JPH0524339A - Recording material with coloring property - Google Patents

Abstract

PURPOSE:To provide a recording material with coloring property which gives coloring with a sufficient strength for actual use, right after a coloring operation, and the colored part of which is ranged form visible to near IR. CONSTITUTION:The characteristic of the present recording material with coloring property is that the recording material contains 1, a compound which can form aluminum ions, 2 an oxidizer, and 3, an organic compound which produces an organic acid by heat.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, a dye precursor (hereinafter, referred to as a color-forming dye), which is almost colorless in itself but can express a certain color by a chemical reaction, is combined with a color-developing agent to develop the color. As a color-forming recording material, it has been widely put to practical use on heat-sensitive and pressure-sensitive recording paper and the like.

By the way, in recent years, a bar code has been widely used as a means for more advanced information processing, and a device using a semiconductor laser is often used as a device for reading the bar code because of its advantages such as small size, low cost and long life. Tend to be. Since the semiconductor laser emits light in the near infrared region, the dye forming the barcode must absorb the light in the region. However, in the fluoran-based color-forming dye that has been generally used in the conventional heat-sensitive / pressure-sensitive recording paper, the dye formed by the color-forming reaction does not have a practical absorption in the region. In addition, a method of extending the π-electron conjugated system to have absorption in the region is also adopted, but the compound has a high molecular weight and its production is not easy.
The formed dye is unstable and easily discolors, and has poor light resistance.

Therefore, in recent years, a compound having a structure greatly different from that of the conventional one has been proposed as a color forming dye which produces a dye absorbing the light in the region.

JP-A-62-181361 proposes a color forming recording material containing a phenylenediamine derivative or a naphthylenediamine derivative and an acidic substance. This color-forming recording material has a drawback that the change with time after color development is remarkable.

JP-A-63-256486 proposes a color forming recording material containing a phenylenediamine derivative or a naphthylene diamine derivative and a quinoid type electron accepting compound. According to the study of the present inventor, it is difficult for this color forming recording material to cause substantial color development, and it is considered that practical application is not easy.

Further, JP-A-63-94880 discloses a color-forming recording material containing a phenylenediamine derivative or a naphthylenediamine derivative and an organic halogen compound which generates a halogen radical by the action of heat and / or light. It is disclosed. The generated organic halogen radicals such as chlorine radicals abstract hydrogen radicals from surrounding compounds and generate strong acids such as hydrohalic acid such as hydrochloric acid. Therefore, when this recording paper is used for copying books, documents, etc., the durability of the paper is impaired for a long period of time.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel color forming recording material. Another object of the present invention is to provide a color forming recording material which gives a color having a practically sufficient intensity immediately after the color forming operation and has a strong absorption in a wide range from the visible region to the near infrared region. is there.

Still another object of the present invention is to provide a novel color forming recording material which can solve the above problems in the conventional color forming recording materials. Further objects and advantages of the present invention will be apparent from the following description.

[0010]

According to the present invention, the above objects and advantages of the present invention include (a) a compound capable of forming an aminium ion, (b) an oxidizing agent and (c) an organic acid by heat. It is achieved by a color-forming recording material characterized by containing a generated organic compound.

Examples of the compound (a) capable of forming an aminium ion include the following formula (I)

[0012]

[Chemical 3]

An amine compound represented by the following formula (II)

[0014]

[Chemical 4]

The amine compound represented by is preferably used.

When the amine compound is, for example, a compound represented by the above formula (I), the aminium ion produced from it is the following formula (I) '

[0017]

[Chemical 5]

It is represented by

In the above formula (I), R ¹ , R ² and R ³ can each independently represent a hydrogen atom, a lower alkyl group, an acyl group, an aryl group or an aralkyl group.

The lower alkyl group has, for example, 1 carbon atom.
The straight-chain or branched-chain alkyl group of -5 is preferable.

The acyl group has, for example, 1 to 10 carbon atoms.
And the alkyl moiety is preferably a linear or branched aliphatic acyl group, or an aromatic acyl group having 7 to 12 carbon atoms and the aryl moiety optionally substituted with an alkyl group. Examples of the aryl group include a phenyl group, a naphthyl group and a biphenyl group.

The aralkyl group is preferably a group corresponding to, for example, the above aryl group bonded to an alkyl group having 1 to 5 carbon atoms.

The above aryl group and aralkyl group have a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyl group and an alkylcarbonyloxy group in the aromatic ring. , An arylcarbonyloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfone group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, an amino group, an alkyl-substituted amino group, an aryl-substituted amino group, It may have one or more substituents selected from the group consisting of an alkyl-substituted carbamoyl group, an aryl-substituted carbamoyl group, a pyrrolidino group and a piperidino group.

Preferred examples of the halogen atom include fluorine, chlorine and bromine. Examples of the alkyl group, aryl group and acyl group are the same as the above groups. Further, the alkyl moiety contained in the alkoxy group, alkylcarbonyloxy group, alkoxycarbonyl group, alkylsulfonyl group, alkylsulfinyl group, alkyl-substituted amino group, and alkyl-substituted carbamoyl group has, for example, 1 to 1 carbon atoms.
Ten linear or branched alkyl groups may be mentioned as preferred.

The aryl moiety of the aryloxy group, the arylcarbonyloxy group, the aryloxycarbonyl group, the arylsulfonyl group, the arylsulfinyl group, the aryl-substituted amino group and the aryl-substituted carbamoyl group are the same as those exemplified above. Can be mentioned. The same aralkyl moiety as the aralkyl moiety of the aralkyloxy group can be exemplified.

Further, in the above formula (I), R ¹ ,
^{Two of} R ² and R ³ are bonded to each other to form pyrrole, indole, imidazole, carbazole, phenazine,
Heterocycles such as phenoxazine and phenothiazine may be formed.

Examples of the amine compound represented by the above formula (I) include bis (p-diethylaminophenyl) ethylamine, triphenylamine, tris (p-bromophenyl) amine, tris (p-methylphenyl) amine, tris ( p-diethylaminophenyl) amine, N
Examples thereof include phenylphenothiazine and pentaphenylpyrrole.

In the above formula (II), n is an integer from 0 to 2 and A represents an aryl group. As the aryl group, the same groups as those exemplified for the formula (I) can be exemplified.

R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a lower alkyl group, an acyl group, an aryl group or an aralkyl group. As these groups, the same groups as those exemplified for the above formula (I) can be exemplified.

The above aryl group and aralkyl group have a halogen atom, a cyano group, a hydroxyl group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyl group and an alkylcarbonyloxy group in the aromatic ring. , An arylcarbonyloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfone group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, an amino group, an alkyl-substituted amino group, an aryl-substituted amino group, It may have one or more substituents selected from the group consisting of an alkyl-substituted carbamoyl group, an aryl-substituted carbamoyl group, a pyrrolidino group and a piperidino group, and two of R ⁴ and R ⁵ or R ⁶ and R ⁷ are N. Forming a double bond with It may become a Kiriden group, R ⁴ and R ⁵
Or two of R ⁶ and R ⁷ are bonded to each other to form pyrrole, indole, imidazole, carbazole, phenazine,
Heterocycles such as phenoxazine and phenothiazine may be formed. Examples of these groups are the same as those exemplified for the above formula (I).

Examples of the amine compound represented by the above (II) include N, N'-diphenyl-p-phenylenediamine, N, N'-dibenzyl-N, N'-diphenyl-p-phenylenediamine and N-. Acetyl-N'-phenyl-p-phenylenediamine, N- (4-methoxyphenyl) -N'-phenyl-p-phenylenediamine, N- (4-chlorophenyl) -N'-phenyl-p
-Phenylenediamine, N, N, N ', N'-tetrakis (p-diethylaminophenyl) -p-phenylenediamine, 4'-(4 "-anilinophenyl) aminobenzenesulfonic acid, 4 '-(4"- Examples thereof include anilinophenyl) aminobenzoic acid, N, N, N ′, N′-tetomethylbenzidine, tetrakis (p-methylphenyl) hydrazine and the like.

The compound (a) capable of forming an aminium ion as described above can be used alone or in combination of two or more kinds. Further, as the compound (a) capable of generating an aminium ion, the above formula (I) and / or (I
The amine compound of I) and a known color forming recording material can be used in combination.

That is, it is also possible to enhance the absorption in the near infrared region or adjust the hue in the visible region by using a known color forming dye together. Examples of such various known color forming dyes include fluorane compounds, fluorene compounds, and fudaride compounds. Examples of the near infrared absorption dye include 3- (4'-anilinophenyl) amino-6-methyl-7-anilinofluorane, 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 (4
-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-yl] -6-dimethylaminophthalide and the like.

Examples of visible absorption dyes include blue chromogenic dyes such as crystal violet lactone, benzoyl leuco methylene blue and pyridine blue, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane. Red color-forming dyes such as 3-cyclohexylamino-6-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, etc. 3-diethylamino-6-methyl-7-anilinofluorane -G-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-tolyl-
Examples thereof include black color-forming dyes such as N-ethylamino) -6-methyl-7-anilinofluorane, but are not limited thereto. The molar ratio of the amine compound and the various color-forming dyes when the various color-forming dyes are used in combination is preferably in the range of 1: 100 to 100: 1, more preferably in the range of 1:20 to 20: 1. is there.

The color-forming recording material of the present invention further contains an oxidizing agent (b) and an organic compound (c) which generates an organic acid by heat.

Examples of the oxidizing agent (b) include silver perchlorate, silver hexafluoroantimonate, and iron (II) chloride.
I) Lead dioxide, benzoquinone, naphthoquinone, chloranil, tetracyanoquinodimethane, N, N'-diphenylquinone diimine, diphenyl disulfide, benzoyl peroxide, N-methylmorpholine-N-oxide, m-chloroperbenzoic acid And the like can be mentioned as preferable ones.

The oxidizing agent (b) has a molar ratio of the compound (a) capable of forming an aminium ion to the oxidizing agent (b) is preferably 1: 100 to 100: 1, more preferably 1:20 to.
It is used in a ratio of 20: 1.

Examples of the organic compound (c) which generates an organic acid by heat include phenyl hydroxynaphthoate, dibenzyl oxalate and the like, phthalic anhydride,
Examples thereof include acid anhydrides such as maleic anhydride and sulfobenzoic acid cyclic anhydride. It is considered that some of these cause a hydrolysis reaction due to water in the recording material or in the air to generate an organic acid.

The organic acid (c) has a molar ratio of the compound (a) capable of forming an aminium ion to the organic compound (c) of preferably 10: 1 to 1:50, more preferably 2: 1 to. It is used in a ratio of 1:10.

The color-forming recording material of the present invention may further contain, for example, a binder, a sensitizer, a fluorescent dye, a pigment or an anti-adhesive agent, if necessary.

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 coalesce, polyacrylic acid, and latexes of polyacrylic acid ester. As a sensitizer,
Examples thereof include stearic acid amide, benzamide, dibenzyl terephthalate, diphenyl carbonate, phenyl 1-hydroxy-2-naphthoate, 1-benzyloxynaphthalene and 4,4′-dimethoxydiphenyl sulfonic acid.

Examples of fluorescent dyes include diaminostilbene-based, benzimidazole-based, benzidine-based, imidazolone-based and coumarin-based compounds.
Examples of pigments include titanium dioxide, clay, talc,
Examples thereof include calcium carbonate, aluminum hydroxide, silica, polystyrene resin and urea-formalin resin.

Examples of the anti-adhesive agent include zinc stearate, calcium stearate, paraffin wax and the like.

When the color-forming recording material of the present invention is used as a heat-sensitive / pressure-sensitive recording material, a conventionally known method can be used in exactly the same manner. For example, when used as a heat-sensitive recording material, the color-forming recording material of the present invention is dispersed in a suitable solvent,
This may be applied on a substrate such as paper and dried. The amount applied is generally in the range of 1 to 15 g / m ² dry weight.

The color-forming recording material produced according to these methods may of course be provided with an overcoat layer on the surface for the purpose of protecting the recording layer or an adhesive layer on the back surface so that it can be used as a label. In addition, various other known techniques in this field may be appropriately added.

[0046]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 N, N'-diphenyl-p-phenylenediamine 0.05
g, N, N'-diphenyl-p-quinonediimine 0.05
g, phthalic anhydride 0.17 g, stearic acid amide 0.1
0 g, zinc stearate 0.10 g, 10% polyvinyl alcohol aqueous solution 0.8 g and water 1.8 g
A coating solution was obtained by treating the film with ITSCH for 10 minutes.

Next, this coating solution was applied to a high-quality paper using a bar coater (P11210, Tester Sangyo) and air-dried to obtain a heat-sensitive paper. The prepared thermal paper is heated to color using a thermal paper color tester (Okura Denki, TH-PMD), and the reflectance after color development is measured by a UV measuring device (Shimadzu, UV-31).
01) was used to measure at 300 to 1300 nm. FIG. 1 shows the reflection spectrum after color development.

A bar code was printed on the thermal paper using a thermal head of a printer manufactured by NEC (PC-PR102TL). This bar code is a laser diode (780 nm) bar code reader (Symbol Technol.
ogies Inc., LS8200) and LED (660nm)
Bar code reader (Mechano Systems, Touch7
-PC-M10), the reading test was performed, and it was possible to read with any bar code reader.

Example 2 N- (4-chlorophenyl) -N'-phenyl-p-phenylenediamine 0.06 g, chloranil 0.05 g, 2
-Sulfobenzoic acid cyclic anhydride 0.21 g, stearic acid amide 0.10 g, zinc stearate 0.10 g, 10%
A thermal paper was prepared in the same manner as in Example 1 using 0.8 g of an aqueous polyvinyl alcohol solution and 1.8 g of water, and the reflectance after color development was measured. FIG. 2 shows the reflection spectrum after color development.

When a bar code was printed on this thermal paper, it could be read by both a semiconductor laser bar code reader and an LED bar code reader.

[0052]

As is clear from the results of each embodiment,
The color-forming recording materials according to the present invention give coloration of practically sufficient intensity immediately after the color-forming operation, and since the color-forming part has strong absorption in a wide range from the visible to the near-infrared region, It is useful for reading information by devices at all wavelengths, such as bar code readers that use semiconductor lasers that read in. And devices that read in the visible range.

[Brief description of drawings]

FIG. 1 shows a reflection spectrum of a color forming recording material according to Example 1 after color development.

FIG. 2 shows a reflection spectrum of a color-forming recording material according to Example 2 after color development.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location B41M 5/30 6956-2H B41M 5/18 102 6956-2H 108 (72) Inventor Masato Kawamura Yamaguchi Prefecture 6-12 Waki, Waki-cho, Kuga-gun Mitsui Petrochemical Industry Co., Ltd. (72) Inventor Masatoshi Nitahara 6-1-2 Waki, Waki-cho, Kuga-gun Yamaguchi Prefecture Mitsui Petrochemical Co., Ltd.

Claims (3)

[Claims] 1. A color-forming recording material containing (a) a compound capable of generating an aminium ion, (b) an oxidizing agent, and (c) an organic compound capable of generating an organic acid by heat. 2. A compound capable of forming an aminium ion is represented by the following formula (I): The color-forming recording material according to claim 1, which is an amine compound represented by: 3. A compound capable of generating an aminium ion is represented by the following formula (II): The color-forming recording material according to claim 1, which is an amine compound represented by: