JPH08271334A - Ultraviolet ray detecting sheet - Google Patents

Abstract

PURPOSE: To provide an ultraviolet ray detecting sheet which is suitable to working environments with a simple and inexpensive structure, and easily regulated in curl by providing an ultraviolet ray shielding layer capable of being peeled out of the critical surface with the electron beam-hardening resin layer containing a coloring material. CONSTITUTION: This ultraviolet ray detecting sheet consists of an ultraviolet ray emitting material changed in coloring quantity according to the receiving quantity of ultraviolet ray, which is formed on a support body, and it has an electron beam- hardening resin layer containing a coloring material hardly causing a coloring reaction by electron beam emission. An ultraviolet ray shielding layer capable of being peeled out of the critical surface with the electron beam-hardening resin layer is provided. As the coloring material, a pyrazolone derivative leuco compound and an acidic material are used as essential components. A dye is dissolved or dispersed in the electron beam-hardening resin, and the holding of the dye to the support body and the holding of the ultraviolet ray shielding layer are performed at once by the electron beam emission. Although the ultraviolet ray shielding layer is peeled out of the coloring layer at the point of time when an ultraviolet ray receipt measurement is started, a one having a metal such as aluminum evaporated on a film, for example, is used as this layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet ray detecting sheet for displaying the amount of received light by irreversibly changing the discoloration density according to the amount of ultraviolet ray received.

[0002]

2. Description of the Related Art It is known that exposure to a large amount of ultraviolet rays adversely affects the human body such as causing skin cancer.
In recent years, it has been feared that a large amount of ultraviolet rays will be contained in the sunlight due to the destruction of the ozone layer, and a large amount of ultraviolet rays will be contained in the sunlight depending on the season. Therefore, the measurement of the amount of received ultraviolet rays is emphasized.

Conventionally, as an ultraviolet intensity meter, a structure is known in which ultraviolet rays are converted into an electric signal, and the electric signal is digitally converted to be digitally displayed.
However, the above-mentioned ultraviolet intensity meter requires an electronic circuit and a power source, has a complicated structure, is expensive, and is not currently popular. Further, an ultraviolet color changing sheet (JP-A-60-89352) in which a support holds a compound that changes color by the energy of ultraviolet rays is exemplified. However, the exemplified UV discoloration sheet needs to use an organic solvent, which is not preferable from the viewpoint of working environment. Since a further drying process is required,
It is difficult to adjust the curl and curl of the seat, and
The ultraviolet light receiving coloring material may be colored due to heat, so that its use is limited.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above problems and has a simple structure and is more inexpensive.
An ultraviolet detection sheet, which is suitable for a work environment and whose curl can be easily adjusted, is provided.

[0005]

An ultraviolet detecting sheet according to the present invention is a support and a ultraviolet coloring material which is formed on the support and whose amount of coloring changes according to the amount of received ultraviolet rays. It has an electron beam-curable resin layer containing a color-forming material that hardly causes a color-developing reaction upon irradiation with a beam, and an ultraviolet ray shielding layer that can be peeled from the interface with the electron-beam-curable resin layer.

The ultraviolet detection sheet according to the present invention is a support and a UV color-forming material formed on the support, the color development amount of which varies depending on the amount of received UV light. An electron beam-curable resin layer containing a color-forming material that causes a color-developing reaction different from the above, and an ultraviolet ray shielding layer that can be peeled from the interface with the electron beam-curable resin layer. As these coloring materials, it is preferable to use a pyrazolone derivative leuco compound described later and an acidic substance as essential components because they hardly cause a coloring reaction by electron beam irradiation, and at least a hindered phenol compound described below is used as a photosensitizer. It is more preferable to contain one kind in the layer in which the coloration amount changes depending on the amount of received light. Further, it is preferable to use a phenoxazine compound or a phenothiazine compound, which will be described later, as a material to be contained in the layer in which the coloration amount changes depending on the amount of received light, because it causes a coloration reaction of a color different from the coloration by ultraviolet rays upon electron beam irradiation.

[0007]

The support in the present invention is not particularly limited as long as it is a flexible sheet-like material. For example, generally known various kinds of coated paper, fine paper, synthetic paper, metallized paper, colored paper, etc. Paper sheets; plastic films such as polyethylene terephthalate, polypropylene and polyethylene; metal foils such as copper, iron and aluminum; cloth and the like, or a laminated body or a laminated body thereof. Incidentally, these supports are preferably opaque so as to block ultraviolet rays. Further, if necessary, an appropriate undercoat layer may be provided between the support and the layer in which the amount of color development changes depending on the amount of received ultraviolet rays.

The electron beam curable resin used in the present invention is
It is not particularly limited as long as it is a material that dissolves or disperses a material whose coloring amount changes depending on the amount of received ultraviolet rays and that is cured by electron beam irradiation, but work when molding the electron beam curable resin layer Therefore, the viscosity of the electron beam curable resin containing a material that develops color depending on the amount of received ultraviolet rays is 1
0 to 10,000 cps, more preferably 100 to
About 5000 cps is suitable. If it is lower than 10 cps, the resin exudes or is impregnated into the support at the time of bonding and the bonding is insufficient. If it is higher than 10000 cps, the coated surface becomes non-uniform and a uniform bonded surface is obtained. It can be difficult.

The coating amount of the electron beam curable resin containing the material whose coloring amount changes depending on the amount of received ultraviolet rays is not particularly limited, but if it is less than 0.1 g / m ² , the desired effect is sufficiently obtained. In addition, if it exceeds 50 g / m ² , it is not preferable from the economical point of view. Generally, the dry weight is 0.1 to 50 g / m ² , preferably 0.5 to 30 g / m ^2.
It is adjusted within a range. As the electron beam curable resin, for example, the following monomers and oligomers or a mixture thereof are used. (A) Radical-polymerizable monofunctional monomer Acrylic acid, ethyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, triloxyethyl acrylate, Nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, 1,3-dioxolane acrylate, phenoxydiethylene glycol acrylate, benzyl acrylate, butoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, glycidyl acrylate, carbitol acrylate , Isobornyl acrylate, etc.

(B) Radical-polymerizable polyfunctional monomer 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, dicyclopentanyl diacrylate, butylene glycol diacrylate, penta Erythritol diacrylate, trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, etc. .

(C) Radical polymerizable oligomer (prepolymer) Polyester (poly) acrylate and urethane (poly)
Acrylate, epoxy (poly) acrylate, polyol (poly) acrylate and the like.

According to the present invention, a dye whose color density changes depending on the amount of received ultraviolet rays is previously provided on a support, an electron beam curing resin is applied thereon, and then an ultraviolet ray shielding layer is provided to irradiate an electron beam, Compared with the method of holding the shielding layer, by dissolving or dispersing the dye in the electron beam curable resin exemplified above, holding the dye on the support and holding the ultraviolet shielding layer at once by electron beam irradiation. It is very good in what it can do.

[0013]

[Chemical 9]

[In the general formula (1), R ₁ is an alkyl group, an alkoxyalkyl group or an optionally substituted aryl group, and R ₂ and R ₃ are optionally substituted alkyl groups or An aryl group which may have a substituent is represented by R ₄
Is an alkyl group which may have a substituent, an aryl group which may have a substituent or an amino group which may have a substituent, and R ₅ and R ₆ are each an alkyl group, an alkoxyl group or a halogen atom. And p is 0 or an integer of 1 to 5, and q is 0 or an integer of 1 to 4. ]

The material used in the present invention that develops a color depending on the amount of received ultraviolet rays may be any material that develops a color upon irradiation with ultraviolet rays, but a pyrazolone compound represented by the general formula (1) is particularly preferable. This pyrazolone compound is a substantially colorless and non-volatile stable compound, which itself exhibits almost no color development upon irradiation with ultraviolet rays.
However, when the pyrazolone-based leuco compound is dissolved in an electron beam curing resin together with an acidic substance, and the surface cured by irradiation with an electron beam is irradiated with ultraviolet rays, its mechanism of action is not clear, but The action causes a pigmentation reaction of the pyrazolone-based leuco compound to produce an azomethine dye. That is, the color development of the color forming material of the present invention by irradiation with ultraviolet rays is based on the formation of the azomethine dye.

Further, since the azomethine dye once formed is a stable dye that does not become colorless under normal conditions, the dye image can be stored for a long period of time under light-shielding conditions. The reaction for forming this azomethine dye is generated not only when it is irradiated with ultraviolet rays but also when it is heated. Therefore, the pyrazolone leuco compound and the acidic substance are dissolved in the electron beam curable resin, if necessary, the hindered phenol compound is dissolved, and the electron beam irradiation suppresses the generation of the azomethine dye due to heat, and the measurement of the amount of ultraviolet light received. Can be done accurately. The color tone of the dye of the present invention is affected by the type of each essential component, the type of other additives described below, or the mixing ratio thereof, and the like.
It is bluish purple. In addition, the intrinsic sensitivity range of this color former is the ultraviolet region, but since it exhibits a substantially constant sensitivity to ultraviolet rays in the range of 200 to 400 nm, the integrated illuminance is obtained without being affected by its spectral distribution. It is possible.

In the pyrazolone leuco compound represented by the general formula (1), R ₁ represents an alkyl group, an alkoxyalkyl group or an aryl group which may have a substituent. Here, the aryl group means a phenyl group. , A naphthyl group or a heteroaromatic ring residue, and examples of the substituent thereof include an alkyl group, an alkoxyl group and a halogen atom. In addition, as R ₁ , among these, C _{1 to} C ₄
Alkyl groups or phenyl groups are preferred.

R ₂ and R ₃ each represent an alkyl group which may have a substituent or an aryl group which may have a substituent, and the substituent of the alkyl group is an aryl group, an alkoxyl group or a hydroxyl group. Examples of the substituent of the aryl group include an alkylsulfonylamino group, and an alkyl group, an alkoxyl group, and a halogen atom.
As R ₂ and R ₃ , among these, C _{1 to} C which may have a C _{1 to} C ₄ alkoxyl group, a hydroxyl group or a C _{1 to} C ₄ alkylsulfonylamino group as a substituent. An alkyl group of ₄ is preferred.

R ₄ is an alkyl group which may have a substituent,
An aryl group which may have a substituent or an amino group which may have a substituent is shown. As the substituent of the alkyl group, an aryl group, an alkoxyl group, an aryloxy group,
Examples thereof include an acylamino group, an N-substituted carbamoyl group, and an N-substituted sulfamoyl group, and examples of the substituent of the aryl group include an alkyl group, an alkoxyl group, an aryloxy group, a halogen atom, an arylalkyl group, an arylalkoxy group, and aryloxy. Examples thereof include an alkoxyl group, an arylsulfonylalkoxy group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an N-substituted carbamoyl group and an N-substituted sulfamoyl group. Further, examples of the substituent of the amino group include an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, and the like, wherein each alkyl group and aryl group further has a substituent. The substituent of the alkyl group may have an aryl group, an alkoxyl group, an aryloxy group, an acylamino group, an N-substituted carbamoyl group, an N-substituted sulfamoyl group, and the like, and a substituent of the aryl group is an alkyl group. Group, alkoxyl group, aryloxy group, halogen atom, arylalkyl group, arylalkoxy group, aryloxyalkoxy group, arylsulfonylalkoxy group, imide group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, N-substituted carbamoyl group Group, such as N- substituted sulfamoyl group.

A material using a pyrazolone leuco compound having an aroylamino group which may have a substituent or an aryl group which may have a substituent as R ₄ is
It is preferable because it tends to have higher photocolorability than the others. Among them, those having an aryl group which may have a substituent are preferable, and those having a phenyl group which may have a substituent or a naphthyl group which may have a substituent are particularly preferable.

Specific examples of such pyrazolone type leuco compounds include the following. 1-phenyl-3-methyl-4- (4-N, N-dimethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-methyl-4- (4-N, N-diethylamino) Phenylamino) -4-acetylamino-
5-pyrazolone, 1-phenyl-3-methyl-4- (4
-N, N-diethylamino-2-methylphenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-methyl-4- (4-N, N-diethylaminophenylamino) -4-benzoylamino- 5-pyrazolone, 1-phenyl-3-tert-butyl-4- (4-
N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-dodecyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1 −
(2,4,6-Trichlorophenyl) -3-methyl-4
-(4-N, N-diethylaminophenylamino) -4
-Acetylamino-5-pyrazolone, 1,3-diphenyl-4- (4-N, N-dimethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1,3-
Diphenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone,
1,3-diphenyl-4- (4-N, N-dibutylaminophenylamino) -4-acetylamino-5-pyrazolone, 1,3-diphenyl-4- (4-N, N-diethylamino-2-methyl Phenylamino) -4-acetylamino-5-pyrazolone, 1,3-diphenyl-4-
(4-N, N-diethylamino-2-methoxyphenylamino) -4-acetylamino-5-pyrazolone, 1,
3-diphenyl-4- (4-N, N-diethylamino-
2-ethoxyphenylamino) -4-acetylamino-
5-pyrazolone,

1,3-diphenyl-4- [4-N-ethyl-N- (2-hydroxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone, 1,3-
Diphenyl-4- [4-N-ethyl-N- (2-methylsulfonylaminoethyl) aminophenylamino] -4
-Acetylamino-5-pyrazolone, 1,3-diphenyl-4- [4-N-ethyl-N- (2-methoxyethyl) aminophenylamino] -4-acetylamino-5
-Pyrazolone, 1,3-diphenyl-4- (4-N, N
-Diethylaminophenylamino) -4-benzoylamino-5-pyrazolone, 1,3-diphenyl-4- (4
-N, N-diethylaminophenylamino) -4-p-
Toluoylamino-5-pyrazolone, 1-phenyl-3
-P-tolyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone,
1-phenyl-3-p-tolyl-4- (4-N, N-diethylamino-2-methylphenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-p-
Methoxyphenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (2,4-xylyl) -4-
(4-N, N-diethylaminophenylamino) -4-
Acetylamino-5-pyrazolone, 1-phenyl-3-
p-cumenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone,
1-Phenyl-3-o-tolyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-
5-pyrazolone, 1-phenyl-3-p-chlorophenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-p-
Trily-3-phenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-mesityl-3-phenyl-4- (4-N,
N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-p-methoxyphenyl-3
-Phenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1
-(2,4,6-Trichlorophenyl) -3-phenyl-4- (4-N, N-diethylaminophenylamino)
-4-Acetylamino-5-pyrazolone, 1-phenyl-3- [4- (2,4-di-tert-pentylphenoxyacetylamino) phenyl] -4- (4-N, N-diethylaminophenylamino)- 4-acetylamino-5
-Pyrazolone, 1-phenyl-3- [4- (phenylsulfonylamino) phenyl] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5
-Pyrazolone, 1-phenyl-3- (1-naphthyl)-
4- (4-N, N-dimethylaminophenylamino)-
4-acetylamino-5-pyrazolone, 1-phenyl-
3- (2-naphthyl) -4- (4-N, N-dimethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (1-naphthyl) -4-
(4-N, N-diethylaminophenylamino) -4-
Acetylamino-5-pyrazolone, 1-phenyl-3-
(1-Naphtyl) -4- (4-N, N-dibutylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (1-naphthyl) -4- (4-
N, N-diethylamino-2-methylphenylamino)
-4-Acetylamino-5-pyrazolone, 1-phenyl-3- (1-naphthyl) -4- (4-N, N-diethylamino-2-methoxyphenylamino) -4-acetylamino-5-pyrazolone, 1 -Phenyl-3- (1-naphthyl) -4- (4-N, N-diethylamino-2-ethoxyphenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (1-naphthyl)- 4-
[4-N-ethyl-N- (2-hydroxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone, 1-phenyl-3- (1-naphthyl) -4- [4
-N-ethyl-N- (2-methylsulfonylaminoethyl) aminophenylamino] -4-acetylamino-5
-Pyrazolone, 1-phenyl-3- (1-naphthyl)-
4- [4-N-ethyl-N- (2-methoxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone, 1-phenyl-3- (1-naphthyl) -4-
(4-N, N-diethylaminophenylamino) -4-
Benzoylamino-5-pyrazolone, 1-phenyl-3
-(1-Naphthoyl) -4- (4-N, N-diethylaminophenylamino) -4-p-toluoylamino-5
-Pyrazolone, 1-phenyl-3- (2-naphthyl)-
4- (4-N, N-diethylaminophenylamino)-
4-acetylamino-5-pyrazolone, 1-phenyl-
3- (4-methyl-1-naphthyl) -4- (4-N, N
-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (4-methoxy-1-naphthyl) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino- 5-pyrazolone, 1-phenyl-3- (2,4-dimethyl-1-naphthyl) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-
Phenyl-3- (4-isopropyl-1-naphthyl)-
4- (4-N, N-diethylaminophenylamino)-
4-acetylamino-5-pyrazolone, 1-p-tolyl-3- (1-naphthyl) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-mesityl- 3- (1-naphthyl) -4-
(4-N, N-diethylaminophenylamino) -4-
Acetylamino-5-pyrazolone, 1-p-methoxyphenyl-3- (1-naphthyl) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-
5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3- (1-naphthyl) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5
-Pyrazolone, 1-phenyl-3-benzyl-4- (4
-N, N-dimethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-benzyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone ,

1-phenyl-3-benzyl-4- (4-
N, N-diethylamino-2-methylphenylamino)
-4-Acetylamino-5-pyrazolone, 1-phenyl-3-benzyl-4- (4-N, N-diethylaminophenylamino) -4-benzoylamino-5-pyrazolone, 1-phenyl-3-phenethyl-4 -(4-N, N
-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (1-naphthylmethyl) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone 1
-Phenyl-3- (2-naphthylmethyl) -4- (4-
N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-α-methylbenzyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5- Pyrazolone,
1-phenyl-3-benzhydryl-4- (4-N, N
-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-benzyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino -5-pyrazolone, 1-phenyl-3-anilino-4- (4-
N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (2-
Chloroanilino) -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3- (4-methoxyanilino) -4
-(4-N, N-diethylaminophenylamino) -4
-Acetylamino-5-pyrazolone, 1-phenyl-3
-P-toluidino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3-
[2-chloro-5- (2-octadecylsuccinylimino) anilino] -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-benzoylamino-4 -(4-
N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-benzoylamino-4- (4-N, N-dibutylaminophenylamino) -4-acetylamino-5-pyrazolone 1
-Phenyl-3-benzoylamino-4- (4-N, N
-Diethylamino-2-ethylphenylamino) -4-
Acetylamino-5-pyrazolone, 1-phenyl-3-
Benzoylamino-4- [4-N-ethyl-N- (2-
Hydroxyethyl) aminophenylamino] -4-acetylamino-5-pyrazolone, 1-phenyl-3-p-
Toluoylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-p-chlorobenzoylamino-
4- (4-N, N-diethylaminophenylamino)-
4-acetylamino-5-pyrazolone, 1-phenyl-
3- [3- (2,4-di-tert-pentylphenoxyacetylamino) benzoylamino] -4- (4-
N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3- {3- [2- (2,4-di-te
rt-Pentylphenoxy) hexanoylamino] benzoylamino} -4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1- (2,4,6-trichlorophenyl) -3 −
[3- (2,4-di-tert-pentylphenoxyacetylamino) benzoylamino] -4- (4-N, N
-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-phenylacetylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1
-Phenyl-3-pivaloylamino-4- (4-N, N
-Diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 1-phenyl-3-stearoylamino-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone and the like.

Of course, it is not limited to these pyrazolone type leuco compounds, and it is also possible to use two or more kinds in combination. The use ratio of the pyrazolone-based leuco compound in the present invention is not particularly limited,
Although it depends on the molecular absorption coefficient of the pyrazolone-based leuco compound at the time of color development, it is generally 0.05 to 20% by weight, preferably 1 to 1% by weight based on the entire layer that develops color depending on the amount of received ultraviolet rays.
It is preferably used in the range of 0% by weight.

In the present invention, as an acidic substance which is an essential component together with a color former, many are known as a developer for heat-sensitive or pressure-sensitive recording materials or a precursor thereof, and they are easily available. it can. Specific examples of such acidic substances include the following.

4,4'-isopropylidene diphenol, 4,4'-isopropylidene (2-chlorophenol), 4,4'-isopropylidene bis (2,6-dichlorophenol), 4,4'-isopropylidene Redene bis (2,6-dibromophenol), 4,4′-isopropylidene bis (2-methylphenol), 4,4′-isopropylidene bis (2,6-dimethylphenol),
4,4'-sec-butylidene diphenol, 2,2 '
-Bis (4-hydroxyphenyl) -4-methylpentane, 4,4'-cyclohexylidenebisphenol,
4,4′-Cyclohexylidenebis (2-methylphenol), 4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenyl ether, α-naphthol, β-naphthol, 2,2′-thiobis (4.
6-dichlorophenol), 4-tert-octylcatechol, 2,2'-methylenebis (4-chlorophenol), 2,2'-dihydroxybiphenyl, methyl-bis (4-hydroxyphenyl) acetate, ethyl-bis (4 -Hydroxyphenyl) acetate, benzyl-
Bis (4-hydroxyphenyl) acetate, 4,4 '
-(P-phenylenediisopropylidene) diphenol, 4,4 '-(m-phenylenediisopropylidene)
Diphenol, 4-hydroxydiphenyl sulfone,
4,4'-dihydroxydiphenyl sulfone, 2,4 '
-Dihydroxydiphenylsulfone, 4-hydroxy-
4'-methyldiphenyl sulfone, 4-hydroxy-
4'-isopropoxydiphenyl sulfone, 4-hydroxy-3 ', 4'-tetramethylene diphenyl sulfone, 4-hydroxy-3', 4'-trimethylene diphenyl sulfone, 4,4'-dihydroxy diphenyl sulfide, 3,3 '-Diallyl-4,4'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl)
Acetic acid-2-phenoxyethyl ester, p-hydroxy-N- (2-phenoxyethyl) benzenesulfonamide, dimethyl 4-hydroxyphthalate, 1,5-bis (4-hydroxyphenylthio) -3-oxa-pentane, 1,7-bis (4-hydroxyphenylthio)-
3,5-dioxa-heptane, 1,8-bis (4-hydroxyphenylthio) -3,6-dioxa-octane,
(4-Hydroxyphenylthio) acetic acid-2- (4-hydroxyphenylthio) ethyl ester, 4-acetylphenol, 4-tert-octylphenol, 4,4′-
Dihydroxydiphenylmethane, hydroquinone, resorcinol, catechol, pyrogallol, propyl gallate, octyl gallate, isoamyl gallate, stearyl gallate, 4,4 ′-(1,3-dimethylbutylidene) bisphenol, 2,2-bis (4) -Hydroxyphenyl) -4-methylpentane, 4-hydroxy-4 '
-Methoxydiphenyl sulfone, 3,4-dihydroxy-4'-methyldiphenyl sulfone, hydroquinone monobenzyl ether, 4-hydroxybenzophenone,
2,4-dihydroxybenzophenone, 2,4,4'-
Trihydroxybenzophenone, 2,2 ', 4,4'-
Tetrahydroxybenzophenone, 4,4'-dihydroxybenzophenone, methyl 4-hydroxybenzoate,
Ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, sec-butyl 4-hydroxybenzoate,
Pentyl 4-hydroxybenzoate, phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 4-
Tolyl hydroxybenzoic acid, 4-hydroxybenzoic acid p
-Chlorophenyl, phenylpropyl 4-hydroxybenzoate, phenethyl 4-hydroxybenzoate, p-chlorobenzyl 4-hydroxybenzoate, p-methoxybenzyl 4-hydroxybenzoate, p-phenylphenol-formalin resin, p-butylphenol- Acetylene resin Novolak type phenolic resin, phenolic compounds such as phenolic polymers, aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, stearic acid; benzoic acid, 4-tert-butylbenzoic acid , 4-
Trifluoromethylbenzoic acid, 4-chlorobenzoic acid, 4-
Nitrobenzoic acid, 3-sec-butyl-4-hydroxybenzoic acid, 3-cyclohexyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, α-
Naphthoic acid, β-naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, monomethyl terephthalate, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid,
3,5-di-tert-butylsalicylic acid, 3-methyl-5
-Benzylsalicylic acid, 4-pentyloxysalicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl)
Salicylic acid, 3,5-di- (α-methylbenzyl) salicylic acid, 2-hydroxy-1-benzyl-3-naphthoic acid, 3-dodecylsalicylic acid, 3-nonylsalicylic acid,
3-benzyl salicylic acid, 3- (α-methylbenzyl)
Salicylic acid, 3-chloro-5- (α-methylbenzyl)
Salicylic acid, 3,5-di- (α, α-dimethylbenzyl) salicylic acid, 3- (α, α-dimethylbenzyl)-
5-methylsalicylic acid, 4- (3-phenylsulfonylpropoxy) salicylic acid, 4- (5-phenylsulfonyl-3-oxa-pentyloxy) salicylic acid, 4-
(3-p-tolylsulfonylpropoxy) salicylic acid,
4- (5-p-tolylsulfonyl-3-oxa-pentyloxy) salicylic acid, 4- (3-p-methoxyphenylsulfonylpropoxy) salicylic acid, 4- (3-p-
Chlorophenylsulfonylpropoxy) salicylic acid, 4
-(2-phenoxyethoxy) salicylic acid, 4- (2-
p-methoxyphenoxyethoxy) salicylic acid, 4-
(5-p-Methoxyphenoxy-3-oxa-pentyloxy) salicylic acid, 4- (5-phenoxy-3-oxa-pentyloxy) salicylic acid, 5- [p- (2-phenoxyethoxy) cumyl] salicylic acid, 5- [P-
(5-phenoxy-3-oxa-pentyloxy) cumyl] salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid, 5- [p- (4-
p-tolylsulfonylpropoxy) cumyl] salicylic acid, 5- [p- (3-phenylsulfonylpropoxy)
Aromatic carboxylic acids such as cumyl] salicylic acid, 5- [p- (3-p-methoxyphenylsulfonylpropoxy) cumyl] salicylic acid; and salts of phenolic compounds, aliphatic carboxylic acids, aromatic carboxylic acids and polyvalent metals A metal complex compound such as an antipyrine complex of zinc thiocyanate.

Of course, the acid substances are not limited to these, and it is also possible to use two or more kinds in combination.
As the polyvalent metal forming a salt or complex in the acidic substance, a divalent, trivalent or tetravalent metal is preferable, and zinc, calcium, aluminum, magnesium, tin and iron are particularly preferable. In the present invention, the amount of the acidic substance used is not particularly limited, but is 50 to 700% by weight, preferably 1% by weight based on the pyrazolone leuco compound.
It is preferably used in the range of 100 to 500% by weight.

The hindered phenol compound used as the photosensitizer in the present invention means a branched alkyl group having at least one ortho-position of a phenolic hydroxyl group of C _{3 to} C ₅ or a cycloalkyl having C _{5 to} C ₆ . The compounds represented by the following formulas (2) to (5) are mentioned as typical examples of the compounds substituted with a group.

[0029]

[Chemical 10]

[In the general formula (2), R₁Is C₃~ C
_FiveBranched alkyl group of, or C_Five~ C ₆Cycloarch
R group, R₂Is a hydrogen atom, C₃~ C_FiveBranched alkyl
Group or C_Five~ C₆Cycloalkyl group of R₃Is hydrogen
Atom or C₁~ C_FourThe alkyl group of R_Four, R_Five, R
₆, R₇, R₈Is a hydrogen atom or C₁~ C_FourThe alkyl
Represents a group. ]

[0031]

[Chemical 11]

[In the general formula (3), R₁Is C₃~ C
_FiveBranched alkyl group of, or C_Five~ C ₆Cycloarch
R group, R₂Is a hydrogen atom, C₃~ C_FiveBranched alkyl
Group or C_Five~ C₆The cycloalkyl group of R₃Is water
Elementary atom or C₁~ C_FourAlkyl group of A, sulfur source
Child, or C that may branch₀~ C₆The alkylene group of
Show. ]

[0033]

[Chemical 12]

[In the general formula (4), R₁Is C₃~ C
_FiveBranched alkyl group of, or C_Five~ C ₆Cycloarch
R group, R₂Is C₁~ C_FourRepresents an alkyl group of
Sulfur atom or C which may be branched₀~ C₆Arche of
Group. ]

[0035]

[Chemical 13]

[In the general formula (5), R₁, R₂Is C
₃~ C_FiveBranched alkyl group of, or C _Five~ C₆The cyclo
The alkyl group, Z is -NH-, or -O (CH₂)_n
-(Where n is an integer of 1 to 5), and m is 1 to 4
Indicates an integer. However, when m is 1, W is C₁~ C₁₈of
When m is 2, W is a sulfur atom or
C may be changed₀~ C₆Of the alkylene group of
Ki is W is C₁~ C₆Represents a trivalent saturated alkyl group of
When is 4, W represents a carbon atom. ]

These are substantially colorless and non-volatile stable compounds. Many of them are known as antioxidants for rubbers, plastics or preservability improvers for heat-sensitive recording materials, and are easily available. be able to. Specific examples of such hindered phenol compounds include the followings.

1,1,3-tris (3,5-di-tert-
Butyl-4-hydroxyphenyl) butane, 4,4′-
Methylenebis (2,6-di-tert-butylphenol), 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3-
(3,5-Di-tert-butyl-4-hydroxyphenyl) octadecyl propionate, 2,6-di-tert-butyl-4-methylphenol, 3,5-di-tert-butyl-4-hydroxybenzyl alcohol , 2,6-di-
tert-butyl-4-N, N-dimethylaminomethylphenol, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris ( 3,5-di-tert-butyl-4
-Hydroxybenzyl) isocyanurate, tris [3
-(3,5-Di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, pentaerythritol tetrakis [3- (3,5-di-te
rt-Butyl-4-hydroxyphenyl) propionate], 2,6-bis (α-methylbenzyl) phenol, 2,6-di-tert-butyl-4-methoxyphenol, 1,1,3-tris (2- Methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-ethyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2- Methyl-
4-hydroxy-5-tert-butylphenyl) propane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4'-butylidene-bis- (2-tert- Butyl-5-methylphenol), 4,4'-thiobis- (2-tert-butyl-
5-methylphenol), bis [3- (3,5-di-te
rt-Butyl-4-hydroxyphenyl) propionyloxyethyl] sulfide, 2-α-methylbenzylphenol, 2-tert-butyl-4-methoxyphenol,
2,2'-methylenebis- (6-tert-butyl-4-methylphenol), 2,2'-methylenebis- (6-te
rt-butyl-4-ethylphenol), 2,2′-methylene-bis (4,6-di-tert-butylphenol,
2,2'-methylenebis [4-methyl-6- (1,3,
5-trimethylhexyl) phenol], 4,4'-isopropylidene bis (2-tert-butylphenol)
etc. Of course, it is not limited to these hindered phenol compounds, and it is also possible to use two or more kinds in combination.

In the present invention, the use ratio of the hindered phenol compound is not particularly limited, but it is preferably 50 to 700% by weight, preferably 100 to 500% by weight based on the pyrazolone leuco compound. preferable.

The phenoxazine compound or phenothiazine compound used in the present invention is represented by the general formulas (6) to (8). The phenoxazine compound is a stable compound which is yellow and non-volatile. The compound is generally greenish gray and is a nonvolatile stable compound like phenoxazine. When these are dissolved or dispersed in an electron beam curable resin and cured by irradiation with an electron beam, the color changes to green, but when the cured surface is irradiated with ultraviolet light, the benzoyl group or naphthoyl group is released and a blue color is developed. To do.
This color tone is affected by the type of electron beam curable resin, the compounding ratio, etc., but is generally yellow blue to blue purple.

[0041]

Embedded image

[In the general formula (6), R₁~ R_FourHaso
Each C₁~ C₆The alkyl group of R _FiveIs a hydrogen atom, C
₁~ C_FourAlkyl group of C₁~ C_FourThe alkoxyl group
Or a halogen atom. ]

[0043]

[Chemical 15]

[In the general formula (7), R₁~ R_FourHaso
Each C₁~ C₆The alkyl group of R _FiveIs a hydrogen atom, C
₁~ C_FourAlkyl group of C₁~ C_FourThe alkoxyl group
Or a halogen atom. ]

[0045]

Embedded image

[In the general formula (8), R₁~ R_FourHaso
Each C₁~ C₆The alkyl group of R _FiveIs a hydrogen atom, C
₁~ C_FourAlkyl group of C₁~ C_FourThe alkoxyl group
Or a halogen atom. ]

General formulas (6) and (7) used in the present invention
Specific examples of the phenoxazine compound represented by are, for example, 3,7-bis (diethylamino) -10- (4-methylbenzoyl) -phenoxazine and 3,7-bis (diethylamino) -10-benzoyl-phenoxazine. ,
3,7-bis (diethylamino) -10- (4-ethylbenzoyl) -phenoxazine, 3,7-bis (diethylamino) -10- (4-methoxybenzoyl) -phenoxazine, 3,7-bis (diethylamino) -10-
(4-Ethoxybenzoyl) -phenoxazine, 3,7
-Bis (diethylamino) -10- (4-isopropoxybenzoyl) -phenoxazine, 3,7-bis (diethylamino) -10- (4-n-butoxybenzoyl)
-Phenoxazine, 3,7-bis (diethylamino)-
10- (2-methylbenzoyl) -phenoxazine,
3,7-bis (diethylamino) -10- (3-methylbenzoyl) -phenoxazine, 3,7-bis (diethylamino) -10- (4-chlorobenzoyl) -phenoxazine, 3,7-bis (diethylamino) -10-
(2-Chlorobenzoyl) -phenoxazine, 3,7-
Bis (dimethylamino) -10- (4-methylbenzoyl) -phenoxazine, 3,7-bis (dimethylamino) -10-benzoyl-phenoxazine, 3,7-bis (dimethylamino) -10- (4- Methoxybenzoyl) -phenoxazine, 3,7-bis (di-n-butylamino) -10- (4-methylbenzoyl) -phenoxazine, 3,7-bis (di-n-butylamino) -10
-Benzoyl-phenoxazine, 3-diethylamino-
7-Dimethylamino-10- (4-methylbenzoyl)
-Phenoxazine, 3-diethylamino-7-dimethylamino-10-benzoyl-phenoxazine, 3,7-
Bis (N-methyl-Nn-propylamino) -10-
(4-Methylbenzoyl) -phenoxazine, 3,7-
Bis (N-methyl-Nn-propylamino) -10-
Benzoylphenoxazine, 3,7-bis (N-ethyl-N-isoamylamino) -10- (4-methylbenzoyl) -phenoxazine, 3,7-bis (N-ethyl-
N-isoamylamino) -10-benzoyl-phenoxazine, 3,7-bis (diethylamino) -10- (1
-Naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-naphthoyl) -phenoxazine, 3,7-bis (diethylamino) -10- (2-methyl-1-naphthoyl) phenoxazine, 3 , 7-Bis (diethylamino) -10- (4-methyl-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (8-methyl-1-naphthoyl) phenoxazine, 3,7-bis (Diethylamino) -10- (4
-Ethyl-1-naphthoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (1-methyl-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-methyl-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10-
(6-methyl-2-naphthoyl) phenoxazine, 3,
7-bis (diethylamino) -10- (4-ethyl-2)
-Naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-methoxy-1-naphthoyl)
Phenoxazine, 3,7-bis (diethylamino) -1
0- (4-methoxy-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (5-methoxy-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2 -Ethoxy-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-isopropoxy-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino)
-10- (1-Methoxy-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3-
Methoxy-2-naphthoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (6-methoxy-2-
Naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3-ethoxy-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10
-(3-isopropoxy-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2-
Chloro-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (4-chloro-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (5-chloro-1- Naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (8
-Chloro-1-naphthoyl) phenoxazine, 3,7-
Bis (diethylamino) -10- (4-bromo-1-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (2,4-dichloro-1-naphthoyl)
Phenoxazine, 3,7-bis (diethylamino) -1
0- (3-chloro-2-naphthoyl) phenoxazine,
3,7-bis (diethylamino) -10- (5-chloro-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (8-chloro-2-naphthoyl) phenoxazine, 3,7- Bis (diethylamino)
-10- (3-Bromo-2-naphthoyl) phenoxazine, 3,7-bis (diethylamino) -10- (3,5
-Dichloro-2-naphthoyl) phenoxazine, 3,7
-Bis (dimethylamino) -10- (1-naphthoyl)
Phenoxazine, 3,7-bis (dimethylamino) -1
0- (2-naphthoyl) -phenoxazine, 3,7-bis (di-n-butylamino) -10- (1-naphthoyl) phenoxazine, 3,7-bis (di-n-butylamino) -10 -(2-naphthoyl) -phenoxazine,
3-Dimethylamino-7-diethylamino-10- (1
-Naphthoyl) phenoxazine, 3-dimethylamino-
7-diethylamino-10- (2-naphthoyl) -phenoxazine, 3,7-bis (N-methyl-Nn-propylamino) -10- (1-naphthoyl) phenoxazine and the like can be mentioned.

Among these compounds, 3,7-bis (diethylamino) -10- (4-methylbenzoyl)
-Phenoxazine and 3,7-bis (diethylamino)-
10- (1-naphthoyl) phenoxazine is particularly preferably used because it exhibits a particularly excellent color developability.

The phenothiazine derivative represented by the general formula (8) used in the present invention is a dye which develops a blue color tone when used alone. Specifically, the following compounds are exemplified. It 3,7-bis (dimethylamino)
-10-benzoylphenothiazine, 3,7-bis (diethylamino) -10-benzoylphenothiazine,
3,7-bis (di-n-butylamino) -10-benzoylphenothiazine, 3,7-bis (dimethylamino)-
10- (4-methylbenzoyl) phenothiazine, 3,
7-bis (diethylamino) -10- (4-methylbenzoyl) phenothiazine, 3,7-bis (di-n-butylamino) -10- (4-methylbenzoyl) phenothiazine, 3,7-bis (dimethylamino) -10- (4
-Methoxybenzoyl) phenothiazine, 3,7-bis (dimethylamino) -10- (4-ethoxybenzoyl) phenothiazine, 3,7-bis (dimethylamino)
-10- (4-chlorobenzoyl) phenothiazine,
3,7-bis (dimethylamino) -10- (2-methylbenzoyl) phenothiazine, 3,7-bis (dimethylamino) -10- (2-methoxybenzoyl) phenothiazine, 3,7-bis (dimethylamino)- 10- (2
-Chlorobenzoyl) phenothiazine, 3,7-bis (di-n-butylamino) -10- (4-chlorobenzoyl) phenothiazine, 3-diethylamino-7-dimethylamino-10-benzoylphenothiazine and the like.

The compounds are not limited to these compounds, and any compounds included in the general formulas (6) to (8) can be used, and if necessary, 2
It is also possible to use two or more species together.

In the present invention, the ratio of the phenoxazine compound or the phenothiazine compound used is not particularly limited, but generally 0.05 to 20% by weight, preferably 1 to 1% by weight based on the entire layer which is colored by the amount of received ultraviolet rays.
It is preferably used in the range of 10 to 10% by weight.

In the present invention, the sensitivity with respect to the intensity of ultraviolet rays can be adjusted as appropriate by the concentration of the color forming material and the coating amount on the substrate. Although the ultraviolet coloring material of the present invention hardly causes a coloring reaction with visible light, it is possible to perform a more accurate measurement by removing light other than the original purpose of intensity measurement using a filter or the like. Becomes

In the present invention, if necessary, a component such as an ultraviolet absorber may be added within a range that does not impair the color density due to the amount of received ultraviolet light. Ultraviolet absorber, by blending an ultraviolet absorber that absorbs ultraviolet rays of wavelengths other than the purpose,
The amount of ultraviolet rays can be clarified. Examples of the ultraviolet absorber include salicylate-based, benzotriazole-based, henzophenone-based, cyanoacrylate-based, other hexamethylphosphoric triamides, aromatic ester compounds, organic phosphorus-sulfur compounds, [2-2 ′ thiobis (4-tert. -Octylphenolate)]-n-butylamine-nickel compound and the like. The amount of the ultraviolet absorber used is not particularly limited, but is generally 0.2 to 1 with respect to the layer in which the amount of color development changes depending on the amount of received ultraviolet light.
It is suitable to use in the range of 0% by weight. Also, if necessary, a pigment, a wetting agent, a defoaming agent, a dispersant, an antistatic agent,
Various auxiliaries such as leveling agents and lubricants can be appropriately added within a range that does not impair the desired effect.

The ultraviolet shielding layer used in the present invention is not particularly limited as long as it can be peeled from the color forming layer at the start of the measurement of ultraviolet light reception. For example, aluminum or the like can be formed on the film by vacuum vapor deposition, sputtering or the like. Examples thereof include those obtained by vapor-depositing a metal, those obtained by kneading an ultraviolet absorber and a pigment in a film, and metal foils such as aluminum foil. Also, if necessary, printable or
A writable layer may be provided on the side opposite to the color forming layer.

The method for forming the ultraviolet ray shielding layer, the electron beam curable resin layer and the support is as follows: 1) coating the electron beam curable resin on the support and bonding it with the ultraviolet ray shielding layer;
2) A method in which an electron beam-curable resin is applied on the ultraviolet shielding layer and bonded to a support, and 3) an electron beam-curable resin is applied on both the support and the ultraviolet shielding layer and bonded. . The device for laminating is not particularly limited, but it is usually carried out by passing it between two rolls (nip rolls) under appropriate pressure.

The method of applying the wire-curable resin is not particularly limited, and for example, a usual coating means such as a bar coater, a roll coater, an air knife coater, a gravure coater, an offset gravure coater, etc. is appropriately used. In addition, the coating surface and the bonding surface are previously subjected to corona discharge treatment,
It is also possible to control the wettability and adhesion of the electron beam curable resin by pretreatment by radiation treatment, plasma treatment or the like.

The amount of electron beam irradiated is 1 as the absorbed dose.
It is desirable to adjust in the range of about 200 kGy. 1
If it is less than kGy, a sufficient irradiation effect cannot be obtained, and 200 kG
Irradiation exceeding y is not preferable because it may deteriorate substrates such as papers and certain plastic films. As the electron beam irradiation method, for example, a scanning method, a curtain beam method, a broad beam method, or the like is used, and the acceleration voltage at the time of irradiating the electron beam needs to be controlled by the thickness of the base material on the irradiation side. But 150
About 300 kV is suitable. Almost no heat is applied during irradiation, so coloring by heat and curl adjustment of the laminated sheets can be easily performed.

In the ultraviolet ray detecting sheet thus prepared, the ultraviolet ray shielding layer can be easily peeled off from the layer whose coloring amount changes depending on the amount of received ultraviolet rays, and the coloring layer which appears by peeling off the ultraviolet ray shielding layer is exposed to sunlight or mercury. Exposure to various ultraviolet light sources such as lamp light, carbon arc lamp, and xenon lamp light causes a change in color density in the exposed portion. The integrated illuminance and the irradiation intensity can be obtained by comparing the obtained color density change with a standard color density table or a calibration curve prepared for each light source. Therefore, since it is possible to detect ultraviolet rays by the above-mentioned simple operation, it is useful for maintenance and management of various industrially used ultraviolet light sources or for hygiene management such as sunburn prevention purpose.

Further, the surface shape of the film or the like which is the base material for the ultraviolet ray shielding layer is transferred to the surface of the electron beam curable resin layer after the ultraviolet ray shielding layer is peeled off, and therefore the PET film which is generally used. When such a smooth base material is used, a very smooth and highly glossy surface is formed on the surface of the electron beam curable resin layer.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
In addition, unless otherwise indicated, the part and% in an example show weight% and weight part, respectively.

Example 1 0.4 part of zinc 3,5-di- (α-methylbenzyl) salicylate was mixed with isobornyl acrylate (trade name; Ebecr).
yl IBOA Daicel UCB Co., Ltd.) 3
3 parts of polyester acrylate (trade name; Ebecryl EB1810 manufactured by Daicel UCB) and 3 parts of pentaerythritol triacrylate (trade name; manufactured by Aronix M-305 Toagosei Kagaku Co., Ltd.) and mixed well. Then, 0.2 part of 1,3, -diphenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone was added and dissolved. The solution at this time was light brown. 20 g of this solution on a synthetic paper (trade name; made by YUPO FPG80 Oji Yuka Synthetic Paper) with safety light (ultraviolet light)
/ M ² coated and vacuum-deposited polyethylene terephthalate film (25 μm thick 500 aluminum vapor-deposited) was pasted with a laminator so that the surface opposite to the vapor-deposited surface would be the electron beam-curable resin side, and immediately thereafter an electron beam irradiation device (electro Curtain CB-150; manufactured by ESI) was used to irradiate an electron beam with an absorbed dose of 30 kGy from the polyethylene terephthalate film side at an acceleration voltage of 185 KV to obtain an ultraviolet ray detection sheet.

Example 2 In Example 1, 0.4 parts of 4,4'-butylidene-bis (2-tert-butyl-5-methylphenol) was added as a photosensitizer, and the coating amount was 25 g / m ² . An ultraviolet detection sheet was obtained in the same manner except for the above.

Example 3 0.5 part of 3,7-bis- (diethylamino) -10- (4-methylbenzoyl) -phenoxazine was added to nonylphenol EO modified acrylate (trade name; Aronix M).
-111 dissolved in 3 parts of Toagosei Co., Ltd., and then polyester acrylate (trade name; Ebecryl EB181)
0 parts of Daicel UCB Co., Ltd.) and 3 parts of pentaerythritol triacrylate (trade name; Aronix M-305 manufactured by Toagosei Kagaku Co., Ltd.) were added and mixed well. The color of the solution at this time was yellow. This solution was applied on a synthetic paper (trade name; YUPO FPG80 manufactured by Oji Yuka Synthetic Paper) at 15 g / m ² with a safety light (UV cut light), and a vapor-deposited film (trade name; metal me white coat (B)).
(Toyo Metallizing Co., Ltd.) was laminated with a laminator so that the vapor deposition surface would be on the electron beam curable resin side, and immediately thereafter an electron beam irradiation device (Electro Curtain CB-15).
0; manufactured by ESI Co., Ltd.) was used to irradiate an electron beam with an absorbed dose of 30 kGy from the coated surface side of the vapor deposition film at an acceleration voltage of 185 KV to obtain an ultraviolet ray detection sheet.

Example 4 In Example 3, 3,7-bis- (diethylamino)-
10- (4-methylbenzoyl) -phenoxazine 0.
3,7-bis (dimethylamino) -10 instead of 5 parts
-0.5 parts of benzoylphenothiazine was used, and 3 parts of acrylic morpholine (trade name; KU-MO Arakawa Chemical Co., Ltd.) was used instead of 3 parts of nonylphenol EO modified acrylate (trade name; Aronix M-111 Toagosei Kagaku) An ultraviolet detection sheet was obtained in the same manner as in Example 3 except for the above.

Example 5 In Example 3, 3,7-bis- (diethylamino)-
10- (4-methylbenzoyl) -phenoxazine 0.
3,7-bis (diethylamino) -10 instead of 5 parts
An ultraviolet detection sheet was obtained in the same manner as in Example 3 except that 0.5 part of-(1-naphthoyl) phenoxazine was used.

Comparative Example 1 3,5-di- (α-methylbenzyl) in Example 1
An ultraviolet detection sheet was obtained in the same manner as in Example 1 except that zinc salicylate was not used.

Comparative Example 2 0.2 parts of 1,3-diphenyl-4- (4-N, N-diethylaminophenylamino) -4-acetylamino-5-pyrazolone, 4,4'-butylidene-bis (2- tert
-Butyl-5-methylphenol 0.4 parts, 3,5-di- (α-methylbenzyl) zinc salicylate 0.4 parts dissolved in methyl ethyl ketone 50 parts coating liquid under a safety light (UV cut light), Synthetic paper [Product name: YUPO FPG80,
Manufactured by Oji Yuka Co., Ltd.] and the coating amount after drying is 15.0 g / m ²
Was applied using a wire bar and dried in an atmosphere of 100 ° C. for 1 minute. After drying, the coating layer had already developed a purple color.

The ultraviolet detection sheet thus obtained was evaluated by the following methods, and the results are shown in Table 1. [Coloring Density] In Examples 1 and 2 and Comparative Examples 1 and 2, the ultraviolet shielding layer was peeled off, and the coloring layer was irradiated with an ultraviolet irradiation device [LS-D.
1, main wavelength 365nm, lamp output 0.65mW / cm
Made by Irie Seisakusho]
Irradiation for 10 minutes and irradiation for 5 minutes under the same conditions without peeling off the ultraviolet shielding layer. The color density of the irradiated portion was measured with a reflection Macbeth densitometer [RD-914 type]. The higher the value, the higher the color density. Table 1 shows the results.

[0069]

[Table 1]

In Examples 3 to 5, the ultraviolet shielding layer was peeled off and the coloring layer was irradiated with an ultraviolet irradiation device [M01-L212 dominant wavelength 36.
0 nm, lamp output 1000 W / cm manufactured by Iwasaki Electric]. The color density of the irradiated portion was measured with a reflection Macbeth densitometer [RD-914 type]. The results are shown in Table 2.
Shown in

[0071]

[Table 2]

[0072]

The ultraviolet detection sheet of the present invention has a simple structure, and the color density changes depending on the amount of received ultraviolet light. When ultraviolet rays are radiated from above the ultraviolet shielding layer, no color is developed. The amount of received UV light can be measured well,
Can be used as a UV detection sheet.

Claims (5)

[Claims] 1. A support and a color-forming material formed on the support, the color-developing material having a color-developing amount that changes in accordance with the amount of received ultraviolet rays, which hardly causes a color-developing reaction by electron beam irradiation. An ultraviolet ray detection sheet having an electron beam curable resin layer and an ultraviolet ray shielding layer that can be peeled from the interface with the electron beam curable resin layer. 2. A support and an ultraviolet color-forming material formed on the support, the amount of color development of which varies depending on the amount of received ultraviolet light. The electron-beam irradiation causes a color reaction of a color different from that of ultraviolet light. An ultraviolet ray detection sheet having an electron beam curable resin layer containing a coloring material to be generated, and an ultraviolet ray shielding layer that can be peeled from the interface with the electron beam curable resin layer. 3. The ultraviolet ray detecting sheet according to claim 1, wherein the ultraviolet ray coloring material contains a pyrazolone derivative leuco compound represented by the following general formula (1) as a coloring agent and an acidic substance as essential components. Embedded image [In the general formula (1), R ₁ represents an alkyl group, an alkoxyalkyl group or an aryl group which may have a substituent, and R ₂ and R ₃ represent an alkyl group which may have a substituent or a substituent. R ₄ is an optionally substituted aryl group, R ₄ is an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted amino group is R ₅ , R
₆ represents an alkyl group, an alkoxyl group or a halogen atom, p represents an integer of 0 to 5, and q represents an integer of 0 to 4. ] 4. A photosensitizer represented by the following general formula (2):
Less hindered phenol compound represented by (5)
The ultraviolet ray according to claim 3, wherein both of them are contained in the electron beam curable resin layer.
Line detection sheet. [Chemical 2][In the general formula (2), R₁Is C₃~ C_FiveBranch of al
Kill group or C_Five~ C ₆The cycloalkyl group of R₂
Is a hydrogen atom, C₃~ C_FiveBranched alkyl group of, or C_Five
~ C₆Cycloalkyl group of R₃Is a hydrogen atom or C₁
~ C_FourThe alkyl group of R_Four, R_Five, R₆, R₇, R₈
Is a hydrogen atom or C₁~ C_FourIs an alkyl group. ] [Chemical 3][In the general formula (3), R₁Is C₃~ C_FiveBranch of al
Kill group or C_Five~ C ₆The cycloalkyl group of R₂
Is a hydrogen atom, C₃~ C_FiveBranched alkyl group of, or C_Five
~ C₁₂The cycloalkyl group of R₃Is a hydrogen atom or C
₁~ C_FourA is a sulfur atom, or
May be C₀~ C₆Is an alkylene group. ] [Chemical 4][In the general formula (4), R₁Is C₃~ C_FiveBranch of al
Kill group or C_Five~ C ₆The cycloalkyl group of R₂
Is C₁~ C₈Represents an alkyl group of, and Q is a sulfur atom or
Or you may branch C₀~ C₆Represents an alkylene group of
You ] [Chemical 5][In the general formula (5), R₁, R₂Is C₃~ C_FiveMinute
Divergent alkyl group or C _Five~ C₆Cycloalkyl group
, Z is -NH-, or -O (CH₂)_n− To (here
And n represents an integer of 1 to 5. ), M is an integer of 1 to 4
You However, when m is 1, W is C₁~ C₁₈Alkyl group of
When m is 2, W may be a sulfur atom or may be branched.
I C₀~ C₆Is an alkylene group of, when m is 3, W is C
₁~ C₆Represents a trivalent saturated alkyl group of and when m is 4
W represents a carbon atom. ] 5. An ultraviolet coloring material is used as a coloring agent of the general formula
A phenoxazine compound represented by (6) or (7) or
Fewer phenothiazine compounds represented by general formula (8)
The ultraviolet detection sheet according to claim 2, wherein both of them include one kind. [Chemical 6][In the general formula (6), R₁~ R_FourAre each C₁~
C₆The alkyl group of R _FiveIs a hydrogen atom, C₁~ C_FourA
Rukiru group, C₁~ C_FourAlkoxyl group or halogen
Indicates an atom. ] [Chemical 7][In the general formula (7), R₁~ R_FourAre each C₁~
C₆The alkyl group of R _FiveIs a hydrogen atom, C₁~ C_FourA
Rukiru group, C₁~ C_FourAlkoxyl group or halogen
Indicates an atom. ] [Chemical 8][In the general formula (8), R₁~ R_FourAre each C₁~
C₆The alkyl group of R _FiveIs a hydrogen atom, C₁~ C_FourA
Rukiru group, C₁~ C_FourAlkoxyl group or halogen
Indicates an atom. ]