JPS63256486A - Thermal color forming recording material - Google Patents

Abstract

PURPOSE:To obtain a developed color capable of absorbing electromagnetic waves in a long wavelength region, by incorporating a specified phenylenediamine derivative or naphthylenediamine derivative and a quinoid-type electron-acceptive compound. CONSTITUTION:A phenylenediamine derivative or naphthylenediamine derivative of the formula, wherein each of rings A, B and C is independently a benzene ring or naphthalene ring, which may have at least one substituent group selected from a halogen, cyano and carbamoyl which may be substituted by hydroxyl or the like, and each of R and R' is independently hydrogen, a lower alkyl, aryl or aralkyl, and a quinoid-type electron-acceptive compound are incorporated in a recording material for use with a reading machine sensitive to rays ranging from a long wavelength portion of visible rays to near IR rays. The constituents of the recording material form a coloring matter through a reaction when being heated, and the coloring matter thus formed absorbs electromagnetic waves ranging from a long wavelength portion of visible rays to an IR region with a wavelength of not less than 1200 nm, and shows extremely excellent fastness.

Description

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

[Conventional technology]

BACKGROUND OF THE INVENTION With the recent development of both electronics and information management systems, there has been a trend toward frequent use of recording/reading devices that are sensitive to electromagnetic waves with wavelengths ranging from the long wavelength portion of visible light to near-infrared wavelengths.

Various proposals have been made for color-forming dyes that are colorless in themselves, but which form pigments that absorb electromagnetic waves in this wavelength range upon contact with acidic substances. That is, as compounds having such bottle-like properties, phthalide compounds are disclosed in JP-A-51-121,035 and JP-A-51-1.
No. 21,037.

JP-A-51-121,038, JP-A-55-115,
No. 448, JP-A-55-115,449, JP-A-55
-No. 115,450.

JP-A-55-115,451, JP-A-55-115,
452 boat, JP-A-55-115,456, JP-A-57
-167.979, JP-A-58-157,779,
It is known from JP-A-60-8,564 and JP-A-60-22589, and thiofluorane-based compounds are known from JP-A-59-148,695, and fluorene-based compounds are further known. Kaisho 59-199.
757, European Patent Application No. 124377. The applicant has also filed Japanese Patent Application No. 126149/1982 regarding a fluoran compound that forms a dye having the above-mentioned wavelength absorption range.

In addition, the inventors have proposed the action of the substance represented by the formula described in the claims and an acidic substance (Japanese Patent Application No. 61-241945), or the action of an organic halogenide that generates halogen radicals by fire or heat. (Patent application 1986-23)
9172) has been reported to have absorption in the wavelength range of surface electromagnetic waves as described above.

[Problem that the invention seeks to solve]

However, with the development and diversification of electronics and information management systems, there is an increasing demand for recording materials that can absorb electromagnetic waves of longer wavelengths and produce color.

[Means to solve the problem]

Therefore, the present inventors proposed the general formula in the above-mentioned Japanese Patent Application No. 61-241945 or No. 61-239172 (in which Ring M, Ring B and Ring C are each independently a benzene ring or a naphthalene ring, They are halogen atoms,
Cyano group, hydroxyl group, alkyl group, aryl group, alkoxy group, aryloxy group, aralkyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group,
One or more types selected from the group consisting of an amino group, an alkyl-substituted amino group, an aryl-substituted amino group, a pyrrolidino group, a pyrrolidino group, and a carbamoyl group which may have an alkyl group or an aryl group as a substituent. A phenylenediamine derivative or a ethylenediamine derivative, which may have a substituent (R and R' are each independently hydrogen, a lower alkyl group, an aryl group, or an aralkyl group), and the conductor is a color developer. When a quinoid-type electron-accepting compound is used as a compound, it reacts with heat to produce a pigment, which absorbs electromagnetic waves ranging from the long wavelength region of visible light to the infrared wavelength of 1200= or more, and the pigment is extremely excellent. It was found that the material has robustness.

[Structure of the invention]

That is, the present invention provides near-infrared light with a wavelength of 12QOam or more from the long wavelength region of visible light, which appears when the phenylenediamine derivative or naphthylenediamine derivative represented by the general formula (I) and the quinoid type electron-accepting compound react with each other during heating. This is a thermosensitive color-forming recording material that utilizes color development with external electromagnetic liquid absorption.

Specific examples of substituents that the compound represented by formula (1) may have are listed below. Ring As In the substituents bonded to term B and ring C, the alkyl group of the alkyl group, alkylcarbonyloxy group, alkyl-substituted amino group, and alkyl-substituted carbamoyl group directly bonded to the three terms may have a side chain. It is an alkyl group having 1 to 8 carbon atoms which may also have a substituent, and the alkyl group of the alkoxy group directly bonded to the 3 rings is an alkyl group having 1 to 5 carbon atoms which may have a side chain. Reed with alkyl group.

The alkylene group of the aralkyloxy group directly bonded to the 6 rings is an alkyleph group having 1 to 5 carbon atoms which may have a side chain, and the aryl group, aryloxy group, which is directly bonded to the 3 rings, The aryl group of the carbonyloxy group, aryl-substituted amino group and aryl-substituted carbamoyl group is a phenyl group or/and a naphthyl group, which is an alkyl group having 1 to 5 carbon atoms which may have a side chain. group, an alkoxy group having 1 to 5 carbon atoms which may have a side chain, and an alkoxy group having 1 to 5 carbon atoms which may have a side chain
is an aryl group which may be substituted with one or more substituents selected from the group consisting of an amine group which may have an alkyl group as a substituent, a nitrogen atom, and a hydroxyl group. The substituents that the carbamoyl group may have are the same as above. The lower alkyl group represented by the substituents R and R' is an alkyl group having 1 to 5 carbon atoms which may have a side chain or a substituent, and the aryl group includes a phenyl group and a naphthyl group. groups, which include an alkyl group having 1 to 5 carbon atoms which may have a side chain, an alkoxy group having 1 to 5 carbon atoms which may have a side chain, and an alkyl group having 1 to 5 carbon atoms which may have a side chain; The aralkyl group may be substituted with one or more substituents selected from the group consisting of an amino group, a halogen atom, and a hydroxyl group, which may have an alkyl group having 1 to 5 carbon atoms as a substituent. A phenyl group is bonded to an alkylene group having 1 to 3 carbon atoms which may have a side chain, and the phenyl group is an alkyl group having 1 to 5 carbon atoms which may have a side chain; From an alkoxy group having 1 to 5 carbon atoms which may have an @ chain, an amino group which may have an alkyl group having 1 to 5 carbon atoms which may have an @ chain as a substituent, a halogen atom, and a hydroxyl group. may be substituted with one or more substituents selected from the group consisting of:

Some specific examples of these compounds are listed in Table 1.

These compounds can be used singly or in a mixture of several kinds. The color tone of these compounds due to the quinoid type electron acceptor is often dark green or blackish.

1q cH3 (XNa% state ◎ 145-148782
υRO5 [Note] The maximum absorption wavelength in Table 1 is the wavelength when the claim is used as a color developer.

Some of the compounds represented by the general formula (I) are
It is described in Japanese Patent Laid-Open No. 4-98726 or Japanese Patent Application Laid-Open No. 55-58311, and some of its compounds are commercially available as antioxidants for rubber and the like.

Any compound contained in Kino used as a color developer in the present invention may be used. Yl and Y2 may be the same or different, and are an oxygen atom or/and a group represented by the formula -C<, in which 2 is a cyano group or an alkoxy group having 1 to 5 carbon atoms. It is a group-substituted carbonyl group.

Quinoid-type electron-accepting compounds are formed by the combination of Yl and Y2: quinone type where Yl and Y2 are both oxygen atoms, quinodimethane type where both are 10<=, and quinomethane type where one is an oxygen atom and the other is -C<= There are three types of shapes.

The bond in each of the above formulas is a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, or, for example, a chlorine atom,
Electron-withdrawing groups such as bromine atom, nitro group, cyano group, arylcarbonyl group, alkylcarbonyl group, aryloxycarbonyl group, alkyloxycarbonyl group, arylsulfonyl group, alkylsulfonyl group, arylsulfinyl group, alkylsulfinyl group, etc. are bonded to each other, and furthermore, adjacent bonds may be further bonded to form a new aryl ring. Of course, the aryl ring may have the above substituent.

When the quinoid type electron-accepting compound is a quinone type, at least one of the groups bonded to the bond must be an electron-withdrawing group as described above.

Specific examples of the above-mentioned quinoid type electron-accepting compounds include 2,5-dichloro-1,4--:nzoquinone, 2
．． 6-dichloro-1,4-benzoquinone, 2,3,5.
6-tetrachloro-1,4-benzoquinone (commonly known as "chloranil"), 2,3,5.6-titracyano 1,4-
-<Nzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 5.4,5.6-tetracyano-1,2-benzoquinone, 2,3-dichloro-1,4
-Naphthoquinone, 5,6-dipromo2,5-jethoxycarbonyl-1,4-benzoquinone% 516-9phenylsulfonyl-2,5-jethoxycarbonyl-1
, 4-benzoquinone, 7,7,8.8-tetracyano-
1,4-quinodimethane (3,6-bis(lycyanomethylene)-1,4-cyclohexadiene, (commonly known as [tetracyanoquinodimethane J), 7,7,8.8-tetrakis(methoxycarbonyl)-1 , 4-quinodimethane,
9.9,10.10-tetracyano-1,4-naphthoquinodimethane, 9,9.10.10-tetracyano-
2,6-naphthoquinodimethane, 11,11,12,
12-tetracyano-9,10-anthraquinodimethane, 11,11.12,12-tetracyano-2,6-anthraquinodimethane 10-('; cyanomethylene)anthrone, 10-bis-(ethoxycarbonyl) Examples include, but are not limited to, methylene anthrone, 11,11-dicyano-12,12-bis(ethoxycarbonyl)-9,10-ant-2quinodimethane, and the like. These substances can be used singly or in combination.

Specific forms of recording materials that utilize color development by the quinoid type 0 electron-accepting compound of the compound represented by general formula (1) include, for example, heat-sensitive recording materials, photosensitive recording materials, electron beam recording materials, discharge recording materials, etc. can be mentioned. As the base material for these recording materials, paper, synthetic paper, cloth, nonwoven fabric, or polymeric materials such as synthetic resin films and synthetic resin plates 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 mix and use color-forming dyes that absorb 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-5-methyl-7- Green coloring dyes such as dipendylaminofluorane, 3-N-inbutyl-ethylamino-7-phenylaminofluorane, 3-diethylamino-6-methyl-7-10rofluorane, 6-N-butyl- Red coloring dyes such as ethylamino-6-'f-7-chlorofluoran, 3-cyclohexylamino-6-chlorofluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 6-N- Methyl-cyclohexylamino-6-methyl-7-phenylaminofluorane, 6-N-methyl-n-propylamino-6-methyl-7-phenylaminofluorane, 3-N-inbentoethylamino-6- Representative examples include black coloring dyes such as methyl-7-phenylaminofluorane, 3-diethylamino-7-m-)lifluoromethylphenylaminofluorane, and 3-di-n-butylamino-7-chlorophenylaminofluorane. However, it is not limited to these.

The method for producing the heat-sensitive color-forming recording material of the present invention is similar to the case where a conventional color-forming dye is used together with a conventional color developer such as bisphenol A. That is, for example, 3
9-27.579, Japanese Patent Publication No. 45-4,160, Japanese Patent Publication No. 45-14,039, Japanese Patent Application Publication No. 7.087-1987, or Japanese Patent Application Publication No. 106-106-992, etc. Heat-sensitive recording paper can be manufactured according to the method described in the above, but the compound represented by general formula (1) and the color developer do not necessarily have to be contained in the same coating layer, and they are not necessarily contained in the same coating layer. They may be contained separately in two overlapping layers.

In the present invention, the weight ratio of the compound represented by general formula (1) and the quinoy r-type electron-accepting compound is 1:α
The ratio is preferably about 5 to 1:5.

The heat-sensitive color-forming recording material of the present invention 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 label.

〔Effect of the invention〕

The recording material of the present invention has extremely unique coloring characteristics, and a specific example thereof is shown in FIG. This FIG. 1 was obtained in Examples 1 and 2, and shows the general formula (1
Reflection spectrum of color development at 200°C of thermal recording paper produced using the compounds N110 and 1I411L22 in Table 1 as compounds represented by ) and chlor2nyl and tetracyanoquinodimethane as color developers. shows. From Figure 1, the color development of these thermal recording papers is 8.
It can be seen that there is still significant absorption even in the wavelength range of 00 nm or more.

Next, the present invention will be specifically explained with reference to Examples.

Example 1 Suspension A-1 0H"@ME8NhetoH@y,o y clay
11. ! M15%
Polyvinyl alcohol aqueous solution 41.5f water
40
．． Of suspension B-1 Tetrachlorobenzoquinone 1Q, 5
f shoes-aOf 15 tips Polyvinyl alcohol aqueous solution 41.5f
water 4
0. Of suspension B-2 Tetracyanoquinodimethane 1α51
Clay aO
f15 polyvinyl alcohol water faK 41
．． 5F water
40.0f Each of the above compositions was put into a polyethylene bottle together with 150F glass beads (1 to 1.5 m in diameter), sealed tightly and ground for several hours in a paint conditioner manufactured by Rea Devi1 to obtain suspension A- 1. Suspension B
-1 and suspension B-2 were prepared.

Suspension A-1 and Suspension B-1 were mixed at a ratio of 1:2 to form a coating solution, and this coating solution was coated on white paper and dried to produce 1 ft of thermal recording paper.

Further, suspension B-2 was used in place of suspension B-1, and thermosensitive recording paper (2) was prepared in the same manner as above.

Both sides of the thermosensitive recording papers I and II were heated at a temperature of 200° C. to develop color using a dry heat tester (manufactured by Kishino Scientific Instruments Co., Ltd.). The developed color was dark green in both cases. The wavelength of the coloring part of this thermal recording paper 1 is 400.
The reflection curve at ~1200 nm was measured using a spectrophotometer (Hitachi new model %U-3400 and attached integrating sphere). The reflection curve is shown in FIG.

The coated surface (before heating) of these thermosensitive recording papers was pale yellow in the thermosensitive recording paper I, and dark yellow in the thermosensitive recording paper II.

Example 2 Clay 11
．． 5F15% polyvinyl alcohol water soluble i
41.5f water
4αOf Suspension A-2 having the above composition was prepared in the same manner as described above.

In place of Suspension M-1 in Example 1, Suspension M-2 was mixed with Suspension B-1 or Suspension B-2, and thermal recording paper ■ and thermal Recording paper (■) was manufactured and heated to develop color.

The color tone of the thermal paper (■) was slightly reddish black, and that of the thermal recording paper (■) was black. The reflection curves of these colors are shown in FIG.

The coated surfaces (before heating) of these thermal recording papers were green in the thermal recording paper (■) and dark green in the thermal recording paper (■).

[Brief explanation of drawings]

FIG. 1 shows the color reflection curves of the thermal recording paper obtained in Examples 1 and 2, and the curves (c)%(b), (c) and (d) are the thermal recording paper (1), the curve (c) and (d), respectively. (u), (
1) and (F/) color reflection curves. Patent applicant: 2 people other than Shinnichi 1 Kako Co., Ltd.

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (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, aralkyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group,
One or more substituents selected from the group consisting of an amino group, an alkyl-substituted amino group, an aryl-substituted amino group, a pyrrolidino group, a piperidino group, and a carbamoyl group which may have an alkyl group or an aryl group as a substituent. and R and R' are each independently hydrogen, a lower alkyl group, an aryl group, or an aralkyl group) and a quinoid-type electron-accepting compound. Thermosensitive color recording material.