JPS6394880A - Coloring recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material having excellent coloring performance in near inrared portion, by containing a phenylanediamine derivative or a naphthylanediamine derivative shown by a specific formula and an organic halide producing halogen radical through function of heat and/or light. CONSTITUTION:A phenylanediamine derivative or a naphthylanediamine deriva tive shown by formula (I) reacts with an organic compound for producing halo gen radical to produce color and said coloring can absorb electromagnetic wave having wavelength in the range from visible light to near infrared zone. In other word, said recording material contains a phenylanediamine derivative or a naphthylanediamine derivative shown by formula (I) and an organic com pound producing halogen radical through function of heat or light, and the coloring in the range from visible light to the near infrared zone being produced through reaction of them can be utilized.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a recording medium whose main purpose is to be read by equipment. More specifically, it relates to a recording medium that is effective when using a recording/reading device that is sensitive to the long wavelength part of visible light or near infrared rays, and proposes a recording medium that meets the demands associated with the development of information management systems. It is.

[Conventional technology]

2. Description of the Related Art With the recent development of both electronics and information management systems, recording/reading devices that are sensitive to electromagnetic waves with wavelengths ranging from the long wavelength portion of visible light to the near-infrared region are increasingly being used.

Various proposals have been made for color-forming dyes that are colorless in themselves, but which form pigments that absorb electromagnetic waves in the wavelength range of water upon contact with acidic substances. That is, as compounds having such force properties, phthalide compounds are disclosed in JP-A-51-121,035 and JP-A-51-1.
21,037, JP 51-121,038, JP 55-115,448, JP 55-115,44
No. 9, JP-A-55-115,450, JP-A-55-1
15,451, JP 55-115,452, JP 55-115,456, JP 57-167, 97
No. 9, JP-A-58-157.779, JP-A-60-
R364, JP-A No. 60-27.589, and thiofluorane-based compounds are known from JP-A-59-14a-695, and fluorene-based compounds are known from JP-A-59-199.757. No., Yorotsu・
ξIt is known from Patent Application Publication No. 124377.

On the other hand, the use of organic halogen compounds in photosensitive recording materials is disclosed in, for example, Japanese Patent Publication No. 47-1895 and Japanese Patent Application Laid-open No. 50-1.
No. 37126, JP-A No. 57-212434 and JP-A No. 58-132229, and a heat-sensitive recording material that is used with Futa 0 series leuco dye and has color development in the visible region has been proposed. It was proposed in Japanese Patent Publication No. 1983-3791.

[Problems that the invention attempts to solve]

So-called color-forming dyes such as phthalide, fluorine, and fluorane dyes, which are substances that form dyes having the above-mentioned wavelength absorption range, are expensive, and recording materials using them are also not cheap.

[Means to solve the problem]

Therefore, the present inventors compared the coloring dye to 1. We succeeded in producing a recording medium with excellent color development in the near-infrared region by using a substance with a simple structure.

The present inventors have developed the general formula (I) = 6- (in the formula, ring A1, ring B and ring C are each independently a benzene ring or a naphthalene ring, and they are a halogen atom,
Cyano group, hydroxyl group, alkyl group, aryl group, alkoxy group, aryloxy group, arylalkoxy group, alkylcarbonyloxy group, arylcarbonyloxy group, amino group, alkyl-substituted amine group, pyrrolidino group, pi is lydino group, aryl substitution It may have one or more substituents selected from the group consisting of an amino group and a carbamoyl group which may have an alkyl group or a phenyl group as a substituent, and H is bonded to the nitrogen atom in parentheses. is a hydrogen atom, R1 is a lower alkyl group, aryl group or aralkyl group bonded to the elementary atom in parentheses, m and n
are 0.1 or 2, respectively, and m+n is 2)
The phenylenediamine derivative or naphthylenediamine derivative represented by is colored by an organic halogen compound (hereinafter simply referred to as 1 organic halogen compound) that generates halogen radicals, and the coloring absorbs electromagnetic waves with wavelengths ranging from visible light to near-infrared light. The present invention was made based on this discovery. That is, the present invention contains a phenylenediamine derivative or a naphthylenediamine derivative represented by the general formula (1) and an organic halokene compound that generates halogen radicals by the action of heat or light, and which generates halogen radicals by the action of both of them. This is a recording medium that utilizes color development in the infrared region. Here, color development refers to the production of a substance that absorbs electromagnetic waves in the above wavelength range.

Some of the compounds represented by the general formula (D) are
No. 8726 or JP-A No. 55-38311, and some of the compounds are commercially available as antioxidants for rubber and the like.

Specific examples of substituents that the compound represented by formula (1) may have are listed below. In the term A%iB and the substituents bonded to ring C, the alkyl group directly bonded to the three rings, the alkylcarbonyloxy group, and the alkyl group of the alkyl-substituted amino group have a side chain having 1 to 8 carbon atoms. It is an alkyl group which may also have a substituent, and the alkoxy group directly bonded to the three rings and the alkoxy group of the arylalkoxy group are an alkyl group which may have a side chain having 1 to 5 carbon atoms. and the aryl group of the aryl group, aryloxy group, arylcarbonyloxy group, and aryl-substituted amine group directly bonded to item 6 is a phenyl group or/and a naphthyl group, and they have 1 to 1 carbon atoms. Substituted alkyl group which may have 5 side chains, alkoxy group which may have 1 to 5 side chains, alkyl group which may have 1 to 5 side chains It is an aryl group that may be substituted with one or more substituents selected from the group consisting of an amino group, a halogen atom, or a hydroxyl group. The substituents that the carbamoyl group may have are the same as above. The lower alkyl group represented by the substituent R1 is an alkyl group having a side chain of 1 to 5 carbon atoms and may have a substituent, and the aryl group is a phenyl group or a naphthyl group. They include an alkyl group which may have a side chain having 1 to 5 carbon atoms, an alkoxy group which may have a side chain having 1 to 5 carbon atoms, and an alkyl group which may have a side chain having 1 to 5 carbon atoms. The aralkyl group may be substituted with 1 ai or more substituents selected from the group consisting of an amine group, a halogen atom, or a hydroxyl group, which may have an alkyl group as a substituent, and the aralkyl group has 1 carbon atom. A phenyl group is bonded to an alkylene group that may have a side chain of 1 to 3 carbon atoms, and the phenyl group is an alkyl group that may have a side chain of 1 to 5 carbon atoms;
selected from the group consisting of an alkoxy group having 1 to 5 carbon atoms, an amino group which may have an alkyl group which may have a side chain having 1 to 5 carbon atoms as a substituent, a halogen atom or a hydroxyl group It may be substituted with one or more substituents.

Typical specific examples of the compound represented by the general formula (1) of the present invention include the following. The present invention is not limited to these.

The compound of general formula (1) develops color due to an organic halogen compound that generates halogen radicals under the action of heat and/or light. Any organic halokene compound may be used, such as carbon tetrabromide, bromoform, bromochloroform, hexabromoethane,
Hexachlorobenzene, hexabromobenzene, tribromoacetate, hexabromdimethylsulfone, 2.4.6-)lis(trichloromethyl)triazine, and the like are generally known and can be conveniently used in the present invention. However, in general (in the formula, R2 represents a halogen atom, a nitro group or a lower alkyl group, and p is 0 or 1
represents an integer from 5 to 5; when p is 2 or more, R2 represents a different position; Xl, x2 and x3 represent a hydrogen atom, a chlorine atom or a bromine atom; However, xl, x2 and x3 are not all hydrogen atoms) and the organic halogen compound represented by the general formula
or an integer from 1 to 4, and if q is 2 or more, R3
may be different substituents; R4 and R5 are the same or different and each represent a hydrogen atom or a lower alkyl group; Halogen compounds generate halogen radicals under the action of heat and/or light, and are particularly preferred as the color developer of the present invention.

The organic halogen compounds represented by the general formula (II) or/and (III) are disclosed in Japanese Patent Publication No. 1895-1982, Japanese Patent Application Publication No. 137126-1980, Japanese Patent Application Publication No. 212434-1972, and Japanese Patent Application Publication No. 132229-1989. It is also used as a color developer for photosensitive recording in various applications, such as JP-A-61-! 1791
This substance is disclosed in the publication as a color developer for heat-sensitive recording. Typical specific examples thereof include tribromomethylphenylsulfone, trichloromethylphenylsulfone, tribromomethyl-p-chlorophenylsulfone, trichloromethyl-p-chlorophenylsulfone, tribromomethyl-p-nitrophenylsulfone, and tribromomethyl-p-chlorophenylsulfone. Bromomethyl-〇-methylphenylsulfone, tribromomethyl-〇-isopropylphenylsulfone, α, α,
α-tribromoacetophenone, α, α, α-trichloroacetophenone, p-nitro-α, α, α-tribromoacetophenone, p-chloro-α, α, α-trifluoroacetophenone, tribromomethylphenylsulfoxide , trichloromethylphenylsulfoxide, N-bromophthalimide, N-bromo-2-chlorophthalimide, N-bromo-1,2,3,4-tetrachlorophthalimide, 1,3-uchloro-5,5-dimethylhylant Examples include, but are not limited to, in, 1,6-dipromo-5,5-dimethylhylantoin, N-bromosuccinimide, N-chloro-succinimide, and the like.

It is clear how the color-developing effect of the organic halogen compounds that generate halogen radicals by the action of heat and/or light, particularly the compounds represented by the general formulas (II) and (ill), used in the present invention is produced by the mechanism. It's big, but
By applying heat to an organic halogen compound or by irradiating it with high-energy light (e.g. ultraviolet rays, hereinafter referred to as "light"), halogen radicals are generated, and some of these radicals are also converted into hydrogen suppliers (e.g. 2-inder, water, etc.) to produce acidic substances, etc.
It is thought that the compound represented by the general formula (1) develops color due to the additive effect of these halogen radicals and acidic substances. Therefore, the usage ratio of the organic halogen compound to the compound represented by the general formula (I) is not determined in part, and as mentioned in 7 above, the amount of halogen radicals generated by the organic halogen compound by heating or light irradiation is determined. This should be taken into consideration when deciding.

The color-forming recording material of the present invention has extremely excellent color-forming properties, and a specific example thereof is shown in FIG. This figure 1 is obtained in Examples 1 to 4, and shows the compound represented by the general formula f)-Na-fΣNHe
-NH), and to 1 part by weight of tribromomethylphenylsulfone as an organic halogen compound that generates halogen radicals, 0.05, (llLl, 0.
5 is a reflection/absorption curve of a coloring area of heat-sensitive recording paper produced using a proportion of 5 and 1.0 parts by weight. The color development of this recording medium is distinctive in that the color changes from gray-green to greenish black as the proportion of organic halokene compound used increases.

In the case of thermal recording paper manufactured using tribromomethylphenylsulfone as the organic halogen compound 7, the proportion of the organic halogen compound to the compound represented by general formula (1) is based on 1 part by weight of the former. The latter is preferably 0.05 to 3 parts by weight.

Specific forms of the color-forming recording material that utilizes color development by the organic halogen compound of the compound represented by the general formula (1) of the present invention include, for example, a heat-sensitive recording material, a photosensitive recording material, a heat-sensitive transfer recording material, and an electron beam recording material. Examples include material strength. As the base material for these recording materials, polymeric materials such as paper, synthetic paper, cloth, nonwoven fabric, synthetic resin film, and synthetic resin board are often used.

It goes without saying that the compound represented by the general formula (1) can be used alone, but it is also possible to use a mixture of these compounds.
It is also possible to use it in combination with a color-forming dye that absorbs in the near-infrared region during color development as described in the above-mentioned literature.

Conventionally known conventional color-forming dyes include, for example, crystal violet lactone, penzoylliucomethylene blue, 5(or 7)-(1-octyl-2-methylindol-3-yl)-5(or 7)- (4-diethylamino-2-ethoxyphenyl)-5,7-)hydrofuro(3,4-b)-pyridin-7(or 5)-one, a blue coloring dye, 3-diethylamino-5-methyl-7 -dibenzylaminofluorane, 3-N-isobutyl-ethylamino-7-phenylaminofluorane, etc., 3-:)ethylamino-6-methyl-7-chlorofluorane, 3-N- isophthylethylamino-6-methyl-7-chlorofluorane, 6-
Red coloring dyes such as cyclobexidylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-
Phenylaminofluorane, 6-N-methyl-cyclohexylamino-6-methyl-7-phenylaminofluorane, 3-N-methyl-n-propylamino-6-methyl-7-phenylaminofluorane, 6-N -iso is phthyl-ethylamino-6-methyl-7-phenylaminofluorane 3 + :) ethylamino-7-m-trifluoromethylphenylaminofluorane, 3-di-n
-Butylamino-7-chlorophenylaminofluoran persimmon black color-forming dye can be mentioned as a typical example, but it is not limited to these only.

The compound represented by the general formula (summer) of the present invention is, for example, Japanese Patent Publication No. 39-27.579, Japanese Patent Publication No. 43-4,160,
Special Publication No. 45-14,039, JP-A-59-7.087
It can be used to produce heat-sensitive recording paper according to the method described in JP-A No. 59-106,992, etc., but in this case, the organic halogen compound is not limited to heating. Since it produces a color developing effect even when irradiated with light, there is a possibility of background staining (natural color development in unheated areas). However, in thermal recording paper manufactured by normal methods, organic halogen compounds are contained in the thermal recording layer in the form of particles, and other additives such as anti-staking agents are also included. Inevitably, the amount of light irradiation that the organic halogen compound receives is not small, and the staining of the skin is slight. Furthermore, as a method to prevent background staining, there is a method in which the color-forming substance and the color developer are not mixed, but are applied as separate layers on the support (in that case, 2
(It is also possible to provide an appropriate isolation layer between the layers), a method in which one or both of a color-forming substance and a color developer is encapsulated in heat-melting microcapsules, and a method in which an ultraviolet absorber is included in a heat-sensitive recording layer. Examples include a method of overcoating the heat-sensitive recording layer with an ultraviolet absorbing substance, and a method of providing a light protective layer on the surface of the recording layer.

The method of containing these ultraviolet absorbers or the method of overcoating with ultraviolet absorbing substances is described in, for example, JP-A-50-146,412 and JP-A-53-17,34.
No. 6, JP-A No. 6 o-ios No. 388 and JP-A No. 1-1
The method described in Japanese Patent No. 12,487 can be mentioned.

When producing thermal recording paper using the compound represented by the general formula (1), whether it is used alone or in combination with ordinary color-forming dyes, Furthermore, acidic substances used as color developers in the production of thermal recording paper (for example, bisphenol A1, benzyl p-hydroxybenzocyanate, 4-hydroquine-4'-di-propoxydiphenylsulfone, 4-human90ki7-4 ′−
n -7' Toxidi-phenylsulfone, bis(p
-hydroxyphenylthioethoxy)-methylene (including but not limited to) may be used in combination with the organic logone compound.

In order to use the compound represented by the general formula (1) of the present invention for photosensitive recording, for example, Japanese Patent Publication No. 38-24188, Japanese Patent Publication No. 10550-1982, Japanese Patent Publication No. 45978-1978, Japanese Patent Publication No. 80120-1980, Japanese Patent Publication No. 50-126228,
JP-A-52-141633 or JP-A-54-14
It can be used according to the method described in No. 7829. FIG. 2 shows that the color-forming recording material of the present invention develops color when irradiated with ultraviolet rays. This was done in Example 9.

26-Furthermore, in order to use the compound represented by the general formula ([) for thermal transfer, for example, JP-A-58-212,985;
JP-A-59-33,185, JP-A-59-42,99
It can be used according to the method described in No. 5 or JP-A-59-225,986, or for use in photosensitive printing materials, it can be used in accordance with the method described in JP-A-48-12. It can be used according to the method described in IO4.

The recording paper produced according to these methods can be provided with a protective layer on its surface, if necessary, and can also be provided with an adhesive layer on its back surface to make it convenient to use as a cover.

In addition, recording materials manufactured according to these methods are used, for example, in copying books, documents, electronic computers, facsimiles, bar codes, ticket vending machines, digital cameras, etc., and are also used to record information input with high density, such as by the naked eye. It can be applied to a wide range of applications such as anti-counterfeiting, anti-copying, unlocking devices, and laser discs where recorded information is unknown.

Next, the present invention will be explained in detail using Examples, but the present invention is not limited thereto.

Example 1 Glass beads (diameter 1 to 1.5
m) Place it in a polyethylene bottle with 150f, seal it, and turn it red]) Evi1 manufactured by India conditioner was ground for several hours to form suspension A-1 and suspension B-.
I got 1. Next, a coating liquid was prepared by mixing 1 part of the former to 2 parts of the latter.

This coating liquid was applied to white base paper and dried to produce thermal recording paper I.

This thermosensitive recording paper I was heated on both sides at a temperature of 200° C. to develop color using a dry heat tester (manufactured by Kishino Kagaku Kikai Co., Ltd.). The color developed was black with a green tinge. Regarding the coloring part of this thermal recording paper I, the wavelength is 400~
1500nm reflection absorption curve and 700.800.900
The reflection and absorption coefficients at 11,000 nm and 11,000 nm were measured using a spectrophotometer (manufactured by Hitachi Seisakusho, Model U-3400 and the attached integrating sphere).

This reflection/absorption curve is shown in FIG. 1, and the reflection/absorption coefficient is shown in Table 1.

Examples 2 to 4 291 The same procedure as in Example 1 was carried out except that the amount of tribromomethylsulfone used in Example 1 was changed to prepare suspensions B-2, B-3 and B- with the following compositions. 4 was manufactured.

These suspensions were mixed with suspension A-1 in place of suspension B-1 in Example 1 to prepare a coating solution, and the coating solution was coated on thermal recording papers ① and ②.
and ■ were manufactured. Furthermore, these thermosensitive recording papers were colored in the same manner as in Example 1, and the reflection and absorption curves of the colored areas were measured. These reflection and absorption curves are summarized in FIG.

The colors developed for the heat-sensitive recording papers ①, ②, and ① were black border color, green, and yellow-green, respectively.

Examples 5 to 7 Suspensions A-2, A-3 and A-4 having the following compositions were produced in the same manner as in the production of suspension A-1 in Example 1.

Instead of suspension A-1 in Example 1, these suspensions were mixed with suspension B-1 to prepare a coating solution, and thermal recording paper (1),
■ and ■ were manufactured. Furthermore, after coloring these thermosensitive recording papers in the same manner as in Example 1, the colored and non-colored areas were coated with 700, 800, 900 and 110.
Reflection absorption coefficient at 0Qn was measured. The measured values are shown in Table 1. The colors developed by the thermal recording papers ①, ① and ① were respectively bluish black, reddish black and greenish black.

Table 1 Example 8 Substitute for tribromomethylphenylsulfone in suspension B-1 of Example 1 bl) K L5- ) io Mo5
．． A heat-sensitive recording paper (2) was prepared in the same manner as in Example 1, except that 5-dimethylhylantoin was used, and when the paper was further heated and colored, it developed a dark brown color. This dye absorbs near-infrared electromagnetic waves.

Example 9 A coating solution having the above composition was produced by blocking light, and then the coating solution was coated on white base paper and dried to produce photosensitive recording paper. When this recording paper was irradiated with ultraviolet light, it developed a yellow-green color. In the same manner as in Example 1, the reflection and absorption curves of the colored parts were measured. The results are shown in FIG.

〔Effect of the invention〕

Chromogenic recording bodies with significant absorption in the near-infrared can be produced using materials with a simple structure.

[Brief explanation of the drawing]

The attached FIG. 1 shows the color reflection and absorption coefficients of the recording paper obtained in Examples 1 to 7 of the present invention, and FIG. 2 shows the color reflection and absorption coefficient of the recording paper of Example 9. be. Patent applicant: Nippon Sokako Co., Ltd. Kasumi 38"ゝ- Print mouth 95ゞゞ- Erosion

Claims (1)

[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, ring A, ring B, and ring C are each independently a benzene ring or a naphthalene ring, and they are halogen atoms,
Cyano group, hydroxyl group, alkyl group, aryl group, alkoxy group, aryloxy group, arylalkoxy group, alkylcarbonyloxy group, arylcarbonyloxy group, amino group, alkyl-substituted amino group, pyrrolidino group, piperidino group, aryl-substituted amino group and a carbamoyl group which may have an alkyl group or a phenyl group as a substituent, and H is a hydrogen atom bonded to the nitrogen atom in parentheses. (R^1 is a lower alkyl group, aryl group, or aralkyl group bonded to the nitrogen atom in parentheses, m and n are each 0, 1, or 2, and m+n is 2). Alternatively, a chromogenic recording material containing a naphthylene diamine derivative and an organic halogen compound that generates halogen radicals by the action of heat and/or light. 2) The color-forming recording material according to claim 1, wherein the organic halogen compound that generates halogen radicals is represented by the following general formula (II) or/and (III). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, R^2 represents a halogen atom, nitro group, or lower alkyl group, p represents 0 or an integer from 1 to 5, and p When is 2 or more, R^2 may be a different substituent, and Y is a ▲ mathematical formula, chemical formula, table, etc. ▼, ▲ mathematical formula,
Chemical formulas, tables, etc. are available▼ or ▲numeric formulas, chemical formulas, tables, etc. are available▼, and X^1, X^2, and X^3 represent a hydrogen atom, a chlorine atom, or a bromine atom. However, X^1, X^2 and X^3 are not all hydrogen atoms). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, D is -CH_2-CH_2-, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. In the case of two or more, R^3 may be different substituents, R^4 and R^5 represent the same or different hydrogen atoms or lower alkyl groups, and X^4 and X^5 are the same or different chlorine or bromine atoms).