JPS5933841B2 - sunburn monitoring display - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improvement in a sunburn monitoring display using an indolinospiropyran compound, which is a photochromic material.

Strong ultraviolet rays (・If your skin is exposed to sunlight for a long time, such as at the beach in the summer or on snowy mountains in the winter, it can cause skin blackening and inflammation.
It is well known that a so-called sunburn phenomenon occurs.

Various cosmetics and therapeutic agents related to sunburn have been developed, ranging from sunburn prevention and post-sunburn treatment to cosmetics that make it look as if you have sunburn.

In general, the wavelength of ultraviolet rays that can cause sunburn on the skin is 2.
, 900 to 3,200 A, and it is said that those with short wavelengths cause rapid sunburn, and those with long wavelengths promote an increase in pigmentation.

Sunscreen prevents sunburn and reduces its effect on the skin by scattering, absorbing, or blocking ultraviolet rays. Chemicals that have these effects include white pigments such as titanium oxide, zinc white, and talc that scatter light, and organic substances such as para-aminobenzoic acid, benzophenone U, and urocanic acid that absorb light. A method used is to apply a thick layer of oil-based powder to the object to be blocked. A comprehensive combination of these ingredients is sold as a sunscreen cream. However, the degree of sunburn varies from person to person, and the use of the above sunscreen creams may cause inflammation due to chemical damage.In addition, the type of sunscreen cream and It is necessary to change the amount used, and until now these controls have only been achieved by relying on intuition.

Therefore, a sunburn monitoring display using a photochromic material has been proposed as a guideline for selecting and using an appropriate sunscreen cream by sensing the amount of ultraviolet rays in sunlight in advance, but the present invention uses a display with higher sensitivity. This was completed as a result of repeated consideration.

That is, the present invention provides a sunburn monitoring display that uses a visible light filter in combination with a film made of an indolinospiropyran compound, which is a photochromic material, and a resin that has weak ultraviolet absorption. Photochromism is a phenomenon in which the light absorption spectrum of a substance changes reversibly by irradiating it with light.

There are many substances that exhibit this photochromism, such as organic substances, crystalline inorganic substances, and glasses, but in the present invention, an indolinospiropyran compound is used. The indolinospiropyran compound is a substance with high photocoloring efficiency and controllable reaction rate, and is represented by the following general formula (I).

Here, in the formula (I), R3 is suitable for the present invention.
: An alkyl group (C1 to C8).

For example, 1,3,3-trimethylindolino-6'-nitrobenzopyrylspirane exhibits the following photochromic reaction.

When spiropyran absorbs ultraviolet light, the C-0 bond of the spiropyran ring in the molecule is cleaved to form a counter ion within the molecule.

As a result, it becomes a merocyanine dye-type molecular structure as shown in ([), and becomes a colored species with a strong absorption band in the visible light region. Species (return to I. Therefore, before irradiation with ultraviolet light, the surface is transparent, but after irradiation with ultraviolet light, it appears red in a polar medium and blue in a non-polar medium. In general, red bodies undergo decolorization reactions. Since it is dull, it is unsuitable for the present invention, and a blue body is preferable.

Therefore, it is required that the indolinospiropyran compound be selected from those described in d) above, and it is also required that the film be made of a resin with weak ultraviolet absorption. Of course, it is possible to use polar solvents during film formation, such as alcohols such as methanol, ethanol, isopropyl alcohol, and butanol, and ketones such as acetone and methyl ethyl ketone, which scatter after film formation. . The concentration of indolinospiropyran in the resin is 0.2 to 20%, more preferably 0.5 to 20%.
It is 5%. Examples of resins that have weak UV absorption include polymethyl methacrylate (PMMA), polypynylacetate (PVAC), polystyrene (PST), polyvinyl chloride (PVC), ethyl cellulose (EC),
Cellulose acetate (CAC), partially saponified polyvinyl acetate, etc. are dissolved in a suitable solvent, and spiropyran is also dissolved or dispersed therein to form a film.

The coating may be in the form of a single, uniform film, but it may also be dispersed in the form of capsules, and it also becomes stable in strength when applied to a plate or sheet support such as glass or paper.
When cellulose-based paper is used as a support, it does not affect the coloring reaction from the colorless species (I) to the coloring species, and has the effect of stabilizing the coloring species and slowing down the disappearance of the image due to visible light. In place of the above-mentioned resin used as a film-forming material, nitrocellulose that absorbs ultraviolet rays, a resin with poor dispersibility of indolinospiropyran, such as polyvinyl alcohol, polyacrylic acid, etc., can be used as a film-forming material. If used, this is not preferable because it may cause the appearance of colored species other than blue or the sensitivity may become dull, making determination difficult.

Next, when the resin film of indolinospiropyran is used alone, that is, when the film is exposed to direct sunlight, the spiropyran becomes a colored species and becomes colored by the ultraviolet rays contained in the sunlight. On the other hand, there is a drawback that some of the colored species revert to colorless species when exposed to visible light in the sunlight, making the determination inaccurate and taking too much time.

Therefore, the third requirement of the present invention is to eliminate the above drawbacks by irradiating the film through a visible light filter that preferably has maximum absorption of visible light in the vicinity of 500 to 600 nm, rather than exposing the film to direct sunlight. This problem was solved, and a sunburn monitoring display was created that can fairly accurately measure the intensity of ultraviolet rays in sunlight in just a few seconds.
This visible light filter allows ultraviolet rays to pass through, and the colorless species (
500 to 500, which do not affect the reaction from D to the colored species (sha) and are involved in the reverse reaction from the colored species 1[) to the colorless species (r).
Since only visible light of 600 nm is not transmitted, no reverse reaction occurs and accurate ultraviolet intensity can be measured in a short time. In addition, it is possible to measure the intensity of ultraviolet rays regardless of the differences in sunlight between morning, noon, and evening, which has the effect of eliminating the inaccuracy of relying on visual measurements or intuition. Finally, the following two methods are convenient for using the sunburn monitoring display according to the present invention.

The first method is to expose the film to sunlight for a certain period of time, for example, 3 to 10 seconds, through a visible light filter, and measure the amount of ultraviolet rays by comparing the degree of color development with a standard color table prepared in advance. The method is to expose the film to sunlight for a predetermined period of time using a visible light filter and an ultraviolet filter with a concentration gradient, and determine the amount of ultraviolet rays based on the size of the area of the saturated part.

EXAMPLES Hereinafter, the sunburn monitoring display of the present invention will be specifically explained with reference to Examples.

Example 1 1,3,3-trimethylindolino-6-nitrobenzopyrylspiran (
SP-1), and an acrylic resin made of polymethyl methacrylate (PMMA) was used as the resin.

The film was created as follows.

First, PMMA was dissolved in an 80:20 volume ratio mixture of methyl ethyl ketone (MEK) and methyl isopropyl ketone (MIPK) to make a 20% PMMA solution, and 10% of this
A sample was prepared by mixing and dissolving 0.4 part of the spiropyran (SP-1) per 0 parts of spiropyran, soaking a filter paper in the solution, and air-drying it in a dark place. The obtained filter paper supporting film is colorless,
SP-1 was a colorless species (D type) in acrylic resin. Next, as shown in Figure 1, the resulting display was placed on the right half of the slide glass as a dye with maximum absorption at a wavelength of about 550 nm. 3,3-trimethyl-2-[(4-
A visible light filter coated with dimethylanilino)ethylidene]benzoindolenium chloride was formed, and direct sunlight was irradiated through this filter for 5 seconds to form a display A. Color development in part B was observed.

Part A was a part without a visible light filter, and part B was a part with a visible light filter. As a result, the B part had a more vivid blue color than the A part.

In other words, in the case of part A that does not use a visible light film, in the case of light that contains a large amount of visible light, such as sunlight, the color produced by ultraviolet rays is erased and sufficient effects cannot be obtained, but when visible light is cut out, the amount of ultraviolet rays is reduced. It is vividly colored depending on the color. The degree of this coloring changes depending on the intensity of the UV rays and the exposure time, so if you print out a standard coloring chart in advance, you can easily measure the amount of UV rays and it can become a useful display for monitoring sunburn. It became clear. An example of the degree of color development and the amount of UV rays is shown in Figure 2.As shown in Figure 1, the color of display B is exposed to sunlight for 5 seconds through a shutter and visible light filter, and the amount of UV rays is measured using a UV meter. The results of the comparison showed that there was a correlation between the two.

Example 2 1,3,3-trimethyl-5-chloroindolino-6'-nitrobenzopyrylspiran (SP-2) was used as the indolinospiropyran compound, polyvinyl acetate was used as the resin, and the resin was 20% A butyl acetate solution was prepared, and 0.4 part of the above spiropyran (SP-2) was mixed and dissolved in 100 parts of the solution and applied onto a glass plate to form a film about 10 μm thick.

The film obtained after drying in a dark place was of the colorless type (1) type, became the blue type 1 [) type by absorbing ultraviolet light, and exhibited a reversible reaction to become the colorless type (1) by absorbing visible light. Subsequently, the obtained glass plate display was assembled into a device as shown in FIG. 3, and a test was conducted.

In FIG. 3, the visible light filter 1 is the one used in Example 1, and the ultraviolet filter 1 uses 2(4-diethylaminophenyl)benzothiazole as an ultraviolet absorbing substance, and coats it on a glass plate to absorb ultraviolet rays. amount to transmittance 8
The concentration gradient was divided into 60% and 40% from 0 (:f) or more to about 20 (:fl) to have four stages. Furthermore, using the apparatus shown in Fig. 3, the light was exposed for 30 seconds every 2 hours from 8:00 to 16:00 on the day of the end of the day, and the area ratio of the colored part was compared with the amount of ultraviolet rays measured by the ultraviolet ray meter. Obtained the results in the table.

As is clear from the results in Table 1, the correlation between the color development area ratio and the amount of ultraviolet rays is extremely good, and this method makes it possible to easily provide guidelines for the use of sunscreen creams.

Example 3 Films were created using the resins and solvents shown in Table 2 for the three types of spiropyran compounds listed below, and
When testing was conducted using the methods of Example 1 and Example 2,
Both SP-1. The results were similar to SP2, and an excellent sunburn monitoring display was obtained.

[Brief explanation of drawings]

Figure 1 is an explanatory diagram showing a test method to check the effectiveness of visible light filters, Figure 2 is a graph showing the amount of ultraviolet rays and degree of color development when using visible light filters, and Figure 3 is a graph showing visible light filters and density. FIG. 2 is an explanatory diagram showing a method for measuring the amount of ultraviolet rays by using a UV pool with a gradient in combination with Shioichi.

Claims (1)

[Claims] 1. In a display that monitors sunburn and inflammation caused by the chemical effects of sunlight's ultraviolet rays on the skin, a visible light filter is used in combination with a film made of an indolinospiropyran compound, which is a photochromic material, and a resin with weak ultraviolet absorption. A sunburn monitoring display characterized by: