JPH0561149A - Recording material capable of developing color - Google Patents

Abstract

PURPOSE:To obtain the color developing recording material capable of developing practicable sufficiently intense color immediately after making color developing operation and enabling readout of information through instruments using lights of all the wavelengths by incorporating a specified diamine derivative and an oxidant, and an organic acid material solid at normal temperature. CONSTITUTION:The recording material contains the oxidant, the organic acidic material solid at normal temperature, and the diamine derivative represented by formula I in which each of A and B is, independently, aryl; X is arylene, and each of R<1> and R<2> is, independently, H, lower alkyl, aryl, or aralkyl. It is preferred that the oxidant is a quinoid type electron receptor, thus permitting practicable sufficiently intense color to be developed and the color developing part to have strong absorption in the wide region from visible to near infra wavelengths, and therefore, readout of information to be made by instruments using all the wavelengths.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a color forming recording material,
More specifically, the present invention relates to a color-forming recording material useful for a recording / reading device using visible light and / or near infrared light.

[0002]

2. Description of the Related Art A dye precursor (hereinafter referred to as a color-forming dye), which is almost colorless in itself, but can develop a certain color by a chemical reaction, is a color-developing agent which has been conventionally developed. In combination with, it has been widely put to practical use as a color-forming recording material such as heat-sensitive pressure-sensitive recording paper. However, in recent years, a barcode has been widely used as a means of more advanced information processing, and as a device for reading this barcode, a device using a semiconductor laser has advantages such as small size, low cost, and long life. It tends to be heavily used. Since this semiconductor laser emits light in the near-infrared region, the dye forming the barcode must be one that absorbs light in such a region.

However, in the conventional fluoran-based color-forming dyes generally used for heat-sensitive pressure-sensitive recording paper, the dye formed by the color-forming reaction has no practical absorption in the near infrared region. .. In addition, a method in which a compound having an extended π-electron conjugated system has absorption in the near-infrared region is also adopted, but such a compound has a large molecular weight, its production is not easy, and a dye to be produced. Is unstable,
Poor light resistance.

Therefore, in recent years, various compounds having a structure greatly different from the conventional ones have been proposed as color forming dyes forming dyes that absorb light in the near infrared region. For example,
Japanese Unexamined Patent Publication (Kokai) No. 62-181361 proposes a color forming recording material containing a phenylenediamine derivative or naphthylene diamine derivative and an acidic substance, but the change over time after color development is remarkable.

Further, JP-A-63-256486 proposes a color forming recording material containing a phenylenediamine derivative or a naphthylenediamine derivative and a quinoid type electron-accepting compound. According to this, even if the phenylenediamine derivative or the naphthylenediamine derivative is brought into contact with the quinoid type electron-accepting compound, substantial coloration often does not occur, and practical application is not easy.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the conventional color-forming recording material, and provides a color having a practically sufficient intensity immediately after the color-forming operation, and Another object of the present invention is to provide a chromogenic recording material having strong absorption in a wide range from visible to near infrared region after color development.

[0007]

The color-forming recording material according to the present invention comprises: (a) General formula (I) A-NR ¹ -X-NR ² -B (wherein A and B are independently monovalent A diamine derivative represented by the formula (1), X is a divalent arylene group, and R ¹ and R ² are each independently hydrogen, a lower alkyl group, an aryl group or an aralkyl group. Agent, and (c) an organic acidic substance which is solid at room temperature.

That is, the chromogenic recording material according to the present invention comprises the above-mentioned three elements, and these elements react with each other by the coloring operation to form an aminium salt having a strong absorption in a wide range from the visible region to the near infrared region. As a result, it is possible to provide an excellent chromogenic recording material which is useful for a recording / reading apparatus using visible light and / or near infrared rays. The diamine derivative used in the present invention (hereinafter, simply referred to as diamine) is represented by the above general formula (I), wherein A
And B each independently represent a monovalent aryl group, and preferable examples of the aryl group include a phenyl group and a naphthyl group. X is a divalent arylene group, and examples of the arylene group include, for example, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,4-naphthylene group, and 1,5. −
A naphthylene group etc. can be mentioned as a preferable thing.

Such aryl group and arylene group may have one or more substituents on the aromatic ring.
Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, an aralkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a carboxyl group and an alkoxycarbonyl group. , An aryloxycarbonyl group, an alkyl-substituted carbamoyl group, an aryl-substituted carbamoyl group,
Examples thereof include a sulfonic acid group, an alkylsulfonyl group, an arylsulfonyl group, an amino group, an alkyl-substituted amino group, an aryl-substituted amino group, a pyrrolidino group, and a piperidino group. When having a plurality of substituents, they may be the same or different.

Among these substituents, preferred examples of the halogen atom include fluorine, chlorine, bromine and the like. The alkyl group is preferably a linear or branched one having 1 to 4 carbon atoms,
Preferred examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group.

Preferable examples of the aryl group include a phenyl group and a tolyl group. Preferable examples of the aralkyl group include a benzyl group and a phenethyl group.
The alkoxy group preferably has a linear or branched alkyl group having 1 to 4 carbon atoms, and examples of the alkoxy group include a methoxy group, an ethoxy group, and n.
-Propoxy group, isopropoxy group, n-butoxy group,
Preferred examples include isobutoxy group, secondary butoxy group, and tertiary butoxy group.

Preferable examples of the aryloxy group include a phenoxy group, a methylphenoxy group and a naphthoxy group. Preferred examples of the aralkyloxy group include a benzyloxy group and a phenethyloxy group. The alkyl-substituted amino group is preferably an amino group mono- or di-substituted by a linear or branched alkyl group having 1 to 4 carbon atoms, and examples of the alkyl-substituted amino group include a methylamino group. , Dimethylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, n-butylamino group,
Preferred examples include a di-n-butylamino group, an isopropylamino group, an isobutylamino group, a secondary butylamino group, and a tertiary butylamino group.

The aryl-substituted amino group is, for example,
A phenyl group, a tolyl group, an amino group mono- or di-substituted with an aryl group such as a naphthyl group is preferred, and examples of such an aryl-substituted amino group include a phenylamino group, a diphenylamino group, a tolylamino group, and a naphthylamino group. And the like can be mentioned as preferable ones. The acyl group has 1 to 5 carbon atoms, and the alkyl group is a linear or branched aliphatic acyl group or has 7 to 12 carbon atoms.
However, an aromatic acyl group in which the aryl group may be substituted with an alkyl group is preferable. Preferred examples of such an acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a benzoyl group, a toluoyl group, and a naphthoyl group.

The alkoxycarbonyl group is preferably an alkyl group having a linear or branched chain having 1 to 4 carbon atoms. Examples of such an alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group. Group, isopropoxycarbonyl group,
Preferred examples include butoxycarbonyl group, isobutoxycarbonyl group, secondary butoxycarbonyl group, and tertiary butoxycarbonyl group.

Preferred examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a methylphenoxycarbonyl group and a naphthoxycarbonyl group. The alkyl-substituted carbamoyl group is preferably a carbamoyl group mono- or di-substituted with a linear or branched alkyl group having 1 to 4 carbon atoms. As such an alkyl-substituted carbamoyl group,
For example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group,
Propylcarbamoyl group, dipropylcarbamoyl group,
Isopropylcarbamoyl group, butylcarbamoyl group,
Dibutylcarbamoyl group, isobutylcarbamoyl group,
A secondary butyl carbamoyl group, a tertiary butyl carbamoyl group, etc. can be mentioned as a preferable thing.

Aryl-substituted carbamoyl groups are, for example:
A phenyl group, a tolyl group, a carbamoyl group mono- or di-substituted with an aryl group such as a naphthyl group is preferable, and examples of the aryl-substituted carbamoyl group include, for example, a phenylcarbamoyl group, a diphenylcarbamoyl group, a tolylcarbamoyl group, A naphthylcarbamoyl group and the like can be mentioned as preferable ones.

Examples of the alkylsulfonyl group include:
Methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group, butanesulfonyl group and the like can be mentioned as preferable ones. Preferred examples of the arylsulfonyl group include a benzenesulfonyl group, a toluenesulfonyl group, and a naphthalenesulfonyl group.

In the present invention, when the above-mentioned substituent is present on the aryl group A or B in the diamine derivative represented by the general formula (I), it may be at any substitution position. , NR ¹ or NR ² is preferably in the meta position. Thus, when the diamine derivative has a substituent at the meta position with respect to NR ¹ or NR ² , the color-forming recording material obtained according to the present invention generally tends to suppress background fog.

Further, in the general formula (I), R ¹ and
R ^2's each independently represent hydrogen, a lower alkyl group, an aryl group or an aralkyl group. The preferable ones of these groups are the same as those mentioned above. According to the present invention, when R ¹ and R ² are not simultaneously hydrogen atoms, that is, when at least one of the two nitrogen atoms is a tertiary amino group nitrogen, R ¹ and R ² are simultaneously hydrogen atoms. In the case where the two nitrogen atoms are both secondary amino group nitrogen, the obtained color forming recording material generally tends to suppress the background fog.

Examples of the above-mentioned diamine used in the present invention include N, N'-diphenyl-o-phenylenediamine, N, N'-diphenyl-m-phenylenediamine and N, N'-diphenyl-p-. Phenylenediamine, N,
N'-tetraphenyl-p-phenylenediamine, N-phenyl-N-methyl-N'-phenyl-N'-methyl-p-
Phenylenediamine, N-phenyl-N-benzyl-N '
-Phenyl-N'-benzyl-p-phenylenediamine,
N- (4-hydroxyphenyl) -N'-phenyl-p-
Phenylenediamine, N- (4-hydroxyphenyl)
-N'-phenyl-N, N'-dimethyl-p-phenylenediamine, N- (3-methoxyphenyl) -N'-phenyl-
p-phenylenediamine, N- (4-methoxyphenyl) -N'-phenyl-p-phenylenediamine, N-
(4-Ethoxyphenyl) -N'-phenyl-p-phenylenediamine, N- (4-octadecyloxyphenyl) -N'-phenyl-p-phenylenediamine, N-
(4-Cyanophenyl) -N'-phenyl-p-phenylenediamine, N- (4-nitrophenyl) -N'-phenyl-p-phenylenediamine, N- (4-chlorophenyl) -N'-phenyl-p -Phenylenediamine, Np
-Tolyl-N'-phenyl-p-phenylenediamine, N
-(3-chlorophenyl) -N'-p-tolyl-p-phenylenediamine, 4 '-(4 "-anilinophenyl) aminoacetophenone, 4- (4'-anilinophenyl) aminobenzenesulfonic acid, 4- (4'-anilinophenyl) aminobenzoic acid, N- (4-dimethylcarbamoylphenyl) -N'-phenyl-p-phenylenediamine, N-
(4-Aminophenyl) -N'-phenyl-p-phenylenediamine, N- (4-dimethylaminophenyl) -N '
-Phenyl-p-phenylenediamine, N, N'-bis (4
-Dimethylaminophenyl) -p-phenylenediamine, N- (4-aminophenyl) -N-phenyl-N'-
(4-Aminophenyl) -p-phenylenediamine, N
-(4-anilinophenyl) -N'-phenyl-p-phenylenediamine, N, N'-bis (4-anilinophenyl)
-P-phenylenediamine, N- (4- (3-methoxyphenylamino) phenyl-N'-phenyl-p-phenylenediamine, N- (2-methyl-4-methoxyphenyl) -N'-phenyl-p- Examples thereof include phenylenediamine.

Further, N- (3-aminophenyl) -N'-
Phenyl-p-phenylenediamine, N- (3-hydroxyphenyl) -N'-phenyl-p-phenylenediamine, N- (3-dimethylaminophenyl) -N'-phenyl-p-phenylenediamine, N, N ' -Bis (4-chlorophenyl) -p-phenylenediamine, N, N'-bis (3
-Chlorophenyl) -p-phenylenediamine, N, N'-
Bis (4-tolyl) -p-phenylenediamine, N, N'-
Bis (3-tolyl) -p-phenylenediamine, N, N'-
Bis (4-methoxyphenyl) -p-phenylenediamine, N, N'-bis (3-methoxyphenyl) -p-phenylenediamine, N, N'-bis (3,5-dimethylphenyl)
-P-phenylenediamine, N, N'-bis (3,4-dimethylphenyl) -p-phenylenediamine, N- (3-tolyl) -N'-phenyl-p-phenylenediamine, N-
(3,5-Dimethylphenyl) -N'-phenyl-p-phenylenediamine, N- (3,4-dimethylphenyl) -N '
-Phenyl-p-phenylenediamine, N- (3-dimethylaminophenyl) -N'-phenyl-N, N'-dimethyl-p-phenylenediamine, N- (4-methoxyphenyl) -N'-phenyl-N , N'-dimethyl-p-phenylenediamine, N- (3-methoxyphenyl) -N'-phenyl-N, N'-dimethyl-p-phenylenediamine, N, N'-
Bis (4-chlorophenyl) -N, N'-dimethyl-p-phenylenediamine, N, N'-bis (3-chlorophenyl)
-N, N'-dimethyl-p-phenylenediamine, N, N'-bis (4-tolyl) -N, N'-dimethyl-p-phenylenediamine, N, N'-bis (3-tolyl) -N , N'-dimethyl-
p-phenylenediamine, N, N'-bis (4-methoxyphenyl) -N, N'-dimethyl-p-phenylenediamine,
N, N'-bis (3-methoxyphenyl) -N, N'-dimethyl-p-phenylenediamine, N, N'-bis (3,5-dimethylphenyl) -N, N'-dimethyl-p-phenylene Diamine, N, N'-bis (3,4-dimethylphenyl) -N, N'-dimethyl-p-phenylenediamine, N- (3-tolyl)
-N'-phenyl-N, N'-dimethyl-p-phenylenediamine, N- (3,5-dimethylphenyl) -N'-phenyl-N, N'-dimethyl-p-phenylenediamine, N- (3 ,
4-dimethylphenyl) -N'-phenyl-N, N'-dimethyl-p-phenylenediamine, N- (4-chlorophenyl) -N'-phenyl-N, N'-dimethyl-p-phenylenediamine, N, N'-di-β-naphthyl-p-phenylenediamine, N, N'-di-β-naphthyl-N, N'-dimethyl-p
-Phenylenediamine and the like can also be mentioned as specific examples of the diamine derivative in the present invention.

The oxidizing agent used in the present invention may be either an organic or an inorganic oxidizing agent.
For example, quinoid type electron accepting compounds, organic halides, peracids, phosphine oxides, sulfoxides, disulfides, N-oxides and the like can be mentioned.
Further, as the inorganic oxidant, for example, oxygen, halogen,
Examples thereof include halides and metal oxides.

Examples of such oxidizing agents include silver perchlorate, silver hexafluoroantimonate, silver oxide, lead oxide, benzoquinone, methylbenzoquinone, tetrafluorobenzoquinone, dichlorobenzoquinone, anthraquinone, naphthoquinone, chloranil, dichlorodicyano. Benzoquinone, tetracyanoquinodimethane, N, N'-diphenylquinone diimine, N-chlorosuccinimide, diphenyl disulfide, tribromomethylphenyl sulfone, benzoyl peroxide, N-methylmorpholine-N-oxide, m-chloroperoxide Examples thereof include benzoic acid and N-methoxyphenyl-N'-phenylquinonediimine.

In the present invention, of these, quinoid type electron-accepting compounds are preferable, and MNDO is particularly preferable.
-PM3 molecular orbital method (JJP Stewart, J. Comp. Che
m., 10, 209; Mopac Ver. 6.0), and a quinoid type electron accepting compound having an LUMO energy level in the range of -2.80 eV to -1.30 eV is preferable. In the present invention, the molar ratio of the diamine and the oxidizing agent is generally
It is in the range of 1: 100 to 100: 1, preferably in the range of 1:20 to 20: 1.

In the present invention, examples of the organic acidic substance that is solid at room temperature (hereinafter, simply referred to as an acidic substance) include phenols, carboxylic acids, sulfonic acids, and phenol resins. In particular, aromatic carboxylic acids including aromatic oxycarboxylic acids are preferably used. Particularly in the present invention, the acidic substance preferably has a pKa value of 11 or less, and more preferably 5 or less. Specifically, naphthol, bisphenol A, dichlorophenol, 4,4'-sulfonyldiphenol, nitrophenol, oxalic acid, malonic acid,
Maleic acid, benzoic acid, chlorobenzoic acid, nitrobenzoic acid, toluic acid, naphthoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, cinnamic acid, hydroxynaphthoic acid, benzenesulfonic acid, toluenesulfonic acid, phenylphenol- Formalin resin, butylphenol-acetylene resin and the like can be mentioned. In the present invention, the molar ratio of diamine to acidic material is generally in the range 1: 100 to 100: 1, preferably in the range 1:20 to 20: 1.

In the present invention, the diamine can be used alone or in combination of two or more kinds for the color forming recording material. Further, a known color-forming dye other than diamine can be used together to enhance absorption in the near infrared region or adjust the hue in the visible region. As already known color forming dyes other than such diamines,
For example, in addition to fluorane compounds, fluorene compounds,
Examples thereof include phthalide compounds. Examples of the absorption dye in the near infrared region include 3- (4′-anilinophenyl) amino-6-methyl-7-anilinofluorane and 3
-[4 '-(4 "-anilinophenyl) aminophenyl] amino-6-methyl-7-chlorofluorane, 3-diethylamino-7-dibenzylaminothiofluorane, 3-
Diethylamino-7-ethylaminothiofluorane, 3,
6-bis (dimethylamino) fluorene-9-spiro-
3 '-(6'-dimethylamino) phthalide, 3,6-bis (diethylamino) fluorene-9-spiro-3'-(6'-dimethylamino) phthalide, 3,3-bis [1,1-bis ( Four
-Dimethylaminophenyl) ethylene-2-yl] phthalide, 3,3-bis [1,1-bis (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide , 3- (4-dimethylaminophenyl) -3
-[1,1-bis (4-dimethylaminophenyl) ethylene-2-yl] phthalide, 3- (4-dimethylaminophenyl) -3- [1,1-bis (4-dimethylaminophenyl) ethylene-2 Examples include -yl] -6-dimethylaminophthalide and the like.

As the visible region absorbing dye, for example,
Blue chromophores such as crystal violet lactone, benzoyl leuco methylene blue, pyridine blue, 3
-Diethylamino-7-octylaminofluorane, 3
-Green-coloring dyes such as diethylamino-7-dibenzylaminofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7
-Red coloring dyes such as chlorofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-di-n-butylamino-6-methyl-7-anilinofluorane, 3-diethylamino- 7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6 -Methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-N-ethyl-N-isoamylamino-
6-methyl-7-anilinofluorane, 3- (Np-
Black color-forming dyes such as tolyl-N-ethylamino) -6-methyl-7-anilinofluorane can be mentioned.

The molar ratio of the diamine to the other type of color forming dye when the other type of color forming dye is used in combination is generally 1:10.
It ranges from 0 to 100: 1, preferably from 1:20 to 20: 1. The color-forming recording material according to the present invention can be made into a heat-sensitive pressure-sensitive recording material by a conventionally known method. For example, when used as a heat-sensitive recording material, the diamine, the oxidizing agent, and the acidic substance are dispersed in an appropriate solvent together with an additive and a binder which are optionally used together, and this is applied onto a substrate such as paper. Then
Just dry. The amount applied is generally 1 to 1 by dry weight.
It is in the range of 15 g / m ² . Examples of the binder include water-soluble polymers such as polyvinyl alcohol, hydroxyethyl cellulose, sodium polyacrylate, polyvinylpyrrolidone, and isobutylene-maleic anhydride copolymer, as well as polyvinyl acetate, polyurethane, and styrene-butadiene copolymer. Examples thereof include latices such as polyacrylic acid and polyacrylic acid ester.

The heat-sensitive recording material according to the present invention may contain a sensitizer, a fluorescent dye, a pigment, an antiblocking agent and the like as additives, if necessary. Examples of the sensitizer include stearic acid amide, benzamide, dibenzyl terephthalate, diphenyl carbonate, phenyl 1-hydroxy-2-naphthoate, 1-benzyloxynaphthalene, and 4,4′-dimethoxydiphenyl sulfone. it can. As the fluorescent dye, for example, diaminostilbene-based, benzimidazole-based, benzidine-based,
Examples of the imidazolone-based and coumarin-based compounds and pigments include titanium dioxide, clay, talc, calcium carbonate, aluminum hydroxide, silica, polystyrene resin, urea-formalin resin, and the like. Examples thereof include zinc, calcium stearate and paraffin wax.

For use as a pressure-sensitive recording material, one or two components of any one of the above-mentioned diamine, oxidizing agent and acidic substance are microencapsulated, and this is used together with the binder as described above in a paper-like material. It may be applied to a base material to form a top paper, and the remaining components that have not been microencapsulated may be applied to a base material such as paper together with a binder to form a bottom paper. As another method, the microcapsules as described above and the remaining components that have not been microencapsulated may be applied together with the binder on the same paper surface.

Polymers for forming microcapsules include polyurethane, polyamide, polyurea, polystyrene, styrene-methacrylate copolymer, urea-
Formaldehyde resin, melamine resin, etc. can be mentioned. Such a polymer is preferably produced by an interfacial polymerization method or an internal polymerization method. Further, various coacervation methods can be used to form microcapsules from the water-soluble polymer. In this method, as the water-soluble polymer, for example, gelatin, gum arabic, sodium alginate, carboxymethyl cellulose, polyvinylbenzenesulfonic acid, etc. can be used.

The color-forming recording material produced by such a method is provided with an overcoat layer on the surface for the purpose of protecting the recording layer, or an undercoat for smoothing the surface and increasing the heat transfer efficiency. It may be provided with a layer or an adhesive layer on the back side for use as a label.

[0033]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Examples 1-8 and Comparative Examples 1-3 Diamine 0.0132 g, oxidizing agent 0.0132 g, stearic acid amide 0.0264 g, 10 wt% polyvinyl alcohol aqueous solution 0.066 g and water 0.145 g are treated with a ball mill for 20 hours. Then, a dispersion liquid A was obtained.

Separately, 0.5 g of acidic substance, zinc stearate
0.3 g, 10 wt% polyvinyl alcohol aqueous solution 0.5 g
And 5.0 g of water were treated with a ball mill for 20 hours to obtain a dispersion B. Next, 1.0 g of Dispersion B was added to Dispersion A to prepare a coating solution, which was coated on a fine paper using a bar coater (PI1210 manufactured by Tester Sangyo Co., Ltd.) and air-dried, followed by NEC printer (PC-PR102TL). The bar code was printed using the thermal head of FIG. This bar code is a semiconductor laser (780 nm) bar code reader (LS820 made by Symbol Technologies, Inc.).
0) and LED (660 nm) bar code reader (MechanoSystems, Touch7-PC-M10). Table 1 shows the results of the reading test with the semiconductor laser bar code reader.

The diamine and the oxidizing agent used in the above
And acidic substances are as follows. Diamine (1) N, N'-diphenyl-p-phenylenediamine (2) N- (4-methoxyphenyl) -p-N'-phenyl
-P-phenylenediamine (3) N- (4-nitrophenyl) -pn'-phenyl-
p-phenylenediamineOxidant(In parentheses is MNDO-P
LUMO energy level calculated by M3 molecular orbital method
(EV) is shown. ) (A) N, N'-diphenyl-p-quinonediimine (-1.5
4) (b) N- (4-methoxyphenyl) -p-N'-phenyl
-P-quinonediimine (c) chloranil (-2.17) (d) benzoquinone (-1.71) (e) 2,3-dichloro-5,6-dicyanobenzoquinone (f) silver oxide (g) lead oxide ( h) NoneAcidic substance (A) 1-hydroxy-2-naphthoic acid (b) clay (c) None

[0036]

[Table 1]

In Examples 1 to 8, the reading with the LED bar code reader was also good. In addition, the prepared color-forming recording material was applied to a thermal paper color test device (TH
-PMD) is used for color development by heating, and the reflectance before and after color development is 300 using a UV measurement device (UV-3101 manufactured by Shimadzu).
Measured at ~ 1300 nm. The reflection spectra before and after coloring of the color forming recording materials of Example 1 and Comparative Example 1 are shown in FIGS. 1 and 2, respectively. The solid line shows before coloring and the broken line shows after coloring. Example 9 N, N'-diphenyl-p-phenylenediamine 0.05 g,
Chloranil 0.0472 g, 1-hydroxy-2-naphthoic acid 0.2178 g, stearic acid amide 0.20 g, zinc stearate 0.10 g, 10% polyvinyl alcohol aqueous solution 0.75 g and water 1.75 g were crushed with a crusher 10 The coating liquid was obtained by treating for a minute.

This coating solution was applied to a high-quality paper using a bar coater and air-dried to print a bar code. This barcode is a laser diode barcode reader and L
It could be read by any of the ED barcode readers. Also, heat color is developed using a thermal paper color tester,
The reflectance before and after color development was measured. FIG. 3 shows reflection spectra before and after color development. Example 10 A thermal paper was prepared in the same manner as in Example 9 except that 0.193 g of 1-naphthoic acid was used as the acidic substance, and the reflectance before and after color development was measured. FIG. 4 shows reflection spectra before and after color development. Example 11 A thermal paper was prepared in the same manner as in Example 9 except that 0.1923 g of o-phthalic acid was used as the acidic substance, and the reflectance before and after color development was measured. FIG. 5 shows reflection spectra before and after coloring. Example 12 A thermal paper was prepared in the same manner as in Example 9 except that 0.1842 g of o-chlorobenzoic acid was used as the acidic substance, and the reflectance before and after color development was measured. FIG. 6 shows reflection spectra before and after color development. Example 13 A thermal paper was prepared in the same manner as in Example 9 except that 0.0207 g of p-benzoquinone was used as the oxidizing agent, and the reflectance before and after color development was measured. FIG. 7 shows reflection spectra before and after color development. Example 14 A thermal paper was prepared in the same manner as in Example 9 except that N- (4-chlorophenyl) -N'-phenyl-p-phenylenediamine (0.0566 g) was used as the diamine, and the reflectance before and after coloring was measured. It was measured. FIG. 8 shows reflection spectra before and after color development. Example 15 A thermal paper was prepared in the same manner as in Example 9 except that N-p-tolyl-N'-phenyl-p-phenylenediamine (0.0527 g) was used as the diamine, and the reflectance before and after color development was measured. . FIG. 9 shows reflection spectra before and after color development. Example 16 A thermal paper was prepared in the same manner as in Example 9 except that 0.0558 g of N- (3-methoxyphenyl) -N'-phenyl-p-phenylenediamine was used as the diamine, and the reflectance before and after color development was obtained. Was measured. FIG. 10 shows reflection spectra before and after coloring. Example 17 N- (3-aminophenyl) -N'-phenyl-p-phenylenediamine 0.0550 g, chloranil 0.0246
g, 1-hydroxy-2-naphthoic acid 0.1129 g, stearic acid amide 0.05 g, zinc stearate 0.05
g, 10% polyvinyl alcohol aqueous solution 0.40 g and water
0.90 g was treated with a pulverizer for 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-colored using a thermal paper color-developing test apparatus in the same manner as in Examples 1-8. 11
Shows absorption curves at 300 to 1300 nm before and after color development. The solid line is before coloring and the broken line is after coloring. Example 18 N, N'-Dimethyl-N- (4-methoxyphenyl) -N'-
Phenyl-p-phenylenediamine 0.0636 g, chloranil 0.0246 g, bisphenol A 0.2730 g,
Stearic acid amide 0.05g, zinc stearate 0.05
g, 10% polyvinyl alcohol aqueous solution 0.40 g and water
0.90 g was treated with a pulverizer for 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-developed using a heat-sensitive paper color tester. FIG. 12 shows absorption curves before and after color development. Example 19 N, N'-diphenyl-N, N'-dimethyl-p-phenylenediamine 0.0576 g, chloranil 0.0246 g, 1-hydroxy-2-naphthoic acid 0.1129 g, stearic acid amide 0.05 g, stearin Zinc acid 0.05 g, 10% polyvinyl alcohol aqueous solution 0.40 g and water 0.90 g were treated with a pulverizer for 10 minutes to obtain a coating solution.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-developed using a thermal paper color tester. FIG. 13 shows absorption curves before and after color development. Example 20 N, N'-diphenyl-N, N'-dimethyl-p-phenylenediamine 0.0576 g, chloranil 0.0246 g, bisphenol A 0.2730 g, stearic acid amide 0.05
g, zinc stearate 0.05 g, 10% polyvinyl alcohol aqueous solution 0.40 g and water 0.90 g with a crusher.
The coating liquid was obtained by treating for a minute.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-colored using a thermal paper color-developing test device. FIG. 14 shows absorption curves before and after color development. Example 21 N, N'-Dimethyl-N- (4-methoxyphenyl) -N'-
Phenyl-p-phenylenediamine 0.0636 g, chloranil 0.0246 g, 1-hydroxy-2-naphthoic acid
0.1129 g, stearic acid amide 0.05 g, zinc stearate 0.05 g, 10% polyvinyl alcohol aqueous solution
0.40 g and 0.90 g of water were treated with a grinder for 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-colored using a thermal paper color-developing test device. FIG. 15 shows absorption curves before and after color development. Example 22 N, N'-Dimethyl-N- (4-hydroxyphenyl) -N '
-Phenyl-p-phenylenediamine 0.0608 g, chloranil 0.0246 g, 1-hydroxy-2-naphthoic acid 0.1129 g, stearic acid amide 0.05 g, zinc stearate 0.05 g, 10% polyvinyl alcohol aqueous solution 0.40 g And 0.90 g of water were treated with a pulverizer for 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-colored using a heat-sensitive paper color tester. FIG. 16 shows absorption curves before and after color development. Example 23 N-phenyl-N '-(4-methoxyphenyl) -p-phenylenediamine 0.05 g, p-benzoquinone 0.047
2 g, 1-hydroxy-2-naphthoic acid 0.2178 g,
Stearic acid amide 0.20 g, zinc stearate 0.10
g, 10% polyvinyl alcohol aqueous solution 0.75 g and water
1.75 g was treated with a pulverizer for 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-developed by using a thermal paper color tester. When the reflectance before and after color development at 780 nm was measured, it was 40% in the background part and 10% in the color part. Example 24 N, N'-diphenyl-p-phenylenediamine 0.05 g,
Anthraquinone (LUMO energy level -1.39
eV) 0.04 g, 1-hydroxy-2-naphthoic acid 0.2
178 g, stearic acid amide 0.20 g, zinc stearate 0.10 g, 10% polyvinyl alcohol aqueous solution 0.7
5 g and 1.75 g of water were treated with a grinder for 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-developed using a heat-sensitive paper color tester. When the reflectance before and after color development at 780 nm was measured, it was 95% in the background part and 70% in the color part. Example 25 N, N'-diphenyl-p-phenylenediamine 0.10 g,
Silver chloride 0.0275 g, 1-hydroxy-2-naphthoic acid
0.2178 g, stearic acid amide 0.20 g, zinc stearate 0.10 g, 10% polyvinyl alcohol aqueous solution
0.75 g and 1.75 g of water were treated with a pulverizer for 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heat-colored using a heat-sensitive paper color tester. When the reflectance before and after color development at 780 nm was measured, it was 94% in the background part and 72% in the color part. Example 26 N, N'-diphenyl-p-phenylenediamine 0.10 g,
Crusher of cupric chloride 0.0258 g, 1-hydroxy-2-naphthoic acid 0.2178 g, stearic acid amide 0.20 g, zinc stearate 0.10 g, 10% polyvinyl alcohol aqueous solution 0.75 g and water 1.75 g For 10 minutes to obtain a coating liquid.

Next, this coating solution was applied to a high-quality paper using a bar coater, air-dried, and then heated and colored using a thermal paper color tester. When the reflectance before and after color development at 780 nm was measured, it was 85% in the background part and 65% in the color part. In Examples 10 to 26 above, the NE
A bar code was printed using a thermal head of a printer manufactured by Company C (PC-PR102TL). These barcodes are laser diode barcode readers and LEDs
It could be read well by any of the bar code readers.

[0049]

As described above, the color-forming recording material according to the present invention gives a color having a practically sufficient intensity immediately after the color-forming operation, and the color-forming portion is strong in a wide range from the visible region to the near infrared region. Since it has absorption, it is useful for reading information by devices at all wavelengths, such as a bar code reader using a semiconductor laser for reading in the near infrared region and a device for reading in the visible region.

[Brief description of drawings]

FIG. 1 shows reflection spectra before and after color development of a color forming recording material according to Example 1,

FIG. 2 shows reflection spectra of a color forming recording material according to Comparative Example 1 before and after color development.

[Fig. 3]

[Fig. 4]

[FIG. 5]

FIG.

[FIG. 7]

FIG. 8

FIG. 9 and

FIG. 10 shows Examples 9, 10, 11, 12, respectively.
The reflection spectra before and after color development of the color forming recording materials 13, 14, 15 and 16 are shown.

FIG. 11

FIG. 12

FIG. 13

FIG. 14

FIG. 15 and

FIG. 16 is a reflection spectrum before and after color development of the thermal papers according to Examples 17 to 22, respectively, in which a solid line indicates before color development;
A broken line shows after coloring.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Keiki Kishikawa 6-12 Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industries, Ltd. (72) Masatoshi Nitahara Waki-cho, Kuga-gun, Yamaguchi Prefecture 6-1-2 Waki, Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Hiromasa Taruma 6-1-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Masato Kawamura 6-12, Waki, Waki-cho, Kuga-gun, Yamaguchi Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Hisaya Miki 6-1-2, Waki, Waki-cho, Kuma-gun, Yamaguchi Prefecture Mitsui Petrochemical Co., Ltd.

Claims (4)

[Claims] (A) General formula (I) A-NR ¹ -X-NR ² -B (In the formula, A and B each independently represent a monovalent aryl group, and X is a divalent arylene group. And R ¹ and R ² each independently represent hydrogen, a lower alkyl group, an aryl group or an aralkyl group.), (B) an oxidizing agent, and (c) an organic acidic substance which is solid at room temperature. A color-forming recording material containing: 2. The color-forming recording material according to claim 1, wherein the oxidizing agent is a quinoid type electron-accepting compound. 3. LUMO energy level of oxidant calculated by MNDO-PM3 molecular orbital method -2.80 to -1.3.
The chromogenic recording material according to claim 1 or 2, which is a quinoid type electron acceptor of 0 eV. 4. The color-forming recording material according to claim 1, wherein the organic acidic substance is an aromatic carboxylic acid.