JPH09126887A - Material for indicating irradiation amount of ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To readily and inexpensively indicate the irradiation amount of ultraviolet rays by utilizing the distinctive hue change of a material which changes in color depending upon the exposure of the material to ultraviolet rays. SOLUTION: The material for indicating irradiation amount of ultraviolet rays is composed of a combination of a radial generating agent carried in a carrier and a coloring matter which changes in color when the matter reacts to the radical and/or the precursor of the coloring matter and indicates the irradiation amount of ultraviolet rays by changing the color. Since no color changing reaction occurs in the material until the material is irradiated with ultraviolet rays and, when an ultraviolet-ray shielding film is removed from the material, the measurement of the irradiation amount is started, the measurement can be started simply and definitely. Phenothiazine is a colorless material, but gradually changes into red when the material is irradiated with visible light and ultraviolet rays depending upon the combination between the material and radical generating agent. This material is effective for the measurement of irradiation amount of ultraviolet rays over a wide measuring range and a wide ultraviolet wavelength region.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radical that is generated by ultraviolet rays and a dye that reacts with the radical to change color.
Alternatively, the present invention relates to a material for measuring the irradiation amount of ultraviolet rays with a dye precursor.

[0002]

2. Description of the Related Art At present, an ultraviolet irradiator is used for printing and resist-related purposes. The demand for display materials that can control the irradiation amount of ultraviolet rays inexpensively and easily is increasing year by year. Further, in recent years, the irradiation of ultraviolet rays on the ground has been endangered due to the destruction of the ozone layer, and a material for measuring the irradiation amount of ultraviolet rays at low cost has been demanded. Many of foods, chemicals, etc. are deteriorated or decomposed by irradiation of ultraviolet rays, and storage conditions such as storage in a dark place and strictly prohibited from direct sunlight are required. However, as a method for measuring the irradiation amount of ultraviolet rays in the world at present, there is a type using an amplifier and a photoelectric converter with an electric circuit as disclosed in JP-A-47-46481 and JP-A-48-82881. The device itself is large and expensive, and is not suitable for use in monitoring each product. In addition, there are inventions such as JP-A-62-112020 and JP-A-63-179977 as measuring materials by a chemical method, but because of the large content of the chemicals used and the high raw material cost of the chemicals. Not often found in the general market now.

In other words, display materials for inexpensively measuring the irradiation amount of ultraviolet rays have not been widely used in the market. The present invention comprises a layer containing a dye and / or a dye precursor that changes color by reacting with a radical generator carried in a carrier and radicals, and the amount of UV irradiation that displays the amount of UV irradiation as a color change. The present invention relates to a measurement material, and achieves the above object easily and inexpensively.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an ultraviolet irradiation dose measuring material which allows the irradiation amount of ultraviolet rays to be displayed easily and inexpensively by a clear change in hue. That is, since radicals are not generated before irradiation with ultraviolet rays, the reaction of color change does not start, and at the time point of irradiation with ultraviolet rays, radicals defined by the irradiation amount are generated and color change is started, which is simple and clear. The dose measurement can be started immediately. Generally, most of fresh foods, foods stored at room temperature such as confectionery, and chemicals such as paints and adhesives are usually written in a dark place and strictly prohibited from direct sunlight. However, in general, only the environment of the storage place is managed, and it is unclear how much ultraviolet rays were actually irradiated to each article to be managed. That is, articles displayed in stores or the like may be irradiated with ultraviolet rays, but there are few devices in the market that monitor such a situation for each article.

As described above, there has been a demand for a material which can clearly and inexpensively display how much ultraviolet rays each article has been irradiated with.

[0006]

Means for Solving the Problems The inventors of the present invention consisted of a radical generator that generates radicals by ultraviolet irradiation and a dye and / or dye precursor that changes color by reacting with the radicals, and The inventors have found that a color change occurs, and further that the radical irradiation amount can be displayed as a color change by defining the radical generation amount according to the radical concentration according to the ultraviolet irradiation amount. The present invention displays the amount of ultraviolet irradiation as a color change, which is obtained by supporting a radical generator that generates a radical by ultraviolet irradiation and a dye and / or a dye precursor that changes color by reacting with the radical in a carrier. It is a material for displaying the amount of UV irradiation.

Further, the present invention is the above-mentioned ultraviolet irradiation dose measuring material, wherein the carrier is a resin layer laminated on a transparent substrate.
Further, the present invention is the above-mentioned ultraviolet irradiation dose measuring material, wherein the resin layer is a layer composed of an adhesive material. Further, the present invention is the above-mentioned ultraviolet irradiation dose measuring material, wherein the resin layer is a printed layer. Further, the present invention is the above-mentioned ultraviolet irradiation dose measuring material, wherein the dye and / or the dye precursor is a phenothiazine-based coloring dye. Furthermore, the present invention is the above-mentioned ultraviolet irradiation dose measuring material, wherein the carrier contains an amine.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The radical generator used in the present invention has a radical generation amount regulated by its ultraviolet irradiation amount, and an optimum radical generator is set according to a desired measurement wavelength. The wavelength of the ultraviolet light that changes the hue of the dye and / or the dye precursor to be used can be determined. That is, since the decomposition rate of the radical generator depends on the wavelength and the sensitivity, the radical generation amount is defined as a function of the wavelength and the irradiation amount (intensity). As the radical generator, a direct cleavage type aryl alkyl ketone, oxime ketone, acylphosphine oxide, aryl alkyl ketone, thiobenzoic acid S
-Phenyl, titanocene, hydrogen abstraction type aromatic ketone, thioxanthone, benzyl and quinone derivatives, 3-ketocoumarin and the like.

More specifically, as the aryl alkyl ketone, Esacure of a benzoin ether derivative is used.
EB3 (manufactured by Fratelli Lamberti),
Vicure 10 (manufactured by Stauffer), acetophenone derivative Darocure 1173 (E. Me.
made by Rck), Darocure 1116 (E. Mer)
ck), Darocure 953 (E. Merck
Co., Ltd., Irgacure651 (Ciba Geig)
y company), Irgacure 184 (CibaGeig
y company), Irgacure 907 (Ciba Gei)
gy), Esacure KB1 (Fratell
i Lamberti), Esacure KB6
0 (Fratelli Lamberti), Sa
As the oxychemketone, QuantacurePDO (War
d-Blenkinsop), Quantacur
ePPO (made by Ward-Blenkinsop), etc.,
Examples of aromatic ketones include benzophenone and benzophenone derivatives, and BP (Parke-Davis).
Company), Trigonal12 (manufactured by Akzo), Qu
antacureBS (Ward-Blenkinso
p company), QuantacureBTC (Ward-B
Lenkinsop), Trigonal121
(Manufactured by Akzo), Darocure 1664 (EM
erck), Esacure KBO (Fratel)
li Lamberti), Quantacure
Ultracure CTX as a thioxanthone derivative such as BMS (manufactured by Ward-Blenkinsop)
(Manufactured by Sherwin-Williams), Ultr
acureDTX (Sherwin-Williams
QuantacureITX (Ward-Bl)
Examples of the anthraquinone derivative include TBA (manufactured by BASF) and the like.

The radical generator is added to the medium forming the carrier in an amount of 1.0 to 20% by weight, preferably 2.0 to 15.0% by weight to obtain the ultraviolet irradiation dose measuring material of the present invention.

In the present invention, the dye and / or dye precursor, which changes color by reacting with a radical, has a property that hydrogen atoms in the molecule are easily extracted by the radical, and a change in color is recognized at that time. By taking advantage of this, an ultraviolet irradiation dose measuring material of the present invention was obtained. As a mechanism of this color development, the following mechanism is inferred by taking phenothiazine as an example.

[0012]

Embedded image

First, the hydrogen atom in the phenothiazine molecule is abstracted and the nitrogen atom becomes a radical. Next, the radical moves to the sulfur atom, and the valence of the sulfur atom changes from divalent to tetravalent. Then, the conjugation extends to the benzene rings on both sides, the light absorptance of the visible light portion changes, and the hue changes. In addition to this, the reaction used in free radical photography and the like as described in "Color Chemical Encyclopedia" (CMC Publishing) is used in the present invention. That is, the color changes due to a reaction of a radical-diphenylamine-based compound or a radical-triphenylmethane-based compound that exhibits a blue color due to a chain reaction that occurs when a hydrogen atom is abstracted by a radical. In addition, Bell & H also found in the "Color Chemical Encyclopedia"
The color is also changed by the reaction of the radical-dye precursor-sensitizer system by the Owell method.

Examples of dyes and / or dye precursors that develop color upon contact with radicals used in the present invention include phenothiazine-based dyes such as phenothiazine, phenoxazine-based dyes such as phenoxazine, and leuco crystal violet. , Leucomalachite green, crystal violet, leuco crystal violet lactone and other triphenylmethane compounds, and 4- (p-dimethylaminostyryl) quinoline and other quinoline dyes. The dye and / or dye precursor, which changes color by reacting with radicals, is added in an amount of 1.0 to 20% by weight, preferably 2.0 to 15.0% by weight, based on the medium forming the carrier. An ultraviolet radiation dose measuring material of the invention is obtained. At this time, if the content of the dye and / or the dye precursor is 1.0% by weight or less, the coloration is thin and the visibility is poor even if there are sufficient radicals in the test object. There is a limit to the radical concentration that can be detected depending on the amount of dye and / or dye precursor added, and when the amount added is small, there is no change in color tone after color development at a radical concentration above a certain value, and accurate irradiation is possible. The quantity cannot be measured. Therefore, it is necessary to add the dye and / or dye precursor in an amount corresponding to the irradiation dose to be measured.

In the present invention, as the transparent substrate, an olefin film such as polyethylene or polypropylene, a polyester film typified by polyethylene terephthalate, cellophane, polyvinylidene chloride copolymer, polyvinylidene chloride copolymer, polyvinylidene fluoride or polychlorinated material. Examples thereof include plastic films of vinyl, nylon, polyacrylic acid, polymethacrylic acid, and the like. In addition, any material may be used as long as the material has transparency enough to confirm a change in hue. It is also possible to mix an ultraviolet absorber in the base material to control the range of measurement irradiation dose.

In the present invention, the printing layer is a layer using a resin printed by silk screen printing, gravure printing, offset printing or the like as a medium, and the printing pattern and the binder resin used are resins that can be formed by printing. Any layer may be used without limitation.

In the present invention, the decomposition catalyst of the radical generator is added for the purpose of accelerating the decomposition rate of the radical generator and imparting wavelength selectivity, and even if the same radical generator is used, the decomposition catalyst can be added. It becomes possible to control the decomposition. That is, amines and the like that generate hydrogen by abstracting hydrogen by radicals generated from the radical generator can be used. Specifically, as amines, triethanolamine, ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate, isopentylmethylaminobenzoate,
N, N-dimethylbenzylamine, triethylamine,
Tributylamine, N, N-diethylaniline, N, N
-Dimethylaniline, N-phenyldiethanolamine, N-phenyldiisopropanolamine, dimethyl-p-toluidine, diethyl-m-toluidine, triethanolamine, 4-phenylmorpholine, 4,4'-
Bis (diethylamino) benzophenone, N-phenyl-2-naphthylamine, N, N-dibenzylaniline,
One or more of N, N-dibenzyl-2-aminoethanol and the like can be used.

The amines can be used alone or in combination, and the addition amount thereof is 1 to 200 parts by weight, preferably 10 to 100 parts by weight with respect to 100 parts by weight of the dye and / or the dye precursor. To do. As a result, the wavelength range for measuring the irradiation dose of ultraviolet rays and the range of measurement sensitivity of the present invention are greatly expanded.

In the present invention, a radical generator and a dye which changes color by reacting with a radical and / or
Or, as the medium constituting the carrier containing the dye precursor,
Radical generator and dye and /
Alternatively, any dye precursor may be used as long as it is capable of diffusing and maintaining its shape, and is transparent enough to recognize a color change, without any limitation.

Specifically, as an acrylic resin, a polyester resin, a polyether resin, a polyurethane resin, a silicone resin, an epoxy resin, a vinyl resin, a resin used as a binder for ordinary inks, paints, etc., and a general pressure-sensitive adhesive. Any adhesive rubber resin or the like may be used, a mixed system of several kinds of the above resins, a ketone system,
It may or may not be diluted with a commonly used solvent such as ether type, alcohol type, cellosolve type, petroleum type, and water type solvent. Particularly, the adhesive rubber-based resin is advantageous in that it exhibits an adhesive function when the carrier and the transparent substrate are brought into contact with each other.

Specifically, the tacky rubber-based resin is a resin having Tg of room temperature or lower, preferably -10 ° C. or lower, and it is desirable that it is a rubber-like region in the temperature range during use. Examples include tacky acrylic resins, natural and synthetic cis-
1,4-polyisoprene rubber, butyl rubber, halogenated butyl rubber, partially vulcanized butyl rubber, styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SI
S), styrene-ethylene-butylene-styrene block copolymer (SEBS), silicone rubber, chloroprene rubber, nitrile rubber, butadiene rubber, and the like, which are used as the resin for adhesives.
In particular, the tacky acrylic resin can freely set the structure and the molecular weight to change the Tg, and can control the diffusion rate of the radical generator and the dye and / or the dye precursor. It is suitable as a medium for the radical generator and the dye and / or the dye precursor.
The adhesive acrylic resin has a functional group such as a hydroxyl group, a tertiary amino group, a carboxyl group, an amide group, or a nitrile group, and is generally used as an acrylic resin for an adhesive. Acrylic resins having these functional groups include one or more of monomers having a hydroxyl group, a tertiary amino group, a carboxyl group, an amide group, a nitrile group, and the like, and an alkyl (meth) acrylate, vinyl acetate, vinyl propionate. And copolymers with monomers such as vinyl ether and styrene.

The reaction is an ordinary radical polymerization, and there is no limitation on the reaction method, and it can be carried out by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, etc., but it is easy to control the reaction. Solution polymerization is preferred because it can be directly transferred to the next operation. The solvent may be any solvent, such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate, and butyl acetate, as long as it dissolves the resin of the present invention. A single solvent or a mixture of a plurality of solvents may be used. Further, the polymerization initiator used in the polymerization reaction is also known such as benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, organic peroxides such as lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. Anything can be used, and there is no particular limitation.

The adhesive rubber-based resin is partially crosslinked with a crosslinking agent such as an isocyanate and an epoxy compound to improve the adhesive property at the time of contact of the carrier and enhance the cohesive force, the radical generator and the dye, and The diffusion rate of the dye precursor can be controlled. Further, the polyurethane resin has good printability such as gravure printing, and is one of the preferable materials as a medium constituting the carrier from the viewpoint of productivity of the display material. Examples of such a polyurethane resin include “Ramister R Medium”, “New LP Super”, and “LP Queen”, which are trade names of urethane resins for gravure ink manufactured by Toyo Ink Mfg. Co., Ltd.

[0024]

The present invention will be described below with reference to examples. In the examples, “parts” means “parts by weight” and “%” means “% by weight”.

Resin 1 Butyl acrylate 94.1 parts Acrylic acid 5.9 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts Mixture 125 of each above composition heated at 80 ° C. in a nitrogen atmosphere. To the parts, 125 parts of the mixture having the same composition ratio was added dropwise, and after the completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of Resin 1 (solid content 40%).

Resin 2 Methyl acrylate 100.0 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts To 125 parts of the above mixture of each composition ratio heated to 80 ° C. in a nitrogen atmosphere, 125 parts of the mixture having the composition ratio was added dropwise, and after the completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of Resin 2 (solid content 40%).

Example 1 100 parts of a solution of resin 1 in a cool dark place, 12 parts of a 10% ethyl acetate solution of phenothiazine, and Darocur D11.
16 parts of 2 parts are mixed by stirring and coated on a release-treated surface-treated black PET film that does not transmit ultraviolet rays, and the temperature is 90 ° C.
Heat dry for 2 minutes to reduce the film thickness to 25 microns, and then PET.
The surface not covered with the above was also covered with a black PET film that does not transmit ultraviolet rays to obtain an ultraviolet irradiation amount display material 1 sandwiched with the black PET film. In addition, the ultraviolet irradiation dose was measured by the PE used at the time of coating.
It started by peeling off the T film. The change in color due to UV irradiation was observed under the following conditions. The results are shown in Table 2.

(1) Color Change Due to Ultraviolet Light Using an ultraviolet irradiation device (TOSUCURE T3000 manufactured by Toshiba), changes in irradiation amount and hue were observed. The change in hue was evaluated using a color difference meter CR-200 manufactured by Minolta Camera Co., Ltd. in the L ^* a ^* b ^* color system.

Examples 2 to 12, 14 to 15 and Comparative Examples 1 to 2 In a cool dark place, as in Example 1, a 10% ethyl acetate solution of a dye and / or a dye precursor and 10% of a decomposition catalyst of a radical generator. An ethyl acetate solution, a 10% ethyl acetate solution of a radical generator decomposition catalyst, and a resin solution were mixed and stirred at a mixing ratio shown in Table 1, and coated on a release surface-treated black PET film that does not transmit ultraviolet rays. Black PET that is heated and dried at 90 ° C for 2 minutes to a film thickness of 25 microns, and the surface not covered with PET does not transmit ultraviolet rays.
The film was covered with a film to obtain a UV dose display material sandwiched with a black PET film. The measurement of the ultraviolet irradiation dose was started by peeling off the PET film used for coating. The change in color due to UV irradiation was observed under the following conditions. The results are shown in Table 2.

Example 13 Urethane resin Lamister R medium for gravure ink manufactured by Toyo Ink Mfg. Co., Ltd. (solid content 40%) in a cool and dark place
100 parts of a solution of 10 parts of dye and / or dye precursor
% Ethyl acetate solution, 10% of radical generator decomposition catalyst
An ethyl acetate solution, a 10% ethyl acetate solution of a radical generator decomposition catalyst, and a resin solution were mixed and stirred at a compounding ratio shown in Table 1, and a release surface-treated black P that does not transmit ultraviolet rays
It is coated by gravure printing on ET film, heated and dried at 90 ° C for 2 minutes to a film thickness of 25 microns, and black P that does not transmit ultraviolet rays even on the uncovered surface of PET
A UV dose display material was obtained which was covered with an ET film and sandwiched with a black PET film. The measurement of the ultraviolet irradiation dose was started by peeling off the PET film used for coating. The change in color due to UV irradiation was observed under the following conditions. The results are shown in Table 2.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[0034]

EFFECT OF THE INVENTION With the ultraviolet irradiation amount display material of the present invention,
It became possible to easily and inexpensively display the irradiation amount of ultraviolet rays by changing the hue clearly. That is, the present invention does not start the reaction of color change until it is irradiated with ultraviolet rays, and the irradiation amount measurement is started at the time when the film that blocks the ultraviolet rays is peeled off, and the measurement can be started simply and clearly. It was Phenothiazine can display the irradiation dose by coloring from colorless to with time, and is very suitable as a material for indicating the effectiveness of a product. In particular, phenothiazine is initially colorless and, depending on the combination with the radical generator, gradually changes to red with the irradiation of visible light and ultraviolet light, and is sensuously optimal as a display material.

The range of irradiation dose to be measured can be adjusted by selecting an ultraviolet absorber or a resin in the medium constituting the carrier, and the wavelength range to be measured can be adjusted by selecting the radical generator. It was possible to control. From this, it was found that the ultraviolet irradiation amount display material of the present invention is effective for measuring the irradiation amount in a wide irradiation amount measuring range and ultraviolet wavelength region.

Claims (6)

[Claims] 1. An ultraviolet irradiation dose as a color change, in which a radical generator that generates radicals by ultraviolet irradiation and a dye and / or a dye precursor that changes color by reacting with radicals are carried in a carrier. Ultraviolet irradiation amount display material to display. 2. The ultraviolet irradiation dose measuring material according to claim 1, wherein the carrier is a resin layer laminated on a transparent substrate. 3. The ultraviolet irradiation dose measuring material according to claim 2, wherein the resin layer is a layer composed of an adhesive material. 4. The ultraviolet radiation dose measuring material according to claim 2, wherein the resin layer is a printed layer. 5. The ultraviolet irradiation dose measuring material according to claim 1, wherein the dye and / or the dye precursor is a phenothiazine-based coloring dye. 6. The ultraviolet irradiation dose measuring material according to claim 1, wherein the carrier contains an amine.