JPH05148257A - Phthalide compound and recording unit using the same compound - Google Patents

Abstract

PURPOSE:To obtain a new compound useful as colorless dye precursor in a recording unit excellent in light resistance and shelf life for an optical character reader having a reading wavelength region within an infrared region. CONSTITUTION:A compound expressed by formula I [R1 and R2 are H, 1-8C alkyl, halogen, etc.; R3 to R5 are H, halogen, hydroxyl group, 1-8C alkyl, etc.; A is formula II (R9 is H, halogen, hydroxyl group, 1-8C alkyl, etc; R7, R8 and R10 are H, halogen, hydroxyl group, 1-8C alkyl, 3-8C cycloalkyl, etc.)], e.g. N,N'-di(phthalid-3-yl)-N,N'-diphenyl-p-phenylenediamine. Furthermore, the compound expressed by formula I is obtained by reacting a compound expressed by formula III with a compound expressed by formula IV in a solvent such as toluene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phthalide compound useful as a dye precursor or the like and a recording material using the phthalide compound, and when used as a dye precursor of the recording material, it is excellent in storage stability such as light resistance. With excellent whiteness, excellent heat resistance, moisture resistance, chemical resistance, plasticizer resistance, and other storability, and an optical character (or mark) reader with a reading wavelength range in the infrared region On the other hand, the present invention relates to a phthalide compound capable of obtaining a recording material having excellent characteristics.

[0002]

2. Description of the Related Art Conventionally, by utilizing a color reaction between a colorless or light-colored dye precursor and an organic or inorganic acidic substance, information transmitted by mediating energy such as pressure, heat, electricity and light is recorded. Various methods have been proposed for doing this, for example, Kondo, Iwasaki, Paper and Paper Cooperative Magazine, Vol.
1-421, 463-470 (1976), a pressure-sensitive copying sheet, a heat-sensitive recording sheet, an electric heat-sensitive recording sheet, an ultrasonic recording sheet, an electron beam recording sheet, an electrostatic recording sheet, a photosensitive recording. Sheets and even photosensitive printing materials,
A large number of methods such as type ribbon, ballpoint pen ink, crayon, stamp ink have been proposed.

On the other hand, coupled with the rationalization of office processing, in recent years,
The number of cases in which a recorded image of a recording medium is read by an optical character reading device (including mark reading) has increased remarkably, and particularly, an optical character reading device having a reading wavelength in the infrared region is often used. For example, in the distribution industry, the POS system is attracting attention as a powerful tool in order to quickly respond to the needs of consumers, and a price tag printed with OCR characters or a bar code is processed by a computer at the same time as cashier checkout. Although the management efficiency has been improved, a small and inexpensive device having a reading wavelength in the infrared region is used for this reading device.

However, the recorded images (black color image, blue color image, red color image, green color image, etc.) obtained by the above-mentioned recording medium are
For an optical character reader that has a reading wavelength range in the visible range (400 to 700 nm), it can be read as a lead color, but in the infrared range (700 to 900 nm).
For an optical character reader with a reading wavelength range at
It could not be applied because it works as a dropout color regardless of the color tone.

Therefore, as a basic dye used for various recording materials, a dye suitable for an optical character reader utilizing light in the near infrared region is under development, and for example, a divinyl group-containing phthalide derivative ( (Japanese Patent Publication No. 58-5940)
And a phthalide derivative having a fluorene skeleton (JP-A-59-59
-199757) is proposed. However, the recorded images obtained using these compounds are easily discolored by irradiation with light such as sunlight and fluorescent lamps, and therefore satisfactory results have not been obtained.

[0006]

SUMMARY OF THE INVENTION The present invention can be read by an optical character reader having a reading wavelength range in the infrared region, and has excellent storability of recorded images, particularly excellent stability to light irradiation. The recording medium provided is provided.

[0007]

The present invention contains a phthalide compound represented by the following general formula [Chemical formula 1] and at least one phthalide compound represented by the following general formula [Chemical formula 1] as a dye precursor. It is a recording medium characterized by being strict.

[0008]

[Chemical 1]

[Wherein R ₁ and R ₂ are each a hydrogen atom; C ₁
To C ₈ alkyl group; C _{3 to} C ₈ cycloalkyl group;
A halogen atom, a C _{1 to} C ₈ alkyl group, a C _{3 to} C ₈ cycloalkyl group, a C _{1 to} C ₈ alkoxyl group, and an amino group —NR ₁₁ R ₁₂ which may be substituted; R _{3 to} R ₆ are each a hydrogen atom; a halogen atom; a hydroxyl group; a C _{1 to} C ₈ alkyl group; a C _{3 to} C ₈ cycloalkyl group; a C _{1 to} C ₈ alkoxyl group, and A is the following: ] Is shown.

[0010]

[Chemical 2]

Where R₉Is hydrogen atom; halogen atom; water
Acid group; C₁~ C₈Alkyl group of C₃~ C₈Cycloa
Rukiru group; C₁~ C₈Alkoxyl group; amino group -N
R₁₃R ₁₄, R₇, R₈, R_TenAre each a hydrogen atom;
Halogen atom; Hydroxyl group; C₁~ C₈Alkyl group of C₃
~ C₈A cycloalkyl group of C;₁~ C₈The alkoxyl
Indicates a group. In the above [Chemical Formula 2] and [Chemical Formula 3], R₁₁
~ R₁₄Each is a hydrogen atom; C₁~ C₈Alkyl group of C₃
~ C₈Cycloalkyl group; halogen atom, C₁~ C₈
Alkyl group of C₃~ C₈A cycloalkyl group of C;₁~
C₈Optionally substituted with an alkoxyl group of
Or a substituent A, but R₁₁And R₁₂, R₁₃And R₁₄Is it
Pyrrolidino group and piperidyl group with adjacent nitrogen atom
Group or a hexamethyleneimino group may be formed. ]

[0012]

The phthalide compound represented by the above general formula [Chemical Formula 1] is a novel compound, and is a stable compound which is almost colorless and is useful as a dye precursor for various recording materials. Such a compound develops color in the presence of an acidic substance and has a color density of 700 to 90.
It has an excellent property that it has a light absorption in the infrared region of 0 nm and that a recorded image that does not fade even when exposed to light for a long time can be obtained.

Further, the recording material of the present invention has a significant feature in using at least one kind of such a phthalide compound as a dye precursor. By adopting such a constitution, the whiteness is high, Does not cause discoloration of the image area even when stored under high temperature or high humidity environment,
Even if it touches chemicals or plasticizers, it does not cause discoloration in the image area or fog in the blank area, and it has high sensitivity, and is 700-90.
A recording material having a light absorption in an infrared region of 0 nm and not fading even when exposed to light for a long time is obtained.

The phthalide compound of the present invention having the above-mentioned excellent properties can be synthesized, for example, by the following method. As shown in the following reaction formula [Chemical Formula 3], by reacting a phenylenediamine derivative with an o-phthalaldehyde acid derivative, the target phthalide compound can be easily obtained in high yield and high purity, and at a relatively low cost. Can be synthesized. In addition, a solvent may be used in the reaction, if necessary.

[0015]

[Chemical 3]

Specific examples of the phthalide compound represented by the general formula [Chemical formula 1] are shown below. N, N'-di (phthalid-3-yl) -N, N'-diphenyl-p-phenylenediamine, N, N'-bis (6
-Dimethylaminophthalid-3-yl) -N, N'-diphenyl-p-phenylenediamine, N, N'-bis (6-methylphthalid-3-yl) -N, N'-diphenyl-p-phenylenediamine , N, N'-di (phthalid-3-yl) -N, N'-di (2-naphthyl) -p-
Phenylenediamine, N, N'-di (phthalid-3-yl) -N, N'-di (1-naphthyl) -p-phenylenediamine, N, N'-di (phthalid-3-yl) -N-
Phenyl-N '-(4-dimethylaminophenyl) -p
-Phenylenediamine, N, N'-di (phthalide-3-
Yl) -N-phenyl-N '-(4-methoxyphenyl) -p-phenylenediamine, N, N'-di (phthalide-3-yl) -N-phenyl-p-phenylenediamine, N, N'- Di (phthalide-3-yl) -N-phenyl-N '-{4- [N-phenyl-N- (phthalide-3
-Yl) amino] phenyl} -p-phenylenediamine, N, N'-bis (6-dimethylaminophthalide-3)
-Yl) -N-phenyl-N '-{4- [N-phenyl-N- (6-dimethylaminophthalid-3-yl) amino] phenyl} -p-phenylenediamine, N, N'-
Bis (6-methylphthalid-3-yl) -N-phenyl-N '-{4- [N-phenyl-N- (6-methylphthalid-3-yl) amino] phenyl} -p-phenylenediamine, N, N '-Di (phthalid-3-yl) -N,
N'-bis {4- [N-phenyl-N- (phthalide-3
-Yl) amino] phenyl} -p-phenylenediamine and the like. Of course, the phthalide derivative represented by the general formula [Chemical Formula 1] is not limited to these, and two or more kinds may be used together if necessary.

In the recording material of the present invention, the above [Chemical formula 1]
By using the specific phthalide derivative as described above, the hue in the visible portion can be obtained incidentally, but if necessary, various basic dyes exemplified below can be used in combination. 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) -3- (4-diethylamino) 2-Methylphenyl) -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl)- 3- (2-methylindol-3-yl)
Phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-
Bis (1,2-dimethylindol-3-yl) -6-
Dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide , 3- (p-dimethylaminophenyl) -3- (1-methylpyrrole-3-
Yl) -6-dimethylaminophthalide, 3- (p-dibenzylaminophenyl) -3- (1,2-dimethylindol-3-yl) -7-azaphthalide, 3- (4-diethylamino-2-ethoxy) Phenyl) -3- (1-ethyl-2-methylindol-3-yl) -7-azaphthalide, 3,3-bis (1-ethyl-2-methylindol-3-yl) phthalide, N-butyl-3 Triarylmethane compounds such as-{bis [4- (N-methylanilino) phenyl] methyl} carbazole, 4,4'-
Bis (dimethylamino) benzhydryl benzyl ether, N-halophenyl-leuco auramine, N-2,
4,5-trichlorophenyl leuco auramine, 4,
Diphenylmethane compounds such as 4′-bis (dimethylamino) benzhydryl-p-toluenesulfinic acid ester, thiazines such as 3,7-bis (diethylamino) -10-benzoylphenoxazine, benzoylleuco methylene blue, p-nitrobenzoylleucomethylene blue Compounds, 3-methylspirodinaphthopyran, 3
-Ethylspirodinaphthopyran, 3-phenylspirodinaphthopyran, 3-benzylspirodinaphthopyran, 3
-Spiro compounds such as methylnaphtho (6'-methoxybenzo) spiropyran, 3-propylspirodibenzopyran, di-β-naphthospiropyran, 3-methyl-di-β-naphthospiropyran, rhodamine-B-anilinolactam, rhodamine (P-nitroanilino) lactam,
Lactam compounds such as rhodamine (o-chloroanilino) lactam, 3-diethylamino-6-methylfluorane, 3-dimethylamino-7-methoxyfluorane, 3
-Diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6
-Methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3- (N-ethyl-p
-Toluidino) -7-methylfluorane, 3-diethylamino-7- (N-acetyl-N-methylamino) fluorane, 3-diethylamino-7- (N-methylamino) fluorane, 3-diethylamino-7-dibenzyl Aminofluorane, 3-diethylamino-7- (N-methyl-N-benzylamino) fluorane, 3-diethylamino-7- (N-β-chloroethyl-N-methylamino) fluorane, 3-diethylamino-7-diethylaminofluor Oran, 4-benzylamino-8-diethylaminobenzo [a] fluorane, 3- [4- (4-dimethylaminoanilino) anilino] -7-chloro-6-methylfluorane, 8- [4- (4- Dimethylaminoanilino) anilino] benzo [a] fluorane, 3- (N-ethyl-p-toluidi ) -6-methyl-7-phenylamino fluoran, 3- (N-ethyl--p- toluidino)
-6-Methyl-7- (p-toluidino) fluorane, 3
-Diethylamino-6-methyl-7-phenylaminofluorane, 3-dibutylamino-6-methyl-7-phenylaminofluorane, 3-dipentylamino-6-methyl-7-phenylaminofluorane, 3-diethylamino- 7- (2-carbomethoxy-phenylamino) fluorane, 3- (N-ethyl-N-isoamylamino)
-6-Methyl-7-phenylaminofluorane, 3-
(N-cyclohexyl-N-methylamino) -6-methyl-7-phenylaminofluorane, 3-pyrrolidino-
6-methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane,
3-diethylamino-6-methyl-7-xylidinofluorane, 3-diethylamino-7- (o-chlorophenylamino) fluorane, 3-dibutylamino-7- (o
-Chlorophenylamino) fluorane, 3- (N-ethyl-N-isoamylamino) -7- (o-chlorophenylamino) fluorane, 3- (N-methyl-N-propylamino) -6-methyl-7-phenylamino Fluorane, 3-pyrrolidino-6-methyl-7-p-butylphenylaminofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-phenylaminofluorane, 3-pyrrolidino-6 -Methyl-7-pn-butylphenylaminofluorane, 3- (N-methyl-N-)
n-hexylamino) -6-methyl-7-phenylaminofluorane, 3- (N-ethyl-N-n-hexylamino) -6-methyl-7-phenylaminofluorane,
3- (N-ethyl-N-cyclopentylamino) -6-
Methyl-7-phenylaminofluorane, 3- [N-
(3-Ethoxypropyl) -N-methylamino] -6-
Methyl-7-phenylaminofluorane, 3- [N-ethyl-N- (3-ethoxypropyl) amino] -6-methyl-7-phenylaminofluorane, 3-diethylamino-7- [m- (trifluoro Methyl) phenylamino] fluorane, 3-diethylamino-7- (o-fluorophenylamino) fluorane, 3-dibutylamino-7- (o-fluorophenylamino) fluorane, 3
-Diethylamino-6-chloro-7-phenylaminofluorane, 3- (N-ethyl-Np-tolylamino)
-7-Methylfluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7-anilinofluorane, 3- (N-cyclopentyl-N-ethylamino) -6-methyl- 7-anilinofluoran, 3-
(N-ethyl-N-p-tolylamino) -6-methyl-
7-anilinofluorane, 2,2'-bis {4- [6 '
-(N-cyclohexyl-N-methylamino) -3'-
Methyl spiro [phthalide-3,9'-xanthene]-
Fluorane compounds such as 2'-ylamino] phenyl} propane.

In the recording material of the present invention, the acidic substance used in combination with the dye precursor as described above is appropriately selected according to the kind of the recording material, but depending on the media of pressure, heat and electric energy. Bringing a dye precursor and an acidic substance into contact with each other, for example, pressure-sensitive recording medium, heat-sensitive recording medium, energization heat-sensitive recording medium, ultrasonic recording medium, electrostatic recording medium, type ribbon, ballpoint pen ink, crayon, etc. Alternatively, a substance that acts as a Lewis acid is preferably used. Specifically, for example, acid clay, activated clay, attapulgite, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, calcined kaolin, inorganic developer such as talc, oxalic acid, maleic acid, tartaric acid, citric acid. Acids, aliphatic carboxylic acids such as succinic acid and stearic acid, benzoic acid, p-tert-
Butylbenzoic acid, phthalic acid, gallic acid, salicylic acid, 3
-Isopropyl salicylic acid, 3-phenyl salicylic acid,
3-cyclohexylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 4-pentyloxysalicylic acid, 4- (2-p-tolylsulfonylethoxy) salicylic acid, 4- (2-phenoxy) Ethoxy) salicylic acid, 5- [p- (2-p-methoxyphenoxyethoxy) cumyl] salicylic acid, 3-
Phenyl-5- (α, α-dimethylbenzyl) salicylic acid, 3,5-di- (α-methylbenzyl) salicylic acid,
Aromatic carboxylic acids such as 2-hydroxy-1-benzyl-3-naphthoic acid, 4,4'-isopropylidene diphenol, 4,4'-isopropylidene bis (2-chlorophenol), 4,4'-isopropylidene Redenbiss (2
6-dichlorophenol), 4,4'-isopropylidenebis (2,6-dibromophenol), 4,4'-isopropylidenebis (2-methylphenol), 4,
4'-isopropylidene bis (2,6-dimethylphenol), 4,4'-isopropylidene bis (2-tert-
Butylphenol), 4,4'-sec-butylidene diphenol, 4,4'-cyclohexylidenebisphenol, 4,4'-cyclohexylidenebis (2-methylphenol), 4-tert-butylphenol, 4-phenylphenol , 4-hydroxydiphenoxide, α-naphthol, β-naphthol, methyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate,
2,2'-thiobis (4,6-dichlorophenol),
4-tert-octylcatechol, 2,2'-methylenebis (4-chlorophenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol),
2,2'-dihydroxydiphenyl, 4-hydroxydiphenyl sulfone, 4-hydroxy-4'-methyl-
Phenolic compounds such as diphenyl sulfone, 4-hydroxy-4′-isopropoxy-diphenyl sulfone, p-phenylphenol-formaldehyde resin,
Organic developers such as phenolic resins such as p-butylphenol-acetylene resins, and salts of these organic developers with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin and nickel, And hydrohalic acid such as hydrogen chloride, hydrogen bromide, hydrogen iodide, inorganic acid such as boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, aluminum, zinc, nickel, tin, titanium, boron And the like.

In the case of an electron beam recording material or a photosensitive recording material, an electron beam or light produces hydrogen halide such as hydrogen chloride, hydrogen bromide, hydrogen iodide, carboxylic acid, sulfonic acid, phenols and the like. For example, carbon tetrabromide, α, α, α
-Organohalogen compounds such as tribromoacetophenone, hexachloroethane, iodoform, 2-tribromomethylpyridine, and trichloromethylsulfonylbenzene, o-quinonediazide compounds, carboxylic acid or sulfonic acid phenol esters that cause photo-Fries transition, etc. Is preferably used.

Regarding various typical recording materials of the present invention,
The details will be described below. Pressure-sensitive recording materials are disclosed in, for example, US Pat. Nos. 2,505,470, 2,505,471, and 2,
505489, 2548366, 271250.
No. 7, No. 2730456, No. 2730457, No. 3
418250, 3924027, and 401003.
As described in No. 8 and the like, there are various forms, and the present invention can be applied to these various forms of pressure-sensitive recording materials.

Generally, a dye precursor such as triarylmethane lactones, spiropyrans, fluoranes, diphenylmethanes and azines is optionally alkylated with a phthalide derivative represented by the above [formula 1]. , Synthetic oils such as alkylated diphenyls, alkylated diphenylmethanes and alkylated terphenyls, cotton oils, vegetable oils such as castor oils, animal oils, mineral oils, or a mixture thereof, and then dispersed in a binder. Dispersion, or the above solution is contained in microcapsules by various capsule manufacturing methods such as coacervation method, interfacial polymerization method, in-situ method, and the dispersion liquid dispersed in a binder is paper, plastic sheet, resin coated. The pressure-sensitive recording material of the present invention is manufactured by applying it on a support such as paper. That.

Of course, a so-called upper sheet in which the above-mentioned dispersion is applied to one side of the support, a developer coating solution mainly containing a developer is applied to one side of the support, and the above-mentioned dispersion is applied to the opposite side. The so-called intermediate sheet, further, by applying a coating liquid in which the capsule and the developer are mixed on the same surface of the support, or by coating the capsule dispersion and then applying the developer coating liquid, It goes without saying that various forms such as a so-called single copy sheet in which the capsule and the color developer coexist on the same surface are included. The amount of the dye precursor used varies depending on various conditions such as the desired coating amount, the form of the pressure-sensitive recording material, the capsule manufacturing method, the composition of the coating liquid containing various other auxiliaries, and the coating method. It may be selected as appropriate.

In any case, by using the phthalide derivative represented by the above-mentioned [Chemical formula 1], the pressure-sensitive property which is excellent in light resistance for a long time and which can form a recorded image readable by an optical character reader. A recording body can be obtained.

The thermosensitive recording medium is, for example, Japanese Patent Publication No. 44-3680.
No. 44-28880, No. 45-14039, No. 48-43830, No. 49-69, No. 49-70.
No. 52-20142 and the like, there are various forms, and the present invention can be applied to the thermal recording medium of these various forms, and exhibits a recorded image having the above-mentioned excellent properties. A thermal recording material can be obtained.

Generally, a coating solution obtained by dispersing a dye precursor using the phthalide derivative represented by the above [Chemical formula 1] and fine particles of a developer in a medium in which a binder is dissolved or dispersed. The thermosensitive recording medium of the present invention can be produced by coating the composition on a suitable support such as paper, plastic film, synthetic paper, non-woven fabric sheet, or molded article.

The use ratio of the dye precursor and the color developer in the recording layer is not particularly limited, but generally 0.1 to 50 parts by weight, preferably 2 to 10 parts by weight per 1 part by weight of the dye. A coloring agent is used.

Further, for the purpose of improving the color-forming ability, matting the surface of the recording layer, and improving the writability, inorganic metal compounds and inorganic pigments such as oxides, hydroxides and carbonates of polyvalent metals are generally exposed. 0.1 to 5 parts by weight, preferably 0.2 to 2 parts by weight, can be used in combination with 1 part by weight of the coloring agent. Various auxiliaries such as a photo dye and a coloring dye can be appropriately used in combination as necessary. As described above, the thermal recording material of the present invention is generally produced by applying a coating liquid in which fine particles of a basic dye and a color developer are dispersed to a support. Two kinds of coating liquids, which are separately dispersed, may be overcoated on the support, and it is of course possible to manufacture by impregnation and papermaking. Other methods for preparing coating liquid,
The coating method is not particularly limited,
The coating amount is generally about ² to 12 g / m ² in terms of dry weight.

Further, it is of course possible to provide an overcoat layer on the recording layer for the purpose of protecting the recording layer, or to provide an undercoat layer on the support, and various known techniques in the field of heat-sensitive recording material production can be used. Can be appropriately added.
Examples of the binder include starches, celluloses, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salt, vinyl acetate-maleic anhydride copolymer salt, polyacrylic acid salt, styrene-
A butadiene copolymer emulsion or the like is appropriately selected and used.

An electrically-conductive heat-sensitive recording material is disclosed, for example, in JP-A-49-11.
No. 344, No. 50-48930 and the like. Generally, a coating solution in which a conductive substance, a dye precursor and a developer are dispersed together with a binder is applied to a support such as paper, or a conductive substance is applied to the support to form a conductive layer, and The electrothermographic recording material of the present invention is manufactured by applying a coating liquid in which a dye precursor, a color developer and a binder are dispersed. When neither the dye precursor nor the developer melts in a preferable temperature range of 70 to 120 ° C., the sensitivity to Joule heat can be adjusted by using an appropriate heat fusible substance together.

A basic dye is used for the photosensitive recording material. For example, Japanese Patent Publications No. 38-24188, No. 45-10550, No. 45-13258, No. 49-204, and No. 49-62.
12, JP-A-49-28449, JP-A-47-3161.
5, 48-32532, 49-9227, 49-135617, 50-80120, 50.
-87317, 50-126228 and the like.

Other ultrasonic recording materials (French Patent No. 2120)
922), an electron beam recording medium (Belgian Patent 79599).
No. 86), an electrostatic recording material (JP-B-49-3932), a photosensitive printing material (JP-A-48-12104), a marking material (JP-B-47-10766), a type ribbon (JP-A-49-39). No. 3713), ballpoint pen ink (JP-A-48-
83924), crayons (US Pat. No. 3,769,045).
Nos.) And various other recording materials can be produced by the method described in each patent using a dye precursor using the phthalide derivative represented by the above [Chemical formula 1].

[0032]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the invention is not limited to these examples without departing from the gist of the invention. Unless otherwise specified, parts and% in the examples represent parts by weight and% by weight, respectively.

Example 1 N, N'-diphenyl-p-phenylenediamine 2.6
g and 3.8 g of o-phthalaldehyde acid with toluene 5
The reaction was carried out in 0 ml at 80 ° C. for 3 hours. After the reaction, the solvent was distilled off. Then, it is recrystallized from toluene and is colorless crystal having a melting point of 252 to 254 ° C. and N, N′-di (phthalide-3
-Yl) -N, N'-diphenyl-p-phenylenediamine was obtained in an amount of 5.0 g. The yield was 95%.

Example 2 N, N'-diphenyl-p-phenylenediamine 2.6
and 4-methyl-2-hydroxycarbonylbenzaldehyde (4.0 g) were reacted in toluene (50 ml) at 80 ° C. for 3 hours. After the reaction, the solvent was distilled off. Then, it is recrystallized with toluene, and is a colorless crystal, melting point 232-239.
C, N, N'-bis (6-methylphthalid-3-yl)
5.0 g of -N, N'-diphenyl-p-phenylenediamine was obtained. The yield was 90%.

Example 3 N-phenyl-N '-(4-dimethylaminophenyl)
2.7 g of -p-phenylenediamine and 3.8 g of o-phthalaldehyde acid were reacted in 50 ml of toluene at 80 ° C for 3 hours. After the reaction, the solvent was distilled off. Then, it is recrystallized with toluene, and is a colorless crystal having a melting point of 172-179.
4.6 g of N, N′-di (phthalid-3-yl) -N-phenyl-N ′-(4-dimethylaminophenyl) -p-phenylenediamine at 0 ° C. were obtained. The yield was 85%.

Example 4 N-phenyl-N '-(4-methoxyphenyl) -p-
2.9 g of phenylenediamine and 3.8 g of o-phthalaldehyde acid were reacted in 50 ml of benzene at 80 ° C. for 3 hours. After the reaction, the solvent was distilled off. Then, it is recrystallized from toluene, and it is a colorless crystal and has a melting point of 184 to 186 ° C. N, N′-di (phthalid-3-yl) -N-phenyl-
4.3 g of N '-(4-methoxyphenyl) -p-phenylenediamine was obtained. The yield was 78%.

Example 5 3.5 g of N, N-bis (4-diphenylaminophenyl) amine and 6.0 g of o-phthalaldehyde acid were reacted in 50 ml of toluene at 110 ° C. for 3 hours. After the reaction, the solvent was distilled off. Then, the crystals were recrystallized from toluene and were colorless crystals having a melting point of 224 to 228 ° C., N, N′-di (phthalide-3-yl) -N-phenyl-N ′-{4- [N-
6.7 g of phenyl-N- (phthalid-3-yl) amino] phenyl} -p-phenylenediamine was obtained. The yield was 90%.

Example 6 3.5 g of N, N-bis (4-diphenylaminophenyl) amine and 7.0 g of 4-dimethylamino-2-hydroxycarbonylbenzaldehyde were added to 50 ml of toluene.
The reaction was carried out at 110 ° C. for 3 hours. After the reaction, the solvent was distilled off. Then, it is recrystallized from toluene and is colorless crystals having a melting point of 192 to 200 ° C., N, N′-bis (6-dimethylaminophthalid-3-yl) -N-phenyl-N ′-{4.
8.2 g of-[N-phenyl-N- (6-dimethylaminophthalid-3-yl) amino] phenyl} -p-phenylenediamine was obtained. The yield was 95%.

Example 7 Preparation of solution A N, N'-di (phthalid-3-yl) -N-phenyl-N '-{4- [N-phenyl-N- (phthalide-3-)
Il) amino] phenyl} -p-phenylenediamine
10 parts 3-dibutylamino-6-methyl-7-phenylaminofluorane 10 parts Methylcellulose 5% aqueous solution 5 parts Water 40 parts This composition was ground with a sand mill to an average particle size of 1.5 μm.

Preparation of Liquid B: 4,4′-isopropylidenediphenol 30 parts, 5% aqueous solution of methylcellulose 5 parts, water 55 parts This composition was ground by a sand mill to an average particle size of 1.5 μm.

Preparation of Liquid C 1,2-bis (3-methylphenoxy) ethane 20
Parts-methyl cellulose 5% aqueous solution 5 parts-water 55 parts This composition was ground by a sand mill to an average particle size of 1.5 µm.

Formation of recording layer: A solution 65 parts, solution B 90 parts, solution C 80 parts, silicon oxide pigment (oil absorption 180 ml / 100 g) 15 parts, 20% oxidized starch aqueous solution 50 parts, water 10 parts were mixed. It was stirred. The obtained coating liquid was applied to a base paper of 100 g / m ^{2 in} a dry weight of 5 g / m ²
And dried to obtain a heat-sensitive recording paper.

Examples 8 to 12 In the preparation of solution A of Example 7, N, N'-di (phthalid-3-yl) -N-phenyl-N '-{4- [N-phenyl-N- (phthalide -3-yl) amino] phenyl}
Five kinds of thermal recording papers were obtained in the same manner as in Example 7 except that the compound shown below was used instead of -p-phenylenediamine. Example 8; N, N'-di (phthalid-3-yl) -N,
N'-diphenyl-p-phenylenediamine Example 9; N, N'-bis (6-methylphthalide-3-
Yl) -N, N'-diphenyl-p-phenylenediamine Example 10; N, N'-di (phthalid-3-yl) -N
-Phenyl-N '-(4-dimethylaminophenyl)-
p-Phenylenediamine Example 11; N, N'-bis (6-dimethylaminophthalid-3-yl) -N-phenyl-N '-{4- [N-
Phenyl-N- (6-dimethylaminophthalid-3-yl) amino] phenyl} -p-phenylenediamine Example 12; N, N'-di (phthalid-3-yl) -N
-Phenyl-N '-(4-methoxyphenyl) -p-phenylenediamine

Example 13 In preparation of solution A, 3-dibutylamino-6-methyl-
A thermosensitive recording medium was obtained in the same manner as in Example 7 except that 10 parts of 7-phenylaminofluorane was not used.

Comparative Example 1 In the preparation of solution A, N, N'-di (phthalid-3-yl) -N-phenyl-N '-{4- [N-phenyl-N
A thermosensitive recording medium was obtained in the same manner as in Example 7 except that 10 parts of-(phthalid-3-yl) amino] phenyl} -p-phenylenediamine was not used.

Comparative Example 2 In the preparation of solution A, N, N'-di (phthalide-3-yl) -N-phenyl-N '-{4- [N-phenyl-N
3,3-bis [1- (phthalido-3-yl) amino] phenyl} -p-phenylenediamine instead of 10 parts
Example 7 except that 10 parts of (4-methoxyphenyl) -1- (4-dimethylaminophenyl) ethylene-2-yl] -4,5,6,7-tetrachlorophthalide were used.
A thermosensitive recording medium was obtained in the same manner as described above.

The 9 kinds of thermal recording papers thus obtained were pressed against a hot plate at 110 ° C. for 5 seconds (4 kg / cm ² ) to develop color. Table 1 shows the PCS value of this recorded image at 830 nm and the PCS value after exposure to sunlight for 8 hours.

[0048]

[Table 1]

The PCS value is described above as one of the indexes indicating the recording density of the recorded image.
The value is calculated by the following formula.

[0050]

[Equation 1]

The PCS value required for the recorded image cannot be unconditionally determined because it depends on the type of optical character reader used, but it is generally 0.5 in the reading wavelength range.
Must have a value of ~ 1.0, preferably 0.6 ~
1.0, and more preferably in the range of 0.7 to 1.0.

Example 14 N, N'-di (phthalid-3-yl) -N-phenyl-
N '-{4- [N-phenyl-N- (phthalid-3-yl) amino] phenyl} -p-phenylenediamine 10
Part, polymethylene polyphenyl isocyanate 5 parts, 2
2 parts of isocyanatoethyl-2,6-diisocyanatohexanoate and 100 parts of alkyldiphenylethane
Part, and then added to 150 parts of a 3% aqueous solution of polyvinyl alcohol and emulsified and dispersed.

To this emulsion, 1 part of ditriethanolamine was added, and after stirring at room temperature for 30 minutes, the temperature of the system was raised to 70 ° C. and the reaction was continued for 3 hours while continuing stirring. To 100 parts of this dispersion (solid content), 80 parts of wheat starch and 15 parts of carboxy-modified styrene-butadiene copolymer latex (solid content) were added to prepare a capsule with a solid content concentration of 20%. A coating liquid was obtained.

45 g / m of coating liquid containing this capsule
Was coated so as to be 5 g / m ² by dry weight on one side of the ^second sheet, in 200 parts of water to the rear surface 3,5-bis (alpha-methylbenzyl) zinc salt, 20 parts of salicylic acid, 80 parts of kaolin,
A dry weight of a developer coating liquid in which 30 parts of a styrene-butadiene copolymer emulsion (50% solid content) is dispersed is 5 g /
A pressure-sensitive copying paper (medium paper) was obtained by coating so as to be m ² .

Examples 15-19 N, N'-di (phthalid-3-yl) -N-phenyl-
N-{4- [N-phenyl-N- (phthalid-3-yl) amino] phenyl} -p-phenylenediamine was replaced by the following compounds in the same manner as in Example 14 except that the compounds shown below were used. To obtain a pressure-sensitive copying paper. Example 15; N, N'-di (phthalid-3-yl)-
N, N'-diphenyl-p-phenylenediamine Example 16; N, N'-bis (6-methylphthalide-3)
-Yl) -N, N'-diphenyl-p-phenylenediamine Example 17; N, N'-di (phthalid-3-yl) -N
-Phenyl-N '-(4-dimethylaminophenyl)-
p-Phenylenediamine Example 18; N, N'-bis (6-dimethylaminophthalid-3-yl) -N-phenyl-N '-{4- [N-
Phenyl-N- (6-dimethylaminophthalid-3-yl) amino] phenyl} -p-phenylenediamine Example 19; N, N'-di (phthalid-3-yl) -N
-Phenyl-N '-(4-methoxyphenyl) -p-phenylenediamine

Example 20 N, N'-di (phthalid-3-yl) -N-phenyl-
N '-{4- [N-phenyl-N- (phthalid-3-yl) amino] phenyl} -p-phenylenediamine 10
Parts, 3-dibutylamino-6-methyl-7-phenylaminofluorane 3 parts, polymethylene polyphenyl isocyanate 5 parts, 2-isocyanatoethyl-2,6-diisocyanato hexanoate 2 parts and alkyldiphenyl Polyvinyl alcohol 3 dissolved in 100 parts of ethane
% Aqueous solution, and emulsified and dispersed.

To this emulsion was added 1 part of ditriethanolamine, and the mixture was stirred at room temperature for 30 minutes, then the temperature of the system was raised to 70 ° C. and the reaction was continued for 3 hours while continuing stirring. To 100 parts of this dispersion (solid content), 80 parts of wheat starch and 15 parts of carboxy-modified styrene-butadiene copolymer latex (solid content) were added to prepare a capsule with a solid content concentration of 20%. A coating liquid was obtained.

45 g / m 2 of coating liquid containing this capsule
Was coated so as to be 5 g / m ² by dry weight on one side of the ^second sheet, in 200 parts of water to the rear surface 3,5-bis (alpha-methylbenzyl) zinc salt, 20 parts of salicylic acid, 80 parts of kaolin,
A dry weight of a developer coating liquid in which 30 parts of a styrene-butadiene copolymer emulsion (50% solid content) is dispersed is 5 g /
A pressure-sensitive copying paper (medium paper) was obtained by coating so as to be m ² .

Example 21 N, N'-di (phthalid-3-yl) -N-phenyl-
N '-{4- [N-phenyl-N- (phthalid-3-yl) amino] phenyl} -p-phenylenediamine 10
Part was dissolved in 100 parts of isopropylated naphthalene, and added to 350 parts of warm water (50 ° C.) in which 25 parts of pigskin gelatin having an isoelectric point of 8 and 25 parts of gum arabic were dissolved and emulsified and dispersed.

To this emulsion, 1000 parts of warm water was added and the pH was adjusted to 4 with acetic acid, then cooled to 10 ° C., and 10 parts of a 25% aqueous solution of glutaraldehyde was added to harden the capsule. A coating solution containing this capsule was coated on one side of a base paper of 45 g / m ² to a dry weight of 5 g / m ^2, and 200 parts of water on the back side of 3,5-bis (α-methylbenzyl) salicylic acid. 20 parts of zinc salt, 80 parts of kaolin, and 30 parts of styrene-butadiene copolymer emulsion (50% solid content) are dispersed in a developer coating solution having a dry weight of 5 g / m.
^A pressure-sensitive copying paper (medium paper) was obtained by coating so as to be ² .

Comparative Example 3 N, N'-di (phthalid-3-yl) -N-phenyl-
N '-{4- [N-phenyl-N- (phthalid-3-yl) amino] phenyl} -p-phenylenediamine 10
A pressure-sensitive copying paper was obtained in the same manner as in Example 20 except that no part was used.

Comparative Example 4 N, N'-di (phthalid-3-yl) -N-phenyl-
N '-{4- [N-phenyl-N- (phthalid-3-yl) amino] phenyl} -p-phenylenediamine 10
In place of 3,3-bis [1- (4-methoxyphenyl) -1- (4-dimethylaminophenyl) ethylene-
2-yl] -4,5,6,7-tetrachlorophthalide 1
A pressure-sensitive copying paper was obtained in the same manner as in Example 14 except that 0 part was used.

When several capsules of the above 10 types of pressure-sensitive copying paper were overwritten so that the surface coated with the capsule and the surface coated with the developer faced and pressed, a color image was obtained on the surface coated with the developer. Table 2 shows the PCS value of this color image at 830 nm and the PCS value after exposure to sunlight for 8 hours.

[0064]

[Table 2]

Example 22 To 200 parts of a 1% aqueous solution of polyvinyl alcohol was added 200 parts of cuprous iodide and 5 parts of a 10% aqueous solution of sodium sulfite, and the mixture was pulverized with a sand mill until the average particle size became 2 microns. Polyacrylic ester emulsion 8
And 20 parts of titanium oxide were added and sufficiently dispersed, then 50
It was coated on a g / m ² base paper so that the dry coating amount was 7 g / m ² .

A heat-sensitive coating solution prepared in the same manner as in Example 7 was coated on this coated surface so that the dry coating amount was 5 g / m ² , to obtain an electrically-conductive heat-sensitive recording paper. Using a tungsten recording needle electrode, 150 V is applied to this recording paper to apply a needle pressure of 1
When recorded with a cylindrical scanning recording tester at 0 g and a scanning speed of 630 mm / sec, a dark blue-black recorded image was obtained. The PCS value of this recorded image at 830 nm was 0.74, and the PCS value after exposure to sunlight for 8 hours was 0.81.

[0067]

As is clear from the results of the examples,
The recording material of the present invention can be sufficiently applied to an optical character reader having a reading wavelength range in the infrared region, and the recorded image obtained is excellent in light resistance and can be exposed to light for a long time. It was a recording material with extremely high commercial value that did not fade and had excellent storage stability.

Claims (4)

[Claims] 1. A phthalide compound represented by the following general formula [Chemical formula 1]
Compound [Chemical 1][In the formula, R₁, R₂Each is a hydrogen atom; C₁~ C₈The al
Kill group; C₃~ C₈Cycloalkyl group of halogen
Child, C₁~ C₈Alkyl group of C₃~ C₈The cycloal
Kill group, C₁~ C₈Alkoxyl group, amino group -NR
₁₁R₁₂Represents an aryl group which may be substituted with R,₃
~ R₆Are hydrogen atom; halogen atom; hydroxyl group; C₁~
C₈Alkyl group of C₃~ C₈A cycloalkyl group of C;
₁~ C₈Represents an alkoxyl group of
You [Chemical 2]Where R₉Is a hydrogen atom; a halogen atom; a hydroxyl group; C₁~
C₈Alkyl group of C₃~ C₈A cycloalkyl group of C;
₁~ C₈Alkoxyl group; amino group -NR₁₃R ₁₄Shows
And R₇, R₈, R_TenAre each hydrogen atom; halogen atom
Child; hydroxyl group; C₁~ C₈Alkyl group of C₃~ C₈Shi
Chloroalkyl group; C₁~ C₈Is an alkoxyl group.
In the above [Chemical formula 1] and [Chemical formula 2], R₁₁~ R₁₄Is each
Hydrogen atom; C₁~ C₈Alkyl group of C₃~ C₈Shi
Chloroalkyl group; halogen atom, C₁~ C₈The alkyl
Base, C₃~ C₈A cycloalkyl group of C;₁~ C₈The al
Aryl or substituent which may be substituted with a coxyl group
Shows A, but R₁₁And R₁₂, R₁₃And R₁₄Are adjacent
Pyrrolidino group, piperidino group or
A xamethyleneimino group may be formed. ] 2. A recording material containing at least one phthalide compound represented by the general formula [Chemical Formula 1] as a colorless or light-colored dye precursor. 3. The recording medium according to claim 2, wherein the recording medium is a pressure-sensitive recording medium. 4. The recording medium according to claim 2, wherein the recording medium is a thermal recording medium.