JPS58126528A - Chemical ray monitor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a medium which can be irradiated with actinic radiation to produce an image, in particular an image-forming operation that can be reversed, ie it is possible to erase the recorded image. The present invention relates to an instrument that can be used to create or record images using media containing the potentially photochromic aziridine.

Many common biochemicals undergo irreversible changes when irradiated with actinic radiation. Therefore, erasure cannot occur without physical destruction of myself. In addition, in many cases the images formed are latent and therefore require subsequent development.

Photochromes are compounds that reversibly change color when irradiated with actinic radiation. Such directly coloring photochromic materials, however, have the limitation that the stability of systems containing these materials is extremely low, i.e., the image will disappear within minutes or hours at room temperature. Traditionally experienced.

The specially formulated photochromic aziridine compound can be used to record, erase, and add information, and the film can be reused, etc. It was confirmed by Gato ζ.

Moreover, when this compound is rapidly deposited on a support, it can be used for high resolution, long term recording. These films can be used in data storage applications such as V# geo discs or microfiche, particularly in connection with high density data storage. Although direct development is possible, such media can be renewed or removed. The films can further be used as intermediates in photographic and/or copying processes and as reinforcing substances.

This article can also be used with a spectral filter 14 to monitor exposure to actinic radiation.

U.S. Patents 6 and 8 of Schleigh et al.
No. 94,874 describes the use of aziridine in photoreductive formation. In this patent, a reducing self-forming compound is combined with a photochromic aziridine in a binder on a support to form a radiation-sensitive layer. Irradiation with actinic radiation followed by heating gives me. moreover,
No. 3,964,823 discloses that partially crystalline and partially crystallographically ordered nine photochromic aziridines and oxiranes are useful in windshields, sunglasses, and flashing switch applications. Disclosed.

By applying a photochromic aziridine as defined below onto the support, and by utilizing an oxygen blocking material to cover the aziridine coating, the lifetime of the aziridine formed by exposure to actinic radiation can be improved. It was found here that the lifetime of photochromic aziridine in oxygen or air could be increased by at least a thousand times.

According to the invention, at least one of its surfaces has the formula: where R1> and R are independently hydrogen, lower alkyl, phenyl, or ortho- or para-lower alkyl or lower alkoxy-substituted phenyl, and - at least one coating or film of a photochromic aziridine which is an alkylene having from 4 to 7 (inclusive) carbon atoms; is a thermally stable optically conductive material comprising a support integrally therewith covered by a substantially oxygen-impermeable barrier coating sufficiently transparent to actinic radiation to permit passage therethrough. A device is provided that uses a medium for creating or recording erasable information.

This medium can be imaged by exposure to actinic radiation, optically erased, and reimaged, and it is substantially resistant to thermal decolorization.

As used herein, the term "actinic radiation" refers to any radiation having sufficient intensity to cause a chemical reaction in the manner consisting of a W* projectile.

The photochromic aziridine utilized in the present invention is 2R1,2az-6(p-nitrophenyl)-4-phenyl-1,6-diadepicyclo[5°1.0]hex-
6-dyne, which can be structurally represented as substituted phenyl (wherein the term "lower" refers to 1 to 4 carbon atoms), and R1 and R taken together are alkylene having 4 to 7 (inclusive) carbon atoms; There is. These compounds can be converted to r by highy (Re1n@) etc.
, Org, Ohem.

32.2708-10 (1967) and by the methods disclosed in US Pat. No. 3,609,165. The most preferred compound for this invention is the dimethyl derivative, namely 2,2'-dimethyl-6 (p
-nitrophenyl)-4-phenyl-1,6-diadebicyclo(3,1,0)hex-6-ene. Preferred alkylene derivatives include cyclohexyl and cyclopentyl derivatives.

If these aziridines are exposed to an electron beam or ultraviolet light in the dark, they become colorless again: the color change is reversible. Moreover, they can be decolorized thermally or by irradiation with visible light, ie they will revert to their colorless state by use of such methods. Therefore, the colorless form of photochromic aziridine can be converted to the colored form when irradiated with electron beams or ultraviolet light, and the reversible reaction back to the colorless form occurs when aziridine is irradiated with visible light or in the dark. It can be woken up when placed inside or thermally.

This can be depicted as follows:
B dark hν2 where the term B represents the colorless form, B represents the colored form, νl is the radiation frequency limited to ultraviolet light, and ν
2 is a radiation frequency limited to visible light.

It has now been established that in the absence of oxygen, the thermal bleaching reaction can be substantially reduced and the photochromic material can be made dark-stable.
Thus, to illustrate this phenomenon, a vapor-deposited film of a dimethyl derivative was coated on a quartz support, left to stand in air for 24 hours until it became slightly cloudy, and then irradiated to develop a deep blue color. Circle. The sample was placed in an optical container with a controlled atmosphere.

Under a nitrogen atmosphere at room temperature, the transmittance optical intensity (measured at 620 nm) of the colored film remained significantly constant for 7 days; however, when oxygen was introduced, the coloring rapidly disappeared. . These results are shown in FIG.

Alternatively, the same composition film is used in air;
However, at 60° C., upon irradiation with ultraviolet light, the film became instantly colored and then thermally discolored very rapidly. This coloring-decoloring cycle was repeated 6 times, and then the atmosphere was changed from air to nitrogen while maintaining the temperature at 60°C. Irradiation of the film with ultraviolet light in a nitrogen atmosphere resulted in a stable coloration that did not fade over 180 minutes. These surprising results are illustrated in FIG.

To further illustrate the consequences of an oxygen atmosphere for photochromic compounds, P paper strips were saturated with benzene solutions of various aziridines of the above formula and dried. The strips were then irradiated with ultraviolet light to produce a blue morphology. One set of these irradiated strips was kept in a nitrogen atmosphere in the dark, and another set was kept in an oxygen atmosphere. Both sets were kept in the dark at room temperature. The time required for the original optical density to fade was visually evaluated and recorded in Table 1. Great care was taken to minimize exposure of the sample to light during periodic readings.

Chapter ■ Table □ Decolorize optical density to i R1=R,=OH, 40 minutes 〉1 year (Rλ+Rs
) - Fuclopentyl 3 hours 〉June (
Rx+1g)-cyclohexyl 10 hours
~February R1mH3, R=! 0613 10 minutes ~ March R1eH, R snow■05H fu
10 hours January R1-Rtb-0*Ha
20 minutes 6 days R45g0I
Is, is 0H (OR15) 1 10 minutes
6 weeks 1-1ie Rz-OaHa
<10 minutes 2 days R1g=11. R shibang O-
However, even in an inert atmosphere such as nitrogen, a thin deposited film of an initially optically clear aziridine compound can become cloudy or cloudy after some time, e.g. 24 hours. Further measurements were taken. It is believed that such conditions are due to the growth of crystals of the compound.

The initially optically clear films were examined with a scanning electron microscope within 1 hour after deposition. The resulting micrographs showed a homogeneous array of amorphous mounds, the longest dimension of which was smaller than 1 micrometer at the base of the mounds. A similar sample was stored in nitrogen for 24 hours and underwent a visible change from a clear film to a cloudy film. Regular micrographs of the cloudy film showed that the mounds had grown substantially and the bases of the mounds had become irregular. Many mounds joined together to form three or more peaks. Regular arrays essentially disappeared.

Therefore, the surrounding area of the photochromic film is nitrogen, alin,
Maintaining a neutral atmosphere, such as neon, will help suppress thermal decolorization of colored forms, but will not prevent the initially transparent film from becoming cloudy, which will reduce the resolution of the soda. . Although such conditions are undesirable, even such a cloudy film has utility as a self-imposing medium.

By utilizing a barrier coating to form a thin aziridine film that is substantially oxygen impermeable, the stability, i.e., resistance to thermal fading, and the transparency of the film, i.e., its decomposition ability, are improved. It was found to be effectively maintained. A desirable material, such as polyvinyl alcohol or gelatin, which is substantially oxygen-impermeable (applied as a thin film over the photochromic film) and has no effect on aziridine, i.e., prevents crystal growth. effectively prevents crystal growth and also acts as an oxygen barrier to minimize discoloration. For example, films coated with polyvinyl alcohol maintained their transparency and density for over a year.

If aziridine is simply applied from a solvent solution,
The dried film will be microcrystalline in nature. Obviously 1 turbidity, crystal growth, etc. are not important at that moment.

The blocking coating is moderately permeable to actinic radiation, i.e. sufficiently transparent for actinic radiation to pass therethrough, so as to minimize crystallization of quaziridine and thus turbidity, as soon as possible after aziridine deposition and I should apply a barrier coat before building mine.

Dyes can be added to the blocking coating to select the wavelengths that cause coloration of the aziridine. For example, alizoline yellow dye can be added to polyvinyl alcohol paints to minimize background coloration from incandescent room lighting, but still, e.g.
It is possible to make me with 625 nm radiation from.

Moisture would have an adverse effect on the oxygen barrier properties of polyvinyl alcohol, so in practical recording devices radiation-transparent moisture barriers such as chloride 1? It may be desirable to have a film of copolymer of lydene and vinyl chloride co-operatively bring into intimate contact with or surround the article.

In the case of round deposition to produce high-resolution images, the temperature of the receiving support on which the photochromic aziridine is to be condensed is decisive. If the support is too cold or warm, an asymmetric coating will adhere and the thin aziridine film will appear cloudy and/or blotchy. On the other hand, if the temperature of the receiving support is between about -120 DEG and -140 DEG C., transparent, uniform coatings are obtained.

Scanning electron microscopy of the blotchy film at 100x magnification showed that the aziridine was deposited in the form of islands. Clear transparent film and cloudy film 7
Further examination was performed under a scanning microscope at magnifications of 1,000x to 10,000x. The clear, transparent film showed a uniform arrangement of mounds without granulation. The valleys between the mounds were the smallest in area compared to the mounds; and the longest dimension of the mounds was less than 1 μm. The thickness of the film is approximately 0.6
It was μm. A small mountain had a round top, but the base of a small mountain was not necessarily round. Some appeared oval, oblong and somewhat irregular, but they were mostly circular.

Scanning micrographs of the turbid film showed a similar mound structure, but the mounds grew together and clearly showed a dendritic structure. Dendritic structures are considered to have branches of 10 to 12 micrometers or more.

A cloudy and/or blotchy appearance provides light scattering and therefore a significant reduction in the resolution of such films. In contrast, clear transparent films provide minimal light scattering and high resolution.

The table below shows the results for the indicated sublimation conditions when the material was deposited on a quartz microscope slide.
R2m OR3 was used. In Table ■, Rlaa
H and R15a++n 031i aziridine were used. In Table 2, aziridine of R4+R@wa+cyclohexyl was used.

■Table Branch-like structures are clearly shown.

It is.

Film thickness 0.6 μm.

Structure is dominant.

Table m Table 102℃ -130℃ 3 minutes No coating 111℃ -
132℃ 8 minutes Uncoated 128℃ -160℃ 5
Minutes Light homogeneous film 152℃ -132℃ 6.5
Minutes Clear transparent film 161℃ -169℃ 6.5
Cloudy nine film with separation points 131℃ 25℃ 6
．． 5 minutes Asymmetric turbidity 9th coating ■ Table 161°C -136°C 6.5 minutes Light, homogeneous film 148°C -133°C 6.5 minutes Clear transparent film 150°C -166°C 6.5 minutes Adhesion to support A slightly cloudy film with unreliable color 150°C -75°C 6.5 minutes Kana-hiki film, but no adhesion to the support is required 150°C 25°C 6.5 minutes The film does not adhere to the support and from the above table, The condensation temperature of the intermediate is preferably about -1 at least when dimethyl derivatives are used.
It is believed to be in the range of 20°C to about -140°C. This condensation temperature will vary somewhat depending on the particular aziridine used to form the film, as shown in Tables 1 and 2.

If vapor deposition is not required to make the recording medium, the aziridine is simply dissolved in an organic solvent, such as benzene, at a concentration sufficient to give a homogeneous microcrystalline coating, applied to the surface of the support, and In this case a porous support,
For example, it is desirable to use saturated solutions to maximize coloration on paper. The film-forming oxygen barrier material can then be applied over the microcrystalline aziridine layer in a single coating operation or, desirably, in multiple coatings to maximize stability.

Alternatively, cellulose nitrate, acrylonitrile,
The aziridine can be coated from a dispersion containing a film-forming binding material such as polyC-nyl alcohol and the like. In this case, it is essential that the aziridine be in microcrystalline form on the support in order to function in the present invention, and therefore the binder material should avoid one in which the aziridine is soluble. be. The concentration of particulate aziridine in the dispersion must be sufficient to provide a homogeneous microcrystalline aziridine coating on the support.

In this latter case, a separate oxygen-blocking protective coating is a must! Therefore, it is desirable to use a film-forming bonding material that is itself substantially impermeable to oxygen, such as polyC-nyl alcohol.

The receiving supports used in this invention may be flexible or rigid, and may be reflective, opaque, or transparent, and in the case of simple solution coating, porous as well. Good quality images can be produced on aziridine-coated supports such as glass, quartz, polycal diimide-subbed polyester films, tin oxide-coated quartz and glass, and aluminum-coated polyester. The physical properties of the support surface will of course affect the texture of the thin photochromic film. If, for example, the film is to be deposited on a quartz support with rough polishing scratches, fine graining due to such polishing will be clearly observed on the film.

Relatively low-intensity ultraviolet irradiation produces a legible image. For example, when using dimethyl derivatives, about 10 to about 20 millijoules/am" (at 325 nm)
Irradiation in the range of 100 to 100% will yield us with excellent resolution. Irradiance as low as 5 millijoules (ZCIIJl) provides an easy-to-read image.

Kolak KTFR7 photoresist and electron-
Samples of photochromic recording media were made using monochrome resists such as epoxylated polydetadiene and polymethyl methacrylate. These supports were simply vapor coated with photochromic aziridine and subsequently overcoated with polyginyl alcohol.

This structure allows instant "record-after-read" inspection of information when making articles such as, for example, recording disk masters that require the recording of error correction codes. This structure is also useful for checking the quality of the lithography and printing plates prior to development of the final relief sequence. The aziridine and polyvinyl alcohol layers can be simply removed together with the unpolymerized corrosion resistant coating material following the testing process.

The substance of the invention will now be more particularly described with the help of the following non-limiting examples, in which all parts are by weight unless otherwise stated. In all cases, photochromic film preparation was carried out in a laboratory equipped with a yellow safety light to exclude extraneous UV radiation.

Sublimation was carried out in a glass laboratory cabinet. This device can be connected to a vacuum pump or dry nitrogen or air line through a three-way cock in a thick-walled external chamber. The interior of this chamber has a removable cold tentacle that can be further cooled by passing cold, dry nitrogen through its inner wall.

The temperature of the cold tentacles was measured with a thermocouple. The Pegi sample to be sublimated was placed at the bottom of the external chamber and the support was attached tightly to the cold tentacles to maximize thermal contact.

Example 1 A small amount (0,259') of 2,2'-dimethyl-6 (p-
Nitrophenyl)-4-phenyl-1,3-diazobicyclo(3,1,0)hex-5-ene was placed at the bottom of the sublimation apparatus. A clean 2111 thick quartz support was firmly attached to the flat cold tentacle of the sublimation tube with conductive adhesive tape. The apparatus was assembled and evacuated to approximately 0.15) liters. Cold nitrogen gas was passed through the jacket of the cold tentacle until the temperature of the exhaust gas stabilized at about -160°C. At this point, a hot oil bath (140° C.) is used to warm the aziridine and sublimate it onto the quartz support.

Under these conditions, the transparent aziridine film has approximately 0
．． A thickness of 6 microns was deposited in 2 minutes.

The oil bath was removed and the cold nitrogen line was replaced with a room temperature compressed air line to rapidly warm the cold tentacle to room temperature.

At that point, air was admitted to the chamber and the support with the aziridine-7 vellum was removed. This is optically clear. The support was then immediately immersed in a 4 weight aqueous solution of polyvinyl alcohol to provide an oxygen barrier layer and prevent further crystal growth of the photochromic aziridine.

The support was then dried and re-soaked to ensure uniform coverage over the entire area.

Electron micrographs of freshly deposited aziridine films (prior to coating with polyvinyl alcohol) show that they are typically about 0.6 microns thick and of homogeneous structure. Films left in air or nitrogen (without a protective coating of T!e ribinyl alcohol) change from optically clear to cloudy within 24 hours. Sylvania XP475/BLB 15 milliju k/
A clear, sharp blue color was obtained on a colorless transparent background using ``Yll''. Following exposure, the samples were stored in the dark in air at room temperature. Fidelity remained substantially intact; only at the edges of the sample where the thickness of the polyvinyl alcohol coating was reduced, or at coating stains, I was bleached.

I prepared a similar aziridine-film support as described above. The columnar support was then placed in a light-opaque box, which had a window made of a UV-blocking-visible-transmitting filter (Kodak L; 8-3-69). The box containing the board was placed in sunlight for about an hour. The box was then opened under yellow light in a dark room. My color has been completely erased, that is, I have disappeared. The board was heated and reexposed to UV light as previously described and again obtained a clear sharp edge.

Pseudo II (gholt') was not detected. ,Chi,
The method could be repeated many times without appreciable loss in the quality of my results.

The resolution of the aziridine-film-formed quartz plates was measured by recording and then reading a stationary liquid grid. 525 n of helium-cadmium lede under yellow safety light
Two interfering extended beams from m-rays (expanl@
d beam) to form a striped pattern. The sample is 17
Millijoule/cs” K jl issued.

10201/s pairs of companions per 11II were recorded.

This grating was recorded and confirmed by passing a helium-neon ray beam (633 nm) through the sample I made and observing the points diffracted from the zero or sixer beam. The ratio of the intensity of the 1st class beam to the intensity of the 0th class female beam was 0.41.

The reaction time of a quartz plate with an I-rivinyl alcohol-coated aziridine film was measured by measuring the change in its transmittance at 633 nm as a function of time after exposure to a 10 nanosecond UV-nitrogen radar pulse (345 nm). 9. The reaction time for 1 millijoule of radiation (25 millijoules/c + It was found that there was less coloring.

The thermal stability of the exposed blue form was determined in two experiments. In the first experiment, the support with the aziridine film was placed in a special optical sample chamber and exposed to air for 52 hours.
It was kept at ℃. 620 hours after UV irradiation with a xenon light source
Monitor the absorption of the nm peak as a function of time. The sample showed no detectable change during 60 minutes. The film without the polyvinyl alcohol barrier coating completely faded within 50 minutes.

In a second experiment, one of the samples was prepared and then stored in the dark at room temperature for one year.

There was no appreciable thermal discoloration except at the edges of the sample where the barrier layer was thinner.

The optical bleaching rate of poly-nyl alcohol coated photochromic aziridine films exposed to the bleaching action of red (653 nm) light was measured. A pre-exposed nine (blue) sample was placed in the elongated beam path from a helium-neon radar.

The intensity of the beam at the sample plane was measured with a Gamma Scientific 820mm photometric needle. A small portion of the beam incident on the film and the beam exiting the film were sampled by way of a beam splitter. Therefore, the change in transmittance of the beam could be followed as the sample was bleached. Transmit the sample at an optical density of 0.65 to 0°32
Approximately 650 millijoules/alI fowl exposure was required to bleach to a density of 5.

Example 2 2,2'dimethyl-6-(p-nitrophenyl)-4-yUniru-1,3- was prepared as described in Example 1 on two clean 2mm thick quartz supports. IP7 De♂ Cyclo (3,
1,0) Tokiss-3-Enwo coating is good. The coated support was immediately immersed in a 4% by weight aqueous solution of I/c/livinyl alcohol and allowed to dry. The poly-vinyl alcohol coating procedure was repeated several times to give a dry polyvinyl alcohol coating approximately 2 pm thick.

One sample was exposed to an electron beam with an accelerating voltage of 26 KV, a C-me current of 10 microamps, and a gem area of 2.88 α3 (21 mJ/cH1”) at 0.23 KV.
A 2 second exposure (in vacuum) was made. The sample developed an erasable image with a transmission optical modulus of approximately 0.5.

The second sample was subjected to a 2 second exposure (in vacuum) of an electron beam with a 165×VO accelerating voltage, a C-me current of 5 milliamps, and a beam area of 225 μm (7.6 Joules/Cl”). A high quality image was obtained which could be erased by exposure to visible light.

Example 5 2.2'-dimethyl-6(p-nitrophenyl)-4-
A strip of filter paper was immersed in a saturated solution of phenyl-1,3-diazobicyclo[3°1.0]hex-6-ene in benzene and allowed to dry. The resulting strips were then coated by dipping into a 4 weight hydrochloric acid solution of polyvinyl alcohol and dried with a hot mirror.

One strip was soaked in polyvinyl alcohol and dried once, another was soaked six times and another five times. These strips and the unpainted strips were added to Sylpania F4
It was exposed to ultraviolet radiation from T5/BLB dawn to give a reflective optical density of about 0.90 and then stored in an oven at 50° C. in the dark in air.

The second set was stored in a refrigerator at 0° C. in dark air. Samples were removed at various time intervals and reflected optical density measurements were made. The results of these measurements are shown in the following Tables V and 2.

Reflection optical density 0 0.90.1 −− −− −− −−t
O,90,470,40,380,30,2550,9
0,760,680,650,630,6250,90
,780,750,740,730,73 Reflection source density 0 0.90.630,550.480.440.5
61 0.90.8 0.770.740.720.
695 0.90.860.850.840.830
．． 825 0.90.880,870,860,85
0.84 At the end of this experiment, the sample was placed in a 100 watt yellow General Electric "Bug IJit"
e) Optically bleached by exposing to 1 for 1 hour from a distance of 6 inches. When the sample was re-grained, no obvious loss of sensitivity was observed and no pseudo-grain pattern was present.

Example 4 2.2'-dimethyl-6(p-nitrophenyl)-4-
A 1.0 g sample of phenyl-1,5-diazobicyclo[3°1.0]hex-3-ene was ground into fine particles using a mortar and pestle. 10 g of a 4 weight solution of polyvinyl alcohol was added to the aziridine and the mixture was triturated for several minutes to obtain a homogeneous dispersion. The dispersion was applied with a brush to white cardboard and dried with a hot mirror. Soaking and drying was repeated six more times to completely seal off the aziridine from the air.

The media was then contact printed from the negative by exposure to a mercury lamp for 5 seconds in an Oolite J exposure apparatus. A clear, sharp blue color appeared on a white background.

I exposed this to a yellow incandescent General Electric "Bag Light" VC at a distance of 6 inches for an hour and the color faded. And when I built it again, there was no loss of pay or obvious loss of sensitivity. I stored the sample I made in a dark place for a week, but there was no deterioration.

A second portion of this sample was dip coated twice in a solution of 0.15 p alizoline yellow dye dissolved in 25 d of a 4 wt.-water solution of polyvinyl alcohol and repeated drying.

The sample was exposed through a negative to a "Colite" device for 60 seconds. I got a sharp green color on a yellow background. This great background was slightly exposed after 30 minutes of exposure to an overhead "cool white" fluorescent light.

When aziridine is used for radiation monitoring, transit means are placed between the aziridine compound and the source of actinic radiation so that only the characteristics of the radiation to be monitored reach the aziridine compound. At least a zero color standard is prepared and the colors developed by the azolidine compound are compared with this standard. In a preferred embodiment, the color standard is separated from the aziridine compound, such as the background color of the support. If the color developed by the aziridine compound matches a particular color, the user is notified that the preselected amount of radiation exposure has been reached.

The radiation dose which causes a particular aziridine to develop a color standard can be accurately determined by measuring the intensity of the lamp output and the exposure time with an exposure needle at the sample plane. The product of intensity and exposure time gives the exposure (eg Julha). The visual match between the color of the patch (patoh) and the color standard is defined as the "end point".

Several different patches of one special aziridine may be used for a given reference color. Each patch can be covered by a different filter to attenuate the amount of radiation to which the aziridine compound is exposed.

In this way, each patch is certified so that the user is informed of the radiation dose required to color each patch to match the reference color.

Alternatively, several different standards for a particular aziridine would represent different pre-calibrated exposures. However, it is desirable to use a single color standard.

If one or more patches of another aziridine compound are present and the patches have different sensitivities to the actinic radiation to be monitored (layering on top of the patches with attenuation layers of different intensities), Separate color standards are not necessary. In such monitors, the aziridine patch itself can serve as a comparison means to alert the user to a radiation dose that is different from the predetermined radiation dose. Since the optical density of each photochromophage lysine at saturation (deepest blue possible) is relatively constant, a saturated patch can be used as a color standard for another unsaturated patch. The patch with the least attenuating filter will reach saturation first, and the most attenuating filter will reach saturation last. Thus, by photometric calibration, the saturation rounding exposure can be determined for each patch. It is therefore possible to use a monitor comprising a series of patches, which includes a predetermined critical level of nine exposures at some intermediate level. For example, if the acceptable 8-hour irradiation dose is 3.0 milligiers/cs, then 1.0, 2.0,
3.0, 4. O-oh! H5. o! 99h-to/cI
A monitor with a patch that reaches saturation at Im can be used. The patch of color develops and firstly appears out of saturation, and then secondly as usual.

At this point, the user has been exposed to 2 millijoules/cs+"K. The third patch will be slightly bluer and the fourth patch will be much thinner. In some cases, the third patch will be the third patch. Before becoming the same color as the first and second patches, the user should leave the actinic radiation area to avoid exposure to acceptable limits.

The monitor of this aspect of the invention is suitable for psoriasis monitoring.
), in which patients receive photoactive agents and are periodically irradiated with ultraviolet light. New England V Journal Ode Medicine by Parrish Force 291.1207
-11 (1974) describes photochemical treatment of psoriasis. The patient is first treated with a photoactive agent (eg 8-methoxyzopsoralen) by oral or topical medication, followed by irradiation with specific actinic radiation. Generally, near-UV radiation in the range of 520 to 390 nanometers is used. The required radiation dose varies between about 1 and 20 joules and depends on patient tolerance and response to the drug. The method is expected to include an initial intensive treatment phase followed by a long-term sustained regimen. Each patient is initially "titered" to determine the tolerance and effectiveness of treatment. As the amount of UV radiation utilized in treatment is critical both to the efficacy of photoactive agents and to the minimization of toxic reactions such as erythema, accurate monitoring of radiation exposure is important.

Currently, expensive electronic integration devices are being utilized and developed to monitor radiation doses. The monitor of the present invention is suitable for use in this treatment because it is inexpensive, non-toxic to process, reliable and reusable.

The monitor can also be used for solar radiation monitoring, although for this application it is desirable to add an additional filter to prevent bleaching from the large amount of visible light present in sunlight. This device is used by sunbathers or people with hypersensitivity to solar radiation, and a moderate change in the color of the aziridine compound indicates the dose of erythematous radiation.

This monitor may also be used to compare the rate of color change of installed panels and indicate necessary adjustments to solar concentrator panels.

The photochromic aziridine used in the present invention is about 450
Being sensitive to actinic radiation down to the nanometer range: such instruments with suitable filters can be used to monitor the radiation received by plants. Cumulative irradiation around 465 nanometers (blue) is indicated by a change from colorless to blue, and selectively around 675 nanometers (
Red) Peripheral illumination is related to the degree of decolorization from blue to colorless. In this way, light exposures that affect growth such as chlorophyll formation, photomorphogenesis, phototropism, etc. can be monitored.

This device may also be used to monitor ultraviolet light therapy given to infants undergoing treatment for yellow scars. This f! Another use for the equipment is the inspection of ultraviolet radiation by factory workers and electron beam radiation used in various manufacturing processes.

Example 5 Psoriasis treatment monitor Aziridine compound, 2,2'-dimethyl-6(p-nitrophenyl)-4-phenyl-1,3-diadepicyclo(3,1,0)hex-6-ene(0 , 25#) was ground into fine particles using a mortar and pestle.

An aqueous polyvinyl alcohol (Pvum) solution (3I in 4s solution) was added to the aziridine compound and the mixture was triturated for several minutes to form a homogeneous dispersion. The dispersion was applied with a brush onto securities paper and dried with a thermal mirror. The entire support was then immersed in an aqueous solution of 44PVM and dried by means of a thermal mirror. The aziridine compound was completely isolated from oxygen by repeating the soaking and drying process six more times.

A patch (approximately 0.25.11) of aziridine coated support was applied to a color standard sheet. The color standard sheet was stock paper coated with blue Benjamin Moore Formula 9-31 flat latex paint. This paint was chosen because the color morphology of this paint and the aziridine dispersion visually matches at a reflected optical density of KO,84 when viewed visually through the filter system (described below). be. Approximately 1.5 cm + 5 patches coated with aziridine
The patch was applied to a strip of 7-5 cm x 7-5 cm color standard sheet so that the patch was completely surrounded by a colored background, and the entire strip was then coated with a 4-inch aqueous PV solution.

Attenuating filters were constructed by first preparing a master mixture and then serially diluting it to obtain a reasonable concentration.

The master mixture was made as follows: Hiren W8
(.55.511-Dupont 4, 4'-methylenebis-, cyclohexyl inocyanate) was charged to a 250d three-necked flask and heated to 50°C with stirring. Polycazorolactone polyol (83,0g - molecular weight approx. 5
60), the temperature rose to 84°C. After stirring for 2 hours, the temperature dropped to 65°C. Diptyltin dilaurate (0,249) was then added. Hyp-a-xyethyl methacrylate (1 M, 37-4 F) was slowly added to the stirred mixture and allowed to react for approximately 45 minutes. The resulting syrupy mixture was named Olivimer "mu". Oriimer [MuJ (5,05#) t-5,.

59.7-7, Iw, [F]-E: / w -(y
- Beer-2-1 Rolidon (obtained from GM Corporation). Anifine ethyl ether (0,5Ii) and a,a-jethoxyacetophenone (0,1,Si2) were added to this mixture. The resulting solution contains Zenacryl Yellow 3 () (0,00 mg).

φ48055, 2. ON), 2,4-dihydroxybenzophenone (0,424g) and Alizoline Yellow 5
08 (σ, f, φ14055, 0.0386F) was subsequently added and stirred until dissolved.

This solution was mixed with oligoimer[mu]J(43,3,p), amm
(45,51) and α,α-jethoxyacetophenone (0,8669) to form a master mixture. The master mixture was prepared as shown in Table 1.
c1: 102 Oripmer "mu": 11 mu + 1 weight 4
Dilutions were made with various amounts of seeding agent made with 4a,a-jethoxyacetophenone.

1 9.9997 0 2 10.0002 0.57985
7.99?9 1.22234 7.
0002 1.7B305 5.9999
2.8716 Each of these solutions was applied onto Mylar using a φ44 Meyer (M@y@r) rod and coated with Silpa Air 1F15T 8/BIJ under a nitrogen atmosphere.
Apply coating to the lamp row for 2.5 minutes on the side and 10 minutes on the back.
Then, the coated side was added and irradiated for 5 minutes. The resulting cured film provides a relatively uniform spectral response to near ultraviolet light.

Then cut it to the appropriate size to fit over the photochromic aziridine patch. A film of the thickest mixture is conveniently applied to the patch at one end of the support, with regular density reductions across the other patches.

The spectral reaction forming filter is made by dissolving the following components in a mixture of 1;1 oligomer "mu" and H2N mu. ，
48055 ): 0.0782 F dihydroxy pen f phenone; 0.213 II phenyl salicylate: 0.252 F anisoin ethyl ether: and 0.260 N a,a-jethoxyacetophenone.

The resulting solution was applied onto the My Two using a φ44 Mayer rod and the Sylpania IF1 was coated in a nitrogen atmosphere.
Cured with a bank of 5T 8/BXJ lamps. The coated side was irradiated for 10 minutes and the back side for 5 minutes. When the obtained film was peeled off from the My Two, it had a thickness of 0.068 dew. A portion of this film O, L5m x 7.5aII, was attached to an attenuation filter.

The entire assembly was wrapped in a single layer of Mylar to form the monitor.

A pair of Sylpania P R40n'X1-235 monitors
Irradiated with Tunzo. These lamps have a radiation spectrum similar to lamps used for psoriasis treatment.

When the monitor is illuminated with radiation, the photochromic aziridine turns blue. The patch under the attenuation filter 5 first matches the color of the color standard and then from 4 to 1 with increasing exposure time. By the time the patch under filter 1 matched the color of the standard, the 17 other patches had darkened so it was quite easy to visually determine when their "end point" had passed. .

Macbeth RD with cyan filter in that the color of the photochromic aziridine patch matched the color standard
Reflected optical density (hereinafter referred to as "optical density") measured through the filter of the monitor by a -51°911 degree meter.
was 0.88.

I irradiated the monitor with Sylpania IFR40BIJ-2552 until the color of all the patches passed through the "end point". The optical density of each punch was measured and the monitor was stirred in the dark for 72 hours. At the end of this time, the Kft and chemical concentration were measured again. -1ta is recorded in Table 1. There was a slight change in optical strength after being kept in the dark for 72 hours. Then turn the monitor yellow G, l.

It was irradiated with a "backlight" at a distance of 15 steel for 2 hours. Optical density was measured. The results (shown in Table 1) show that discoloration occurs under visible light irradiation;
1.28 1.39 After irradiation with visible radiation 0.26
Comparing the spectral response of the device in 0.26 0.26 0.26 0.2 with the main clinical response of human skin after ingestion of 8-methoxydesporalen shows that the radiation III dose in the treatment of psoriasis is It turns out that it would be an excellent monitor for decision making.

Example 6 An aziridine compound, 2,2'-dimethyl-6(p-nitrophenyl)-4-phenyl-1,3-diazobicyclo(3,1,0)hex-6-ene, in an aqueous polyvinyl alcohol solution. Dispersed.

This solution was applied to white cardboard and sealed in complete EFTA as described in Example 5.

A monitor was then constructed as follows: The entire light-sensitive support was scanned with an iSking Teso. The masking section in the area where the color standard should be applied was removed. All surfaces were coated with Benjamin Mu 79-61 matte latex paint. Next, masking Teso (parts of the patch that are sensitive to light)
was removed.

All supports were then dip coated in 4% PTA and dried (repeated three times).

The filters to be placed over the individual patches (combining a spectral response shaping filter and an attenuation filter into one) were constructed as follows.

The dye stock solution mixture contains the following ingredients: modified cellulose acetate (ma
il,, oelLac@tate)'s 20.5-
Made by adding to 1324N in acetone solution: 14.8391 g Zenacryl Yellow (Berncolors, Inc. - Pernacryl Yellow, 4G): 14.42989 Alizoline Yellow (Berncolors, Inc.)
Ink, - Vernachrome Yellow, 6G): 2.3421 g dihyroxypenzophenone: and 2.0992 # phenyl salicylate.

The mixture was warmed and stirred to dissolve the dye and then passed through a pressure filter.

A series of dilutions of this stock mixture were prepared in various amounts at 20.5
% modified cellulose acetate/acetone solution. Solutions of these samples were knife coated to a wet thickness of 3.65 m and then air dried in an oven at 80°C (0.0457 m
dry). The sample was placed on top of the aziridine dispersion and yR
40sxJ-255 runs! were chosen to give representative endpoints for each film when exposed at . The dilution levels used in this example are shown below.

20.5-denaturation in acetone 1 100 02
93.5 8.73
85.0 15.04
76.0 24.05
85.0 33.0 Samples of these films were cut to size and adhered to aziridine patches with Dow Corning Silastic 732RTV adhesive. A layer of 2 mil MyTwo was adhered to all filters with silastic adhesive and the entire assembly was cured under pressure for 24 hours.

This monitor has a pair of IFR40BL-235 lamps.
．． Irradiation was performed at a rate of 0.08 milliwatts/α3 (measured with a Gun! Scientific 820 mm meter needle) until each end point was reached. The sample was then optically decolorized using a "backlight".

In the fourth cycle, the optical density of each patch was measured periodically (through a filter) with an RD-100 trowel meter. The sample was subsequently optically bleached and subjected to a fifth UT/irradiation. At the end of the fifth irradiation, the samples were covered in the dark and left at room temperature for 69 hours. Optical density readings were then taken. These minus data are summarized in the table below.

The underlined reading for each sample is the predetermined visual "end point." Thus, in these 10 measurements, the visual endpoint was between 0.89 and the optical endpoint.
．． 92 (<396), and the degree of discoloration in the dark was minimal.

Fourth irradiation cycle 0 0.28 0.27 0.30 0.28 0
．． 260.196 0.45 0.39 0.36 0
．． 52 0.510.595 0.62 0.
56 0-46 0.40 0.361.
28 0.83 0.73 0.55 0.48 0
．． 421.58 0.92 0.80 0.60 0
．． 52 0.462.18 0.92 0.6
8 0.62 0.524.05 0
．． 85 0.76 0.674.75
0.91 0.81 0.705.74
0.87 0.766.72
0.89 0.779.87
0.900 0.29
0.28 0.31 0.28 0.280
．． 196 0.44 0.57 0.34 0
．． 54 0.2?0.595 0.62 0.5
3 0,42 0.41 0. ! 141.4?
0.91 0.78 0.58 0.52
0.462.18 0.92 0
．． 70 0.61 0,525.96
0.88 0.78 0.684
．． 45 0.89 0.7
9 0.685.75
0.86 0.736.72
0,92 0.788.90
0
．． 8510.6
0.90 optical density (1,860,880,880,820,86) Example 7 Psoriasis Treatment Monitor Approximately 0.0
A radiation-sensitive support was prepared by applying the aziridine-PV dispersion to a thickness of 25 m and subsequently applying Pvm. Prime the polyester as described in Example 5 with latex paint to create a color standard background. Ten holes (approximately 0.25 x 3) were drilled in this reference strip and a clear double-coated pressure sensitive adhesive tape was adhered to the uncoated surface over the holes. The patch of photosensitive support was then pressed into the hole in the reference strip and held in place with a pressure sensitive adhesive. Transparency paper strip (crane (0r)
1-5s+x7.5cm+) was placed on the surface to be coated.

The filter system on the irradiation side consisted of the spectral response shaping filter of Example 5 and the neutral density step wedge.
density 5tep ws4go) filter (Stauffer φ95). A neutral density graduated wedge filter was placed on a spectrally responsive shaped filter system with each stage covered with a different photosensitive patch. The reading side was covered with a visible light transparent VV-absorbing filter made by adding the cured stock mix of Example 5 to the spectrally responsive shaped filter and held in place by double coated pressure sensitive adhesive tape.

The assembled monitor is FR40BIJ-2352 of Example 5.
yrK1.8x10-'7)/cs+" (1 at 0 rate
It was irradiated for 6 minutes. The color intensities of the various sections could be easily distinguished by visual inspection. Reflection optical density was subsequently read through the filter using a Macbeth RD-519□ density needle with a cyan filter. The results are shown in Table ①.

Table 1 1.10 2 1.12 3 1.02 4 1.00 5 0.88 6 0.82 7 0.79 8 0.74 9 0.69 10 0.64 Background 1.06 Example 8 Solar irradiation monitor yellow dye, cetoflavy T (0-I-+ 4900
5 +0.022511) was dissolved in a 4% aqueous solution of Zccopvum. This dyed pvm solution was then mixed with aziridine compound (0,259) to make a photosensitive support as described in Example 5.

Alizoline yellow (O, X, φ14055, 0.03451
) was dissolved in 1111 of 1=1 ethanol:acetone. This solution was mixed with 69-modified cellulose acetate 2.851i dissolved in acetone and coated onto a Mylar web using a 44 Mayer rod (dry film thickness - 0.01 m).

A film of aziridine yellow/modified cellulose acetate was then overlaid onto the patch of cetoflavine-aziridine support. The first patch was covered with one piece of film, and the second with two pieces, with an AS-7-54 (Corning Glass Factory - Corning φ9863) VV-transparent, light-blocking filter over all sections. placed.

I built this assembly outdoors in full sun (winter in Minnesota). After a 25 minute exposure the photosensitive patch under the single layer film was significantly darker, but under the two layer film it was only K11k<. Macbeth RD-51 reading of reflective optical density? Density needle (cyan filter)
was passed through an alizoline yellow (0, 14055)-modified cellulose acetate film using Data is number X! ! to be recorded.

Table X Start 0.23
0.25 exposure 2:10-2:35 p.m. f, 40
0.29 RMB 2:50-4:20 PM 1.5
1 0.54 Transmittance measurement as a function of wavelength is 3.1
% alizoline yellow-with two layers of modified cellulose acetate 5.2
A 0.015 wa film combination of % Cetoflavin/PVM was used. These transmittance values were multiplied by the aziridine-PV membrane response values to obtain approximate instrument spectral response values.

Example 9 Six of the aziridine compounds in Pvum were prepared as in Example 5.
Seed dispersions were made, each of which
The ratio of P Vm was varied. These are approximately 0.05. It was coated on cardboard to a thickness of . A spectral response shaping filter (Example 5) was placed on a sample of each dispersion. They were then exposed to the dawn light of Example 5 and optical density readings were taken. According to reading (Table M) K, it is illustrated that it is possible to extend the end point by using an old-fashioned filter.
However, the amount of aziridine used in the photosensitive support varies;
And I can see these differences with my own eyes! can be understood.

Chapter xi Table 0.0186IO, 178, 92, 60, 120, 26
0,880,0070g0.178IO,980,12
0,220,590,0018,FO,178/
0.25 0.12 0.15 0.27 When performing the above measurements, the spectral response shaping filter was removed before measuring the optical density.

Example 10 Plant lighting indicator for red light response (color erasing method)
The paper was soaked and the solvent was allowed to evaporate. This strip K15p
Vum was applied and dried with a hot mirror. The 77 μm coating was repeated three times. The samples were exposed to an optical immersion of 0.70 (RD 100 density needle).

Strips of 3M trademark infrared transparent film Type 577 were stacked on top of the exposed aziridine at various thicknesses to create stepped-wedge attenuation filters for red light.

An aos-3-6907 blocking, visible light transparent filter was placed on top of the wedge. Line the entire assembly with cardboard! And then I changed my mind.

Place one of these O indicators in a stirrup in a window facing north, exposed to light, and one facing south, exposed to ft (both at 45°).
The slope is 9). They were exposed to light from sunrise to sunset during a lightly cloudy January day. There was significantly more discoloration in the sample for south exposure.

Both samples showed the same decolorization, but the degree of decolorization was even worse than that seen on the monitor exposed to light on a cloudy pO day.

This experiment was repeated on a completely sunny day. Samples exposed to light on the south side experienced complete surface bleaching in all areas with up to 10 layers of blue transparent material above them. For the north exposed sample, a slight trace of discoloration occurred below the 4 layer area. No appreciable discoloration occurred in areas covered by four or more layers.

Example 11 Plant lighting indicator for blue light response A support was prepared as described in Example 6.

Arizoline yellow (4,0N Bernchrome yellow) and 4.
0I tetrahydroxyben f phenone is atom Kl
14.5-Modified cellulose acetate solution. This solution was used as the stock solution used to create a combined spectral shaping and attenuation filter. This solution was diluted with 14.5% modified cellulose acetate to create a representative sample. These samples were coated with a knife to a temperature of 0.58 K when wet (0,056 s + s dry).
It was coated and dried in an 80°C oven for 2 hours. Two samples were selected from these films.

Basic blue 7 (0,1,φ4・2595,0.362#
) was dissolved in a 24.2° solution of modified cellulose acetate 159.411 in acetone and coated with 0.3050 K wet (0.046 W + dry) using a knife coater. This filter, which is removed during reading, has the highest capacity for aziridine! llIC Attenuates visible light in the red range of the spectrum which is optically decolorized.

(However, it is essentially transparent in the near-UV and far beyond the visible range.) A filter of natoxypenzophenone in alizoline yellow/modified cellulose acetate is placed over the indicator and the A layer of 0.05m5 Mylar was placed on top. A layer of basic back 7 film was temporarily placed over the entire assembly. These indicators are then connected to a pair of G's, 1. ◆ Kll was detected at 7 cm from a 400 W cool white fluorescent lamp (total output 5.24 mW/cm" at the sample surface). The reflected light of the aziridine 711 layer was periodically scanned (through the filter). .These readings are the nth WIK
Showing 1100 υ 0.440.82 1.
001.152 80 20 0.52Q,
96 1.121.32 The Basic Blue 7 filter was removed and the sample was decolored with G, IC, "Backlight".

Example 12 Hekis-3-2 (0.25 pm) was ground into fine particles using a mortar and pestle. An aqueous solution of polyvinylal 4-roll (3 g of a 4% solution) was added to the aziridine and the mixture was then milled for several minutes to form a homogeneous dispersion. This dispersion was applied to securities paper with a brush and dried with a hot mirror. The entire support was then immersed in an aqueous PVA solution and dried with a hot mirror. This soaking and drying process was repeated 6 additional times to completely insulate the aziridine from air. Patches from this material were applied to comparative ICs as in Example 5 and the entire support was coated with the 41PVM solution. The entire monitor support was coated with a UV-attenuating coating made for the psoriasis treatment monitor of Example 5, Sample 1 (0,068 cm) to prevent staining by room light. It was covered by a single layer of visible light transparent di-ilm. Different thicknesses of My2 were then stacked on top of each of the photosensitive patches to give a stepwise attenuation of one electron beam.

This assembly was fixed on a cardboard support, and then heated using a 7-cynins electrocurtain type high-energy electron beam irradiation curing device (acceleration voltage -175 @V, H-A).
11th style-4,32X 10-'7 y pair/ax"
.

1.11 irradiation - 0.84 Joule/cy+") through a cleaned irradiation chamber. After irradiation, the reflected optical density was set to
Measurements were taken on each patch of the monitor (through the filter) using a 51911 degree needle (blue filter position).

The samples were then reirradiated under the same conditions (cumulative electron beam irradiation - 1,68 Joules/cN"). The effect of these irradiations on the optical density of the various sections is shown in Table xm.

Stone X Front beam attenuation layer 1 0.094m 0.18 1.28
--2 0.129 m O,221,031,
2330,170m O,240,340,4040
,221wx O,340,340,3350,24
6 simple 0.38 0.38 0.376 0
．． 272 wx O, 360, 360, 3670, 2
97m O, 390, 420, 4280, 322m
Samples at O, 350, 39, 0, 5 were optically bleached with G, m, "backlight" and reconstituted.

The samples lost little or no sensitivity.

In addition to the above-mentioned use of this monitor as an indicator of cumulative exposure, one monitor support can also be used as a beam transmission indicator.

[Brief explanation of drawings]

FIG. 1 is a graph showing that the coloring of the recording material film produced according to the present invention is stable in a nitrogen atmosphere at room temperature, but rapidly disappears in an oxygen atmosphere; This is a graph showing that the same film as shown in the figure is stable in a nitrogen atmosphere even if it repeatedly undergoes rapid coloring and decoloring due to ultraviolet irradiation in air at 60°C. Agent Asamura Kōgai game name

Claims (9)

[Claims] (1) at least one formula [wherein R1 and Rs are independently hydrogen, alkyl having 1 to 6 (inclusive) carbon atoms, phenyl or ortho- or para-lower alkyl or lower alkoxy-substituted phenyl; a support having a photochromic aziridine compound attached thereon; or R4 and Rs together are alkylene having 4 to 7 (inclusive) OR atoms; an oxygen barrier that, in combination with the compound, substantially prevents contact between said aziridine compound and oxygen; and at least one color standard for comparison with the color change of said aziridine compound caused by irradiation with actinic radiation. Integrative reusable instrument for monitoring characteristic actinic radiation. (2) Claim 1 further comprising a removable visible light 11 filter covering said aziridine compound.
The equipment described in item 1). (3) Claim No. 1 further comprising means for reducing the amount of chemical impinging on said aziridine compound.
). 4. The device of claim 3, further comprising a plurality of discrete test zones of said aziridine compound deposited on said support. (5) By having in combination therewith a series of attenuating filters which eliminate the extra actinic radiation to be monitored, KFt, the said test band is made progressively less sensitive to the actinic radiation to be monitored. The device according to claim (4). (6) The test zones are made progressively less sensitive to the actinic radiation being monitored by varying the concentration of aziridine compound in each test zone.
). (7) The device according to claim (1), wherein Rx and R are methyl. (8) The device according to claim (1), wherein R1 and R together represent cyclopentyl or cyclohexyl. (9) The device according to claim (1), wherein the oxygen barrier is polyvinyl alcohol. (to) The device according to claim 9, further comprising a moisture barrier in addition to the aziridine compound and the oxygen barrier.