruction of the ozone layer and the like by coloring.

Further, according to the present invention, the response of a photochromic compound or a fluorescent dye to ultraviolet light can be changed by using weak electric power. This makes it possible to easily and inexpensively obtain an ultraviolet sensor having a wider measurement range.

[Brief description of the drawings]

FIG. 1 shows an example of an ultraviolet sensor of the present invention.

FIG. 2 shows an application example of the photochromic composition of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 UV sensor 2 cell (small chamber) 3 solar cell 4 booster circuit 5 metal frame 6 glass plate 7 photochromic composition

Claims (7)

[Claims] 1. A cured photochromic composition comprising a solvent, a photochromic compound dissolved in the solvent, and a resin. 2. An ultraviolet sensor containing the photochromic composition according to claim 1 and curing the composition. 3. A photochromic compound, a solvent, a resin,
And at least one chamber containing and curing at least one photochromic composition according to claim 1 having substantially the same concentration, and at least two electrodes provided in each of the chambers. An ultraviolet sensor including a power supply unit for applying a voltage to each small chamber through an electrode, and a control unit for controlling a voltage applied to each small chamber. 4. A photochromic compound, a solvent, a resin,
And a plurality of chambers containing and curing at least two photochromic compositions according to claim 1 having at least one of different concentrations, and at least two electrodes provided in each of the chambers. An ultraviolet sensor including a control unit that controls a voltage applied to each small chamber through an electrode, and a power supply that supplies power to the control unit. 5. The ultraviolet sensor according to claim 2, further comprising a filter that transmits ultraviolet light in a specific frequency range, and responsive to only the ultraviolet light in the specific frequency range. 6. An ultraviolet-color-forming coating, characterized in that a photochromic composition comprising a solvent, a photochromic compound dissolved in the solvent, and a resin is diluted with the solvent to a concentration at which the composition can be applied. 7. A method for producing a cured photochromic composition in which a photochromic compound is dissolved, a solvent in which the photochromic compound is dissolved is mixed into a curable resin, and the resin mixture is cured.