JP3048274B2 - Recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a recording material. More specifically, the present invention relates to a recording material having improved storage stability.

[0002]

2. Description of the Related Art Hitherto, recording materials utilizing color development by contact between an electron-donating color-forming compound and an electron-accepting compound are well known as pressure-sensitive recording materials, heat-sensitive recording materials, and electrothermal recording materials. . As the electron-donating color-forming compound of these recording materials, an electron-donating color-forming compound that emits green or an electron-donating color-forming compound that emits vermilion or red is widely used as a single substance or a mixture. For example, 3-N, N-diethylamino-7-
N, N-dibenzylaminofluoran is a color-forming compound that develops a green color and is known to be useful as a color-forming compound for recording materials (Japanese Patent Publication No. 46-461).
No. 4, JP-B-46-12312).

However, when this compound is used as a coloring material for a recording material, for example, a pressure-sensitive recording material, the microcapsule surface (CB surface) is very unstable to light and turns red by light irradiation. In addition, there is a problem that the color no longer develops green even when it is brought into contact with an electron accepting compound (a color developer) after light irradiation. Further, there is a disadvantage that the color image is also unstable to light. Also, for example, 3-
N, N-diethylamino-6-methyl-7-chlorofluorane is a color-forming compound that develops a vermilion or red color, and is known to be useful as a color-forming compound for recording materials (Japanese Patent Publication No. Sho 45). -4701). However, when this compound is used as a coloring material for a recording material, for example, a thermosensitive recording material, a thermosensitive recording material having low color sensitivity and suitable for high-speed recording cannot be obtained, and further improvement is strongly desired. That is the current situation.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a recording material having improved raw storability and storage stability of a color image in view of the above-mentioned problems.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on a recording material, particularly an electron-donating color-forming compound, and have reached the present invention. That is, the present invention relates to a recording material utilizing color development by contact between an electron-donating color-forming compound and an electron-accepting compound, wherein the fluoran represented by the general formula (1) or (2) is used as the electron-donating color-forming compound. The present invention relates to a recording material using at least one compound.

[0006]

Embedded image (Wherein R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and R ₁ and R ₂
May form a 5- or 6-membered heterocyclic ring with the N atom, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

The fluoran compound represented by the general formula (1) used as the electron-donating color-forming compound is a compound represented by the following general formula: wherein R ₁ and R ₂ are an alkyl group having 1 to 6 carbon atoms and an alkoxyalkyl group having 3 to 5 carbon atoms. Or a fluoran compound wherein R ₃ is a hydrogen atom or a methyl group, -NR ₁ R ₂ is a pyrrolidino group, a piperidino group or a morpholino group, and R ₃ is a hydrogen atom or a methyl group; ₁ and R ₂ are alkyl groups having 1 to 6 carbon atoms, fluoran compounds R ₃ is a hydrogen atom or a methyl group, R ₁ is an alkyl group having 1 to 6 carbon atoms, R ₂ is 3 carbon
A fluoran compound wherein R ₃ is a hydrogen atom or a methyl group; R ₁ is an alkyl group having 1 to 6 carbon atoms; R ₂ is a cyclohexyl group; and R ₃ is a hydrogen atom or a methyl group. It relates to a recording material that is a certain fluoran compound.

In the compound represented by the general formula (1) according to the present invention, when R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms, the alkyl group may be linear or branched; For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, n- Examples include a nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group. In particular, methyl group, ethyl group,
Alkyl groups having 1 to 6 carbon atoms such as n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl and n-hexyl are preferred.

When R ₁ and R ₂ represent an alkoxyalkyl group having 3 to 12 carbon atoms, for example, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxy group Ethyl group, 2-n-hexyloxyethyl group, 2-n-decyloxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-n-butoxypropyl group, 3 And -n-hexyloxypropyl group. In particular, a 2-methoxyethyl group, 2-
An alkoxyalkyl group having 3 to 5 carbon atoms such as an ethoxyethyl group, a 3-methoxypropyl group, and a 3-ethoxypropyl group is preferred. Further, R ₁ and R ₂ have 5 carbon atoms.
In the case of representing a cycloalkyl group of 1 to 12, examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group and a cyclododecyl group. Cyclohexyl groups are particularly preferred.

In the compound represented by the general formula (1),
When R ₁ and R ₂ form a 5- or 6-membered heterocyclic ring together with an N atom, preferred examples of the 5- or 6-membered heterocyclic ring include, for example, a pyrrolidino group, a piperidino group, a morpholino group And the like. In the compound represented by the general formula (1), R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group,
Examples thereof include an n-butyl group, and particularly, a hydrogen atom,
A methyl group is preferred.

As specific examples of the compound represented by the general formula (1) according to the present invention, the following compounds can be exemplified, but the present invention is not limited thereto. - Compound No. of compound 1.3-N, N-dimethylamino -7-N-cyclohexyl--N- phenylamino fluoran 2.3-N, N-diethylamino -7-N-cyclohexyl--N- phenylamino Fluoran 3.3-N, N-di-n-propylamino-7-N-cyclohexyl-N-phenylaminofluoran 4.3-N, N-di-n-butylamino-7-N-cyclohexyl- N-phenylaminofluorane 5.3-N, N-di-isobutylamino-7-N-cyclohexyl-N-phenylaminofluorane 6.3-N, N-di-n-pentylamino-7- N-cyclohexyl-N-phenylaminofluoran 7.3-N, N-di-isopentylamino-7-N-cyclohexyl-N-phenylaminofluoran 8.3-N , N-Di-n-hexylamino-7-N-cyclohexyl-N-phenylaminofluoran 9.3-N, N-Di-n-heptylamino-7-N-cyclohexyl-N-phenylaminofluoran 10 .3-N, N-di-n-octylamino-7-N-cyclohexyl-N-phenylaminofluoran

11.3-N, N-di-n-nonylamino-7-N-cyclohexyl-N-phenylaminofluoran 12.3-N, N-di-n-decylamino-7-N-cyclohexyl- N-phenylaminofluorane 13.3-N, N-di-n-undecylamino-7-N-cyclohexyl-N-phenylaminofluorane 14.3-N, N-di-n-dodecylamino- 7-N-cyclohexyl-N-phenylaminofluoran 15.3-N, N-di- (2'-methoxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluoran 16.3-N, N-di- (2'-ethoxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluoran 17.3-N, N-di- (3'-methoxypropyl) amino-7- N-cyclohexyl-N-phenylaminofluorane 18.3-N, N-di- (3'-ethoxypropyl) amino-7-N-cyclohexyl-N-phenylaminofluorane 19.3-pyrrolidino-7 -N-cyclohexyl-N-phenylaminofluoran 20.3-piperidino-7-N-cyclohexyl-N-phenylaminofluoran 21.3-morpholino-7-N-cyclohexyl-N-phenylaminofluoran 22.3 -N-methyl-N-ethylamino-7-N-cyclohexyl-N-phenylaminofluoran 23.3-N-methyl-NN-propylamino-7-N-cyclohexyl-N-phenylaminofluoran 24.3-N-methyl-N-isopropylamino-7-N-cyclohexyl-N-phenylamino Ruoran 25.3-N-methyl--N-n-butylamino -7-N-cyclohexyl--N - phenylamino fluoran

26.3-N-methyl-N-isobutylamino-7-N-cyclohexyl-N-phenylaminofluoran 27.3-N-methyl-N-sec-butylamino-7-N-cyclohexyl-N -Phenylaminofluoran 28.3-N-ethyl-NNn-propylamino-7-N-cyclohexyl- -N-phenylaminofluoran 29.3-N-ethyl-N-isopropylamino-7-N- Cyclohexyl-N-phenylaminofluoran 30.3-N-ethyl-Nn-butylamino-7-N-cyclohexyl-N-phenylaminofluoran 31.3-N-ethyl-N-isobutylamino-7- N-cyclohexyl-N-phenylaminofluoran 32.3-N-ethyl-N-sec-butylamino-7-N-cycl Rohexyl-N-phenylaminofluoran 33.3-N-n-propyl-N-isopropylamino-7-N-cyclohexyl-N-phenylaminofluoran 34.3-Nn-propyl-Nn- Butylamino-7-N-cyclohexyl-N-phenylaminofluoran 35.3-Nn-propyl-N-isobutylamino-7-N-cyclohexyl-N-phenylaminofluoran 36.3-N- n-propyl-N-sec-butylamino-7-N-cyclohexyl-N-phenylaminofluoran 37.3-N-isopropyl-Nn-butylamino-7-N-cyclohexyl-N-phenylamino Fluoran 38.3-N-isopropyl-N-isobutylamino-7-N-cyclohexyl-N-phenylaminofluoran 39.3-N-N-butyl-N-isobutylamino-7-N-cyclohexyl-N-phenylaminofluoran 40.3-N-methyl-NN-pentylamino-7-N-cyclohexyl-N- Phenylaminofluoran

41.3-N-Ethyl-N-isopentylamino-7-N-cyclohexyl-N-phenylaminofluoran 42.3-N-Ethyl-Nn-hexylamino-7-N-cyclohexyl- N-phenylaminofluoran 43.3-N-ethyl-NNn-octylamino-7-N-cyclohexyl-N-phenylaminofluoran 44.3-N-ethyl-N- (2'-ethoxyethyl) Amino-7-N-cyclohexyl-N-phenylaminofluorane 45.3-N-isobutyl-N- (2'-methoxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluoran 46.3 N-methyl-N- (2'-n-hexyloxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluorane 47.3 -N-methyl-N- (2'-n-decyloxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluoran 48.3-N-ethyl-N- (3'-methoxypropyl) amino- 7-N-cyclohexyl-N-phenylaminofluoran 49.3-N-ethyl-N- (3'-ethoxypropyl) amino-7-N-cyclohexyl-N-phenylaminofluoran 50.3-N -Ethyl-N- (3'-n-hexyloxypropyl) amino-7-N-cyclohexyl-N-phenylaminofluoran 51.3-N-ethyl-N-cyclopentylamino-7-N-cyclohexyl-N- Phenylaminofluorane 52.3-N-methyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluorane 5 .3-N-Ethyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluoran 54.3-Nn-propyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylamino Fluoran 55.3-N-n-butyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluoran

56.3-N-isobutyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluorane 57.3-N-n-pentyl-N-cyclohexylamino-7-N-cyclohexyl -N-phenylaminofluorane 58.3-N-hexyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluoran 59.3-N-n-decyl-N-cyclohexylamino- 7-N-cyclohexyl-N-phenylaminofluoran 60.3-N-ethyl-N-cycloheptylamino-7-N-cyclohexyl-N-phenylaminofluoran 61.3-N-ethyl-N-cyclo Octylamino-7-N-cyclohexyl-N-phenylaminofluoran 62.3-N-ethyl-N- Cyclodecylamino-7-N-cyclohexyl-N-phenylaminofluoran 63.3-N-ethyl-N-cyclododecylamino-7-N-cyclohexyl-N-phenylaminofluoran 64.3-N, N- Dimethylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 65.3-N, N-diethylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 66.3-N , N-Di-n-propylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 67.3-N, N-di-n-butylamino-6-methyl-7-N- Cyclohexyl-N-phenylaminofluoran 68.3-N, N-di-isobutylamino-6-methyl-7-N-cyclohexyl-N- Phenylaminofluoran 69.3-N, N-di-n-pentylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 70.3-N, N-di-isopentylamino- 6-methyl-7-N-cyclohexyl-N-phenylaminofluoran

71.3-N, N-Di-n-hexylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 72.3-N, N-Di-n-heptylamino- 6-Methyl-7-N-cyclohexyl-N-phenylaminofluoran 73.3-N, N-Di-n-octylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 74 .3-N, N-di-n-nonylamino-6-ethyl-7-N-cyclohexyl-N-phenylaminofluoran 75.3-N, N-di-n-decylamino-6-n-propyl- 7-N-cyclohexyl-N-phenylaminofluoran 76.3-N, N-di-n-undecylamino-6-n-butyl-7-N-cyclohexyl-N-phenylaminofluoran 7 7.3-N, N-di-n-dodecylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 78.3-N, N-di- (2'-methoxyethyl) amino -6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 79.3-N, N-di- (2'-ethoxyethyl) amino-6-methyl-7-N-cyclohexyl-N-phenylamino Fluoran 80.3-N, N-di- (3'-n-propoxypropyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 81.3-N, N-di- (3'-n-butoxypropyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 82.3-pyrrolidino-6-methyl-7-N-cyclohexyl-N-phenyl Aminofluorane 83.3-Piperidino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 84.3-morpholino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 85.3 -N-methyl-N-ethylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran

86.3-N-methyl-NNn-propylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 87.3-N-methyl-N-isopropylamino-6 Methyl-7-N-cyclohexyl-N-phenylaminofluoran 88.3-N-Methyl-NNn-butylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 89.3 -N-methyl-N-isobutylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 90.3-N-methyl-N-sec-butylamino-6-methyl-7-N- Cyclohexyl-N-phenylaminofluoran 91.3-N-ethyl-Nn-propylamino-6-methyl-7-N-cyclohexyl-N-phenylamido Fluoran 92.3-N-ethyl-N-isopropylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 93.3-N-Ethyl-Nn-butylamino-6-methyl- 7-N-cyclohexyl-N-phenylaminofluoran 94.3-N-ethyl-N-isobutylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 95.3-N-ethyl -N-sec-butylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 96.3-N-n-propyl-N-isopropylamino-6-methyl-7-N-cyclohexyl- N-phenylaminofluoran 97.3-N-n-propyl-Nn-butylamino-6-methyl-7-N-cyclohexyl-N-phenyl Nylaminofluoran 98.3-Nn-propyl-N-isobutylamino 6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 99.3-Nn-propyl-N-sec-butyl Amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 100.3-N-isopropyl-NNn-butylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran

101.3-N-isopropyl-N-isobutylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 102.3-Nn-butyl-N-isobutylamino-6-methyl -7-N-cyclohexyl-N-phenylaminofluoran 103.3-N-methyl-NN-pentylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 104.3 N-ethyl-N-isopentylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 105.3-N-ethyl-NN-hexylamino-6-methyl-7-N- Cyclohexyl-N-phenylaminofluoran 106.3-N-ethyl-Nn-octylamino-6-methyl-7-N-cyclohexyl -N-phenylaminofluoran 107.3-N-ethyl-N- (2'-n-propoxyethyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 108.3- N-ethyl-N- (2'-isopropoxyethyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 109.3-N-methyl-N- (2'-n- Hexyloxyethyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 110.3-N-methyl-N- (2'-n-decyloxyethyl) amino-6-methyl-7- N-cyclohexyl-N-phenylaminofluoran 111.3-N-ethyl-N- (3'-methoxypropyl) amino-6-methyl-7-N-cyclohexyl-N -Phenylaminofluoran 112.3-N-ethyl-N- (3'-ethoxypropyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 113.3-N-ethyl-N- (3'-n-hexyloxypropyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 114.3-N-ethyl-N-cyclopentylamino-6-methyl-7-N-cy Clohexyl-N-phenylaminofluoran 115.3-N-Methyl-N-cyclohexylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran

116.3-N-ethyl-N-cyclohexylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 117.3-N-n-propyl-N-cyclohexylamino-6 Methyl-7-N-cyclohexyl-N-phenylaminofluoran 118.3-N-n-butyl-N-cyclohexylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 119.3-N -N-pentyl-N-cyclohexylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran 120.3-NN-hexyl-N-cyclohexylamino-6-methyl-7-N-cyclohexyl -N-phenylaminofluoran 121.3-Nn-octyl-N-cyclohexylamino 6-Methyl-7-N-cyclohexyl-N-phenylaminofluoran 122.3-Nn-decyl-N-cyclohexylamino-6-ethyl-7-N-cyclohexyl-N-phenylaminofluoran 123.3 -N-ethyl-N-cycloheptylamino-6-ethyl-7-N-cyclohexyl-N-phenylaminofluoran 124.3-N-ethyl-N-cyclooctylamino-6-ethyl-7-N- Cyclohexyl-N-phenylaminofluoran 125.3-N-ethyl-N-cyclodecylamino-6-n-propyl-7-N-cyclohexyl-N-phenylaminofluoran 126.3-N-ethyl-N -Cyclododecylamino-6-n-butyl-7-N-cyclohexyl-N-phenylaminofluoran

The fluoran compound represented by the general formula (1) according to the present invention is typically a benzoic acid derivative represented by the following general formula (2) (formula 3) and a benzoic acid derivative represented by the general formula (3) ( The N-cyclohexyldiphenylamine derivative represented by Chemical formula 4) is combined with a dehydrating condensing agent, for example, concentrated sulfuric acid, concentrated sulfuric acid to which fuming sulfuric acid is added, polyphosphoric acid, phosphorus pentoxide, anhydrous aluminum chloride, and the like, particularly preferably. The reaction can be carried out in concentrated sulfuric acid, and after the reaction, the reaction product is discharged into ice water, and the obtained cake is subjected to an alkali treatment to produce the cake.

[0021]

Embedded image (Wherein, R ₁ and R ₂ have the same meaning as in the case of the general formula (1))

[0022]

Embedded image (Wherein, R ₃ has the same meaning as in the case of the general formula (1),
R ₄ represents an alkyl group having 1 to ₄ carbon atoms)

The dehydration-condensation reaction is usually carried out in a temperature range of about 0 to 100 ° C. for several hours to several tens of hours. When the reaction is carried out in concentrated sulfuric acid, it is particularly preferable to carry out the reaction at a temperature in the range of about 0 to 50 ° C. Since the reaction time depends on the reaction temperature, it is necessary to perform the reaction for a sufficient time. The alkali treatment to be performed after the dehydration condensation is performed at a temperature of about 0 to 100 ° C., preferably about 40 to 100 ° C. with an aqueous solution of potassium hydroxide, sodium hydroxide or the like to adjust the pH to about 9 to 13, The reaction time depends on the reaction temperature, but usually takes tens of minutes to several hours. The alkali treatment may be performed in the presence of an organic solvent such as benzene, toluene, xylene, and chlorobenzene. In this case, the generated fluoran compound can be extracted into the organic solvent. The fluoran compound thus produced can be purified, if necessary, by a known purification method such as recrystallization or column chromatography to increase the purity.

The recording material of the present invention is characterized by using at least one fluoran compound represented by the general formula (1) as an electron-donating color-forming compound. However, to the extent that the desired effects of the present invention are not impaired,
Various known electron-donating color-forming compounds can be used as a mixture with the fluoran compound represented by the general formula (1). The ratio of the fluoran compound represented by the general formula (1) to the known various electron-donating color-forming compounds varies depending on the type of the recording material.
The proportion of the fluoran compound represented by the general formula (1) is usually preferably 5% by weight or more, more preferably 20% by weight or more, and more preferably 40% by weight for adjusting the color tone of a color image. % Is particularly preferable.

The electron-donating color-forming compound other than the fluoran compound represented by the general formula (1) used in the present invention includes a triarylmethane compound, a diarylmethane compound, a rhodamine-lactam compound, and a fluoran compound. And indolylphthalide compounds, pyridine compounds, spiro compounds, fluorene compounds and the like. For example, as a triarylmethane compound,
3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide [also known as crystal violet lactone], 3,3-bis (4-dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) −
3- (1,3-dimethylindol-3-yl) phthalide, 3- (4-dimethylaminophenyl) -3- (2-
Methylindol-3-yl) phthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl)
-3- (1-Methylpyrrole-3-yl) -6-dimethylaminophthalide, 3,3-bis [2,2-bis (4-
Dimethylaminophenyl) ethenyl] -4,5,6,7
-Tetrachlorophthalide and the like.

As the diarylmethane compound, 4,
4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,
4,5-trichlorophenylleuco auramine and the like. Examples of rhodamine-lactam compounds include rhodamine-B-anilinolactam, rhodamine- (4-nitroanilino) lactam, and rhodamine-B- (4-chloroanilino) lactam.

Examples of the fluoran compounds include 3,6-dimethoxyfluoran, 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, Diethylamino-7-chlorofluoran, 3-
Diethylamino-6-methyl-7-chlorofluoran,
3-diethylamino-6,7-dimethylfluoran, 3
-N-cyclohexyl-NN-butylamino-7-methylfluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3-diethylamino-7-di-n −
Hexylaminofluoran, 3-diethylamino-7-
Anilinofluoran, 3-diethylamino-7- (2-
Chloroanilino) fluoran, 3-diethylamino-7
-(3-chloroanilino) fluoran, 3-diethylamino-7- (2,3-dichloroanilino) fluoran,
3-diethylamino-7- (3-trifluoromethylanilino) fluoran, 3-di-n-butylamino-7-
(2-chloroanilino) fluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-di-n
-Butylamino-6-chloro-7-anilinofluoran,

3-Diethylamino-6-methoxy-7-
Anilinofluoran, 3-di-n-butylamino-6-
Ethoxy-7-anilinofluoran, 3-pyrrolidino-
6-methyl-7-anilinofluoran, 3-morpholino-6-methyl-7-anilinofluoran, 3-dimethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl- 7-anilinofluoran,
3-di-n-butylamino-6-methyl-7-anilinofluoran, 3-di-n-pentylamino-6-methyl-7-anilinofluoran, 3-di-n-octylamino-6 -Methyl-7-anilinofluoran, 3-N-ethyl-N-methylamino-6-methyl-7-anilinofluoran, 3-Nn-propyl-N-methylamino-
6-methyl-7-anilinofluoran, 3-N-n-propyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isopropyl-N-methylamino-6-methyl- 7-anilinofluoran, 3-Nn-
Butyl-N-methylamino-6-methyl-7-anilinofluoran, 3-Nn-butyl-N-ethylamino-
6-methyl-7-anilinofluoran, 3-Nn-butyl-Nn-propylamino-6-methyl-7-anilinofluoran,

3-N-isobutyl-N-methylamino-
6-methyl-7-anilinofluoran, 3-N-isobutyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isopentyl-N-ethylamino-
6-methyl-7-anilinofluoran, 3-Nn-hexyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-Nn-octyl-N-ethylamino-6 Methyl-7-anilinofluoran, 3-N-cyclohexyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-Nn-propylamino-6-methyl-7- Anilino fluoran,
3-N-cyclohexyl-Nn-butylamino-6-
Methyl-7-anilinofluoran, 3-N-cyclohexyl-NN-pentylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-Nn-hexylamino-6-methyl- 7-anilinofluoran,
3-N-cyclohexyl-Nn-heptylamino-6
-Methyl-7-anilinofluoran, 3-N-cyclohexyl-NNn-octylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-Nn-
Decylamino-6-methyl-7-anilinofluoran,

3-N-2'-methoxyethyl-N-methylamino-6-methyl-7-anilinofluoran;
N-2'-methoxyethyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-2'-ethoxyethyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-2'-ethoxyethyl-N-ethylamino-6-methyl-7-anilinofluoran, 3
-N-3'-methoxypropyl-N-methylamino-6
-Methyl-7-anilinofluoran, 3-N-3'-ethoxypropyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-2'-methoxyethyl-N
-Isobutylamino-6-methyl-7-anilinofluoran, 3-N-2'-tetrahydrofurfuryl-N-ethylamino-6-methyl-7-anilinofluoran, 3
-N- (4'-methylphenyl) -N-ethylamino-6
-Methyl-7-anilinofluoran, 3-diethylamino-6-ethyl-7-anilinofluoran, 3-di-ethylamino-6-methyl-7- (2 ', 6'-dimethylphenylamino) fluoran , 3-di-n-butylamino-6-methyl-7- (2 ', 6'-dimethylphenylamino) fluoran, 3-di-n-butylamino-7-
(2 ′, 6′-dimethylphenylamino) fluoran,
2,2-bis [4 ′-(3-N-cyclohexyl-N-
Methylamino-6-methylfluoran) -7-ylaminophenyl] propane.

As the indolylphthalide compound,
3,3-bis (1-ethyl-2-methylindole-3
-Yl) phthalide, 3,3-bis (1-octyl-2-
Methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3
-(2-ethoxy-4-dibutylaminophenyl) -3
-(1-ethyl-2-methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-octyl-2-methylindole-
3-yl) phthalide and the like.

Examples of the pyridine compound include 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-octyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2 -Ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3-
(2-hexyloxy-4-diethylaminophenyl)
-3- (1-Ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-
2-phenylindol-3-yl) -4 or 7-azaphthalide, 3- (2-butoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 Or 7-azaphthalide.

Examples of the spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran,
Benzyl-spiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like. As the fluorene compound, 3 ′, 6′-bisdiethylamino-5
-Diethylaminospiro (isobenzofuran-1,9 '
-Fluoren) -3-one, 3 ', 6'-bisdiethylamino-7-diethylamino-2-methylspiro (1,
3-benzoxazine-4,9'-fluorene). These electron-donating color-forming compounds may be used alone or as a mixture of two or more kinds for the purpose of adjusting the color tone of a color-formed image.

In the recording material of the present invention, the electron-accepting compound may be an organic electron-accepting compound such as a phenol derivative, an organic acid or its metal salt, a complex, a urea derivative, or an inorganic electron-accepting compound such as an acid clay. No. For example, 4-tert-butylphenol, 4-
tert-octylphenol, 4-phenylphenol,
1-naphthol, 2-naphthol, hydroquinone, resorcinol, 4-tert-octylcatechol, 2,
2'-dihydroxybiphenyl, 2,2-bis (4'-
Hydroxyphenyl) propane [also known as bisphenol A], 1,1-bis (4′-hydroxyphenyl) cyclohexane, 2,2-bis (4′-hydroxy-3′-
Methylphenyl) propane, 2,2-bis (4′-hydroxyphenyl) acetic acid ethyl ester, 4,4- (4 ′
-Hydroxyphenyl) pentanoic acid-n-butyl ester, 4-hydroxybenzoic acid benzyl ester, 4-hydroxybenzoic acid phenethyl ester, 2,4-dihydroxybenzoic acid phenoxyethyl ester, 4-hydroxyphthalic acid dimethyl ester, phthalic acid monoester Benzyl ester, phthalic acid monophenyl ester,

Hydroquinone monobenzyl ether, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (2-methyl-4-hydroxyphenyl) sulfide, bis (3-phenyl-4-hydroxyphenyl) sulfide, bis (3 -Cyclohexyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-n- Propoxydiphenylsulfone, 4-hydroxy-4'-
Isopropoxydiphenylsulfone, 4-hydroxy-4′-n-butoxydiphenylsulfone, 3,4-
Dihydroxy-4'-methyldiphenylsulfone, bis (2-hydroxy-4-tert-butylphenyl) sulfone, bis (2-hydroxy-4-chlorophenyl)
Sulfone, 4-hydroxybenzophenone, 2,4-
Dihydroxybenzophenone, 1,7-di (4-hydroxyphenylthio) -3,5-dioxaheptane, 1,
Phenol derivatives such as 5-di (4-hydroxyphenylthio) -3-oxapentane,

Salicylic acid, 3-isopropylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-tert
-Butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 3-methyl-5-α-methylbenzylsalicylic acid, 4- [2 ′-(4-methoxyphenyloxy)
Ethyloxy] salicylic acid, co-condensation resin of salicylic acid and styrene, organic acids such as 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, monobenzyl phthalate and monophenyl phthalate, and metals thereof. Salts (for example, metal salts such as nickel, zinc, aluminum and calcium), complexes such as zinc thiocyanate antipyrine complex and acetylacetone molybdate complex, phenylthiourea, di (3-trifluoromethylphenyl) thiourea, and 1,4- Organic electron-accepting compounds such as urea derivatives such as di (3′-chlorophenyl) -3-thiosemicarbazide, and inorganic electron-accepting compounds such as acid clay, attapulgite, activated clay, aluminum chloride, zinc chloride and zinc bromide are preferred. It can be mentioned as a compound. These electron accepting compounds may be used alone or in combination of two or more.

Examples of the recording material of the present invention include a heat-sensitive recording material, a pressure-sensitive recording material, an energized heat-sensitive recording material, a light-sensitive pressure-sensitive recording material, a heat-sensitive recording transfer recording material, and the like. A pressure-sensitive recording material, an energized heat-sensitive recording material, and a photosensitive pressure-sensitive recording material, particularly preferably a heat-sensitive recording material and a pressure-sensitive recording material. Examples of the pressure-sensitive recording material include, for example, U.S. Patent Nos. 2,505,470 and 2,505,471.
Nos. 2505489, 2548366, 27
12507, 2730456, 2730457
Nos. 3103404, 3418250, 39
There are various forms described in JP-A Nos. 24027 and 4010038, and the present invention can be applied to these various forms of pressure-sensitive recording materials. In general,
It comprises at least one pair of sheets separately containing an electron-donating chromogenic compound and an electron-accepting compound on a suitable support such as paper, plastic sheet, synthetic paper and the like.

The sheet containing the electron-donating color-forming compound (upper sheet, CB sheet) is prepared by converting the electron-donating color-forming compound into a synthetic oil such as alkylated naphthalene, alkylated biphenyl, alkylated diphenylmethane, alkylated terphenyl, and the like. , Cotton oil, castor oil and other vegetable oils, animal oils, mineral oils or a mixture thereof, and dissolved in a solvent and dispersed in a binder or the above solution is subjected to coacervation, interfacial polymerization, in- It is manufactured by applying a dispersion liquid contained in microcapsules and dispersed in a binder by various encapsulation methods such as a situ method on a suitable support such as paper, plastic sheet, or synthetic paper. In the microcapsules, in addition to the electron-donating color-forming compound, an ultraviolet absorber, an antioxidant, and the like may be added as additives. Particularly, from the viewpoint of improving the stability of the electron-donating color-forming compound in the capsule before use and improving the coloring of the capsule, etc., a benzotriazole-based ultraviolet absorber, a hindered amine-based antioxidant, a hindered phenol-based antioxidant, aniline It is preferable to add a system-based antioxidant, a quinoline-based antioxidant, or the like. On the other hand, sheets containing an electron-accepting compound (lower sheet, CF sheet) are prepared by adding an electron-accepting compound to a binder such as polyvinyl alcohol or a styrene-butadiene copolymer latex together with a pigment, if necessary. It is manufactured by applying a dispersion of an electron-accepting compound (developing agent) dispersed therein onto a suitable support such as paper, a plastic sheet, or synthetic paper.

Of course, a so-called intermediate sheet in which the above-mentioned electron-donating color-forming compound dispersion or the above-mentioned capsule dispersion is coated on one surface of the support and the dispersion of the electron-accepting compound is coated on the other surface, Is coated with a mixed dispersion of a capsule dispersion of an electron-donating chromophoric compound and a dispersion of an electron-accepting compound or a capsule dispersion of an electron-donating chromophoric compound on the same surface of the support. A form such as a so-called single copy sheet in which a capsule of an electron-donating color-forming compound and an electron-accepting compound coexist on the same surface of a support by coating a dispersion or the like is also included. The use ratio of the electron-donating color-forming compound to the electron-accepting compound is determined by various conditions such as the desired coating amount, the form of the pressure-sensitive recording material, the encapsulation method, the composition of the coating solution including various auxiliaries, and the coating method. May be selected as appropriate according to the conditions. It is easy for a person skilled in the art to determine this usage.

As the heat-sensitive recording material, for example, Japanese Patent Publication No. Sho 4
Nos. 4-3680 and 44-27880, 4
There are various forms described in JP-A-5-14039 and JP-A-48-43839, and the recording material of the present invention can be applied to heat-sensitive recording materials of these various forms.
In the case of a heat-sensitive recording material, the ratio of the electron-donating color-forming compound to the electron-accepting compound is usually from 50 to 100 parts by weight of the electron-donating color-forming compound.
700 parts by weight, preferably 100 to 500 parts by weight. For the purpose of improving the color-forming sensitivity, in addition to an electron-donating color-forming compound and an electron-accepting compound directly involved in color formation, a heat-fusible compound (melting point of about 70 to 150) may be used as a sensitizer.
C., more preferably a compound having a melting point of about 80 to 130 ° C.) is preferably added to the heat-sensitive recording material of the present invention in order to obtain a heat-sensitive recording material compatible with high-speed recording. In this case, usually, the electron-donating color-forming compound 10
0 parts by weight, 10 to 700 parts by weight of the heat-fusible compound,
It is desirable to use 20 to 500 parts by weight.

Examples of such heat-fusible compounds include, for example, nitrogen-containing compounds such as stearic acid amide, palmitic acid amide, stearyl urea, N-ethylcarbazole, 4-methoxydiphenylamine, and benzyl 4-benzyloxybenzoate. , 2-naphthoic acid phenyl ester, 1-hydroxy-2-naphthoic acid phenyl ester, oxalic acid dibenzyl ester, oxalic acid di (4-
Methylbenzyl) ester, oxalic acid di (4-chlorobenzyl) ester, glutaric acid diphenacyl ester,
Ester compounds such as di (4-methylphenyl) carbonate and dibenzyl terephthalate; hydrocarbon compounds such as 4-benzylbiphenyl, m-terphenyl, fluorene and fluoranthene; 2-benzyloxynaphthalene; 2- (4′- Methylbenzyloxy) naphthalene, 1,4-diethoxynaphthalene, 1,2-bis (3′-methylphenoxy) ethane, 1-phenoxy-
2- (4-ethylphenoxy) ethane, 4- (4'-methylphenoxy) biphenyl, 1,4-bis (2'-chlorobenzyloxy) benzene, 4,4'-di-n-butoxydiphenylsulfone, , 2-diphenoxybenzene, 1,4-bis (3'-methylphenyloxymethyl) benzene, 4-chlorobenzyloxy- (4'-
Ether compounds such as ethoxybenzene). These heat-fusible compounds may be used alone or in combination of two or more.

The heat-sensitive recording material can be manufactured by a known method without using a special method. Generally, an electron-donating color-forming compound, an electron-accepting compound, and the like, each in a water-soluble binder, ball mill,
By means of a sand mill or the like, a coating liquid can be prepared by usually pulverizing and dispersing the particles to a particle size of 3 μm or less, preferably 1.5 μm or less and mixing. As such a water-soluble binder, specifically, for example, polyvinyl alcohol,
Hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylamide, methylol-modified polyacrylamide, Starch derivatives, casein, gelatin, methylcellulose, carboxymethylcellulose,
Gum arabic, carboxyl group-modified polyvinyl alcohol and the like can be exemplified.

Further, if necessary, the recording layer of the heat-sensitive recording material of the present invention may contain a pigment, a water-insoluble binder, a metal soap, a wax, a surfactant, an ultraviolet absorber, a hindered phenol, an antifoaming agent and the like. Added. As pigments, zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, titanium oxide, talc, laurite, kaolin, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, alumina, silica, amorphous Silica, urea-formalin filler, polyethylene particles, cellulose filler and the like are used. As the water-insoluble binder, synthetic rubber latex or synthetic resin emulsion is generally used, and styrene-butadiene rubber latex, acrylonitrile-butadiene latex,
Methyl acrylate-butadiene rubber latex, vinyl acetate emulsion and the like are used.

As the metal soap, higher fatty acid metal salts are used, and zinc stearate, calcium stearate,
Aluminum stearate or the like is used. Examples of the wax include paraffin wax, microcrystalline wax, carboxy-modified paraffin wax, carnauba wax, polyethylene wax, polystyrene wax, and higher fatty acid esters. Examples of the surfactant include a sulfosuccinic acid-based alkali metal salt, a fluorine-containing surfactant, and the like.

Examples of the UV absorber include cinnamic acid derivatives, benzophenone derivatives, benzotriazolylphenol derivatives and the like.

The hindered phenol is preferably a phenol derivative in which at least one of the ortho positions of the phenolic hydroxyl group is substituted with a branched alkyl group.
3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl)
Butane, 1,1,3-tris (2-ethyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3
-Tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) propane, 2,2′-methylene-bis (6-tert-butyl-4)
-Methylphenol), 2,2′-methylene-bis (6
-Tert-butyl-4-ethylphenol), 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-tert
-Butyl-4-hydroxybenzyl) benzene, 1,
3,5-tris (4-tert-butyl-3-hydroxy-
2,6-dimethylbenzyl) isocyanuric acid, bis (2
-Methyl-4-hydroxy-5-tert-butylphenyl) sulfide and the like.

In the heat-sensitive recording material, the method for forming the recording layer is not particularly limited, and the recording layer can be formed according to a conventionally known technique. For example, a coating solution for a heat-sensitive recording layer is coated on a support with an air knife coater,
Blade coater, bar coater, gravure coater,
The recording layer can be formed by coating and drying with an appropriate coating device such as a curtain coater or a wire bar. Further, the invention is not particularly limited with respect to the coating amount of the coating liquid, generally, 1.5~12g / m ² by dry weight, it is adjusted preferably in the range of 2.5~10g / m ^2. Paper, plastic sheet, synthetic paper, etc. are used as the support. If necessary, a protective layer may be provided on the front and / or back surface of the heat-sensitive recording layer, and an undercoat layer may be provided between the support and the heat-sensitive recording layer. Various known techniques in a method for manufacturing a recording material can be provided.

The heat-sensitive recording material is disclosed in, for example,
It is manufactured by the methods described in JP-A-11344 and JP-A-50-48390. In general, conductive compounds,
An electron-donating color-forming compound, a coating liquid in which an electron-accepting compound is dispersed together with a binder is coated on a suitable support such as paper, or a conductive compound is coated on the support to form a conductive layer. It is manufactured by applying a coating liquid in which a binder is dispersed with an electron-donating color-forming compound and an electron-accepting compound. The sensitivity can be improved by using the above-mentioned heat-fusible compound in combination.

A photosensitive pressure-sensitive recording material is disclosed in, for example,
It is manufactured by a method described in JP-A-17979836. Generally, photopolymerization initiators such as silver bromide, silver behenate, Michler's ketone, benzoin derivatives, and benzophenone derivatives are crosslinked with polyfunctional monomers such as polyallyl compounds, poly (meth) acrylate, and poly (meth) acrylamide. Agent, an electron-donating color-forming compound, and, if necessary, both a solvent and a polyether urethane, which are encapsulated in a synthetic resin capsule such as polyurea,
And at least one pair of sheets separately containing an electron-accepting compound. After image exposure, utilizing the difference between curing and uncuring of the capsule by light, using the electron-donating color-forming compound in the unexposed area, it is brought into contact with the electron-accepting compound applied on the support to form a color. It is to let.

[0050]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples and Examples, but the present invention is not limited to these Examples. Production Example 1 Production of Compound of Exemplified Compound No. 2 35.5 g of 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid was dissolved in 150 ml of concentrated sulfuric acid at 10 ° C., and then N- (4 -Methoxyphenyl) -N
-Cyclohexyl-N-phenylamine [general formula (3)
In the compound, R ₃ is a hydrogen atom, R ₄ is a methyl group,
Melting point 89-91 ° C.]
Stirred at C for 30 hours. The reaction mixture was discharged into 1000 ml of ice water, the precipitated solid was collected, washed with water, and the wet cake was added to 10% aqueous NaOH (400 ml), and further 500 ml of toluene was added, followed by 3 hours at 60 to 70 ° C. Stirred. The toluene layer was separated, washed with warm water until neutral, the toluene layer was separated, and toluene was distilled off under reduced pressure. After 200 ml of methanol was added to the residue and left at room temperature, the precipitated crystals were separated by filtration. Then, the crystals are recrystallized from isopropanol to give the desired 3-N, N-diethylamino-7-form as almost colorless crystals.
30 g of N-cyclohexyl-N-phenylaminofluoran compound was obtained. Melting point: 152 to 154 ° C. This fluoran compound is 4% in a 95% acetic acid aqueous solution.
The absorption maximum was shown at 40 nm, 470 nm, and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and quickly developed a green color on silica gel.

Preparation Example 2 Preparation of Compound of Exemplified Compound No. 4 In Preparation Example 1, 2- (4′-N) was replaced with 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. , N-Di-n-butylamino-2 '
(Hydroxybenzoyl) benzoic acid was used to produce a 3-N, N-di-n-butylamino-7-N-cyclohexyl-N-phenylaminofluoran compound according to the method described in Production Example 1. . Melting point 167-169 ° C. This fluoran compound is 4% in 95% acetic acid aqueous solution.
The absorption maximum was shown at 40 nm, 470 nm, and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and quickly developed a green color on silica gel.

Preparation Example 3 Preparation of Compound of Exemplified Compound No. 26 In Preparation Example 1, 2- (4′-N) was used in place of 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. -Methyl-N-isobutylamino-
Other than using 2'-hydroxybenzoyl) benzoic acid,
According to the method described in Production Example 1, 3-N-methyl-N-
An isobutylamino-7-N-cyclohexyl-N-phenylaminofluoran compound was produced. Melting point 212-
214 ° C. This fluoran compound is 4% in 95% acetic acid aqueous solution.
The absorption maximum was shown at 40 nm, 470 nm, and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and quickly developed a green color on silica gel.

Preparation Example 4 Preparation of Compound of Exemplified Compound No. 44 In Preparation Example 1, 2- [4'-N was replaced with 2- (4'-N, N-diethylamino-2'-hydroxybenzoyl) benzoic acid. -Ethyl-N- (2′-ethoxyethyl) amino-2′-hydroxybenzoyl] benzoic acid, except that 3-N
-Ethyl-N- (2'-ethoxyethyl) amino-7-
An N-cyclohexyl-N-phenylaminofluoran compound was produced. Melting point: 117-120 ° C. This fluoran compound is 4% in 95% acetic acid aqueous solution.
The absorption maximum was shown at 40 nm, 470 nm, and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and quickly developed a green color on silica gel.

Production Example 5 Production of Compound of Exemplified Compound No. 45 In Production Example 1, 2- [4′-N was replaced with 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. -Isobutyl-N- (2'-methoxyethyl) amino-2'-hydroxybenzoyl] benzoic acid, except that benzoic acid was used.
-N-isobutyl-N- (2'-methoxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluoran compound was produced. Melting point 185-187 ° C. This fluoran compound is 4% in 95% acetic acid aqueous solution.
The absorption maximum was shown at 40 nm, 470 nm, and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and quickly developed a green color on silica gel.

Preparation Example 6 Preparation of Compound of Exemplified Compound No. 54 In Preparation Example 1, 2- (4′-N) was used in place of 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. -N-propyl-N-cyclohexylamino-2′-hydroxybenzoyl) benzoic acid was used in accordance with the method described in Production Example 1 except that 3-N-
-Propyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluoran compound was prepared. Melting point 229-231 ° C. This fluoran compound is 4% in 95% acetic acid aqueous solution.
The absorption maximum was shown at 40 nm, 470 nm, and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and quickly developed a green color on silica gel.

Production Examples 7 to 17 In Production Example 1, instead of 2- (4'-N, N-diethylamino-2'-hydroxybenzoyl) benzoic acid, the results are shown in Table 1 (Tables 1 and 2). Each fluoran compound was produced according to the method described in Production Example 1 except that a benzoic acid derivative was used. The table also shows the coloring hue of each fluoran compound on silica gel.

[0057]

[Table 1]

[0058]

[Table 2]

Preparation Example 18 Preparation of Compound of Exemplified Compound No. 67 35.5 g of 2- (4′-N, N-di-n-butylamino-2′-hydroxybenzoyl) benzoic acid was added to 150 ml of concentrated sulfuric acid at 10 ° C. After dissolving with N- (4-methoxy-2-methylphenyl) -N-cyclohexyl-N-phenylamine [in the general formula (3), a compound in which R ₃ is a methyl group and R ₄ is a methyl group, melting point 118 to 120 ° C] at the same temperature and stirred at 10 to 25 ° C for 30 hours. The reaction mixture was discharged into 1000 ml of ice water, the precipitated solid was collected, washed with water, and the wet cake was added to 10% aqueous NaOH (400 ml), and further 500 ml of toluene was added, followed by stirring at 60 to 70 ° C. for 3 hours. did. The toluene layer was separated, washed with warm water until neutral, the toluene layer was separated, and toluene was distilled off under reduced pressure. Methanol 2 in the residue
After adding 00 ml and leaving the mixture at room temperature, the precipitated crystals were separated by filtration. Further, the crystals are recrystallized from n-butanol to give 3-N, N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofuran as almost colorless crystals. 41 g of the orane compound were obtained. Melting point: 197 to 199 ° C.
It showed an absorption maximum at 5 nm. This toluene solution of the fluoran compound was colorless and transparent, and rapidly developed a vermilion color on silica gel.

Production Examples 19 to 30 In Production Example 18, Table 2 (Table 3, Table 3) was used in place of 2- (4'-N, N-di-n-butylamino-2'-hydroxybenzoyl) benzoic acid. 4, Each fluoran compound was produced according to the method described in Production Example 18 except that the benzoic acid derivative shown in Table 5) was used. Table 2 also shows the coloring hue of each fluoran compound on silica gel.

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

Examples 1 to 6 Pressure-sensitive recording material An upper (CB) sheet and a lower (CF) sheet were produced by the following method of producing a pressure-sensitive recording material, and evaluated by the following evaluation methods. The results are shown in Table 3 (Table 6) and Table 4 (Table 7). [Preparation method of pressure-sensitive recording material] 100 g of a 10% aqueous solution of ethylene-maleic anhydride copolymer and 240 g of water were mixed, and the pH was adjusted to 4 with a 10% aqueous sodium hydroxide solution.
An alkylated diphenylmethane solvent in which 5% by weight of an electron-donating color-forming compound is dissolved (manufactured by Nippon Petrochemical, SAS-2
96) After mixing 200 g and emulsifying with a homomixer,
60 g of a methylol melamine aqueous solution having a solid content of 50% (Euramine T-30, manufactured by Mitsui Toatsu Chemicals, Inc.) is added, and the mixture is kept at 55 ° C. for 3 hours while stirring to obtain a microcapsule dispersion having an average particle size of 5.0 μm. To 100 g of this dispersion, 4.0 g of wheat starch starch, 20 g of 20% oxidized starch paste and 11 g of water were added.
6 g was added and dispersed, and applied to a paper having a basis weight of 40 g / m ^{2 so} that the application amount was 5 g / m ² in terms of solid content.
Get a sheet. On the other hand, using a zinc salt of a co-condensation resin of salicylic acid and styrene as an electron-accepting compound (a color developer), in the presence of a small amount of a polymeric anionic surfactant, pulverizing in water with a sand grinding mill, A 40% by weight aqueous dispersion is obtained. Using this aqueous dispersion, an aqueous paint (solid content 30%) having the following composition was prepared, and the basis weight was 40 g / m ^2.
, And apply the dried coating amount to 5.5 g / m ² to prepare a lower (CF) sheet.

Composition of aqueous coating composition Solid weight (g) Light calcium carbonate 100 Electron accepting compound (developing agent) 20 Oxidized starch 8 Synthetic latex 8 The electron donating color forming compound used in each Example is shown below. Indicated. Example 1: 3-N, N-diethylamino-7-N-cyclohexyl-N-phenylaminofluoran (compound of Exemplified Compound No. 2) Example 2: 3-N, N-di-n-butylamino-7 -N
-Cyclohexyl-N-phenylaminofluoran (compound of Exemplified Compound No. 4) Example 3: 3-N-methyl-N-isobutylamino-7
-N-cyclohexyl-N-phenylaminofluoran (compound of Exemplified Compound No. 26) Example 4: 3-N-ethyl-N- (2'-ethoxyethyl) amino-7-N-cyclohexyl-N-phenylamino Example 5: 3-N-isobutyl-N- (2′-methoxyethyl) amino-7-N-clohexyl-N-phenylaminofluoran (Compound of Exemplified Compound No. 45) Example 6: 3-Nn-propyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluoran (compound of Exemplified Compound No. 54)

[Evaluation Method of Pressure-Sensitive Recording Paper] (Light resistance test of upper sheet)
With respect to the microcapsule surface of the sheet, the color change of each microcapsule surface before and after irradiation with sunlight for 2 hours is examined. Further, the microcapsule surface of the upper (CB) sheet is irradiated with sunlight before and after exposure to sunlight for 2 hours, and then the upper (CB) sheet and the lower (CF) paper are overlapped so as to face each other and pressurized. A color image is formed by passing through a roll, and the color tone of the color image is visually observed. (Lightfastness test of color-developed image) The upper (CB) sheet and the lower (CF) paper of the pressure-sensitive recording paper are overlapped, and a color image is formed by passing through a pressure roll, and the light stability of the color image is obtained. Find out. The color image formed on each lower sheet is irradiated with sunlight for 5 hours and 10 hours, and the color tone of the color image is visually observed.

COMPARATIVE EXAMPLE 1 The procedure described in Examples was followed, except that 3-N, N-diethylamino-7-N, N-dibenzylaminofluoran was used as the electron-donating color-forming compound. CB)
A sheet and a lower (CF) sheet were prepared and evaluated in the same manner. The results are shown in Tables 3 and 4.

[0068]

[Table 6] As is apparent from Table 3, the pressure-sensitive recording material using the fluoran compound represented by the general formula (1) as the electron-donating color-forming compound is compared with the pressure-sensitive recording material using the existing fluoran compound. Thus, it was found that the light stability of the microcapsule surface was very good, and that the light stability in the microcapsule was very good.

[0069]

[Table 7] As is clear from Table 4, the pressure-sensitive recording material using the fluoran compound represented by the general formula (1) as the electron-donating color-forming compound is compared with the existing pressure-sensitive recording material using the fluoran compound. As a result, it was found that the light stability of the color image was very excellent.

Example 7 Pressure-Sensitive Recording Material As an electron-donating color-forming compound, 3-N, N-di-n-
Butylamino-6-methyl-7-N-cyclohexyl-
Using N-phenylaminofluoran (compound of Exemplified Compound No. 67), an upper (CB) sheet and a lower (CF) sheet were produced by the above-described method for producing a pressure-sensitive recording material.
When the microcapsule-coated surface of the CB sheet and the developer-coated surface of the CF sheet were overlapped with each other so as to face each other, and pressure writing was performed, a vermilion color image was obtained on the developer-coated surface.
The light resistance, wet heat resistance and NOx resistance of this color image were excellent, and it was a practically useful pressure-sensitive recording material.

Example 8 Pressure-sensitive recording material As an electron-donating color-forming compound, 70% by weight of 3-N, N-diethylamino-7-N-cyclohexyl-N-phenylaminofluoran and 3-N, N-diethylamino-
Using a mixture of 30% by weight of 6-methyl-7-chlorofluorane, the above method for producing a pressure-sensitive recording material was applied to the above method (CB).
A sheet and a lower (CF) sheet were prepared. When the microcapsule-coated surface of the CB sheet and the developer-coated surface of the CF sheet were overlapped so as to be opposed to each other, and pressure writing was performed, a black color image was obtained on the developer-coated surface. The light resistance, moisture heat resistance and NO _x resistance of this color image are excellent,
It was a practically useful pressure-sensitive recording material.

Example 9 Thermosensitive recording material 100 g of solution A and 250 of solution B prepared by the following preparation method
g, 250 g of each dispersion of liquid C and 23 g of 30% paraffin wax, and apply the mixture to a high-quality paper so that the dry coating amount is 5.0 ± 0.5 g / m ^2, and then the mixture is dried. Recording paper was prepared. The obtained thermosensitive recording paper was evaluated by the following evaluation methods, and the results are shown in Table 5 (Table 8). As the electron-donating color-forming compound in Solution A, 3-N,
N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluoran was used. The color tone of the heat-sensitive recording paper was vermilion.

[Preparation Method of Dispersion] (Composition A) Electron-donating color-forming compound 10 g 10% aqueous solution of polyvinyl alcohol (Kuraray-117) 10 g Water 80 g Total 100 g (B composition) Electron-accepting compound (bisphenol A) 20 g Light calcium carbonate (Okutama Kogyo, TP-123) 40 g 10% polyvinyl alcohol aqueous solution (Kuraray-117) 60 g Water 130 g Total 250 g (C solution composition) Heat fusible compound (2-benzyloxynaphthalene) 20 g 10% Polyvinyl alcohol aqueous solution (Kuraray-117) 10 g Water 220 g Total 250 g The above-mentioned liquid A, liquid B and liquid C are each dispersed by a sand grinding mill so that the average particle diameter becomes 1.5 μ or less to prepare a dispersion liquid. [Evaluation method of thermal recording paper] (Coloring performance test for temperature) Each thermal recording paper was brought into contact with a metal block heated to each temperature for 5 seconds, and the color image density was measured using a Macbeth densitometer (TR-524 type). And measure. The larger the value, the deeper the color.

Comparative Example 2 In Example 9, 3-N, N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenyl used as the electron-donating color-forming compound in Solution A was used. Instead of aminofluoran, 3-N, N-diethylamino-6
A thermosensitive recording paper was prepared by the method described in Example 9 except that -methyl-7-chlorofluorane was used, and evaluated in the same manner. The results are shown in Table 5. The color tone of the heat-sensitive recording paper was vermilion.

[0075]

[Table 8] As is clear from Table 5, the heat-sensitive recording material of the present invention using the fluoran compound represented by the general formula (1) has an advantage in comparison with the heat-sensitive recording material using the existing fluoran compound.
It can be said that it is a heat-sensitive recording material that rapidly develops color at lower temperatures and is suitable for high-speed recording.

Example 10 In Example 9, 3-N, N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenyl used as the electron-donating color-forming compound in Solution A was used. Instead of aminofluoran, the compound of Exemplified Compound No. 2, 3-
N, N-diethylamino-7-N-cyclohexyl-N
A thermosensitive recording paper was prepared according to the method described in Example 9 except that -phenylaminofluoran was used. When this thermosensitive recording paper was brought into contact with a metal block heated to 130 ° C., a green color image was instantaneously obtained. The heat resistance, wet heat resistance and oil resistance of this color image are excellent, and it is a practically useful heat-sensitive recording material.

[0077]

According to the present invention, raw storage stability is good,
In addition, it has become possible to provide a recording material having good storage stability of a color image.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-247051 (JP, A) JP-A-2-57379 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/145 B41M 5/30 CAPLUS (STN) REGISTRY (STN)

Claims (6)

(57) [Claims] 1. A recording material utilizing color formation by contact of an electron-donating color-forming compound with an electron-accepting compound, wherein the electron-donating color-forming compound is a fluoran compound represented by the general formula (1): A recording material characterized by using at least one of the following. Embedded image (Wherein R ₁ and R ₂ represent an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 3 to 12 carbon atoms or a cycloalkyl group having 5 to 12 carbon atoms, and R ₁ and R ₂
May form a 5- or 6-membered heterocyclic ring with the N atom, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) 2. The electron-donating color-forming compound according to the formula (1), wherein R ₁ and R ₂ are an alkyl group having 1 to 6 carbon atoms, an alkoxyalkyl group having 3 to 5 carbon atoms or a cyclohexyl group, 2. The recording material according to claim 1, wherein R ₃ is a fluoran compound in which a hydrogen atom or a methyl group is present. 3. An electron-donating chromophoric compound which is a fluoran compound of the general formula (1) wherein -NR ₁ R ₂ is a pyrrolidino group, a piperidino group or a morpholino group, and R ₃ is a hydrogen atom or a methyl group. The recording material according to claim 1, wherein the recording material is provided. 4. The electron-donating color-forming compound is a fluoran compound in which R ₁ and R ₂ are an alkyl group having 1 to 6 carbon atoms and R ₃ is a hydrogen atom or a methyl group in the general formula (1). The recording material according to claim 1, wherein: 5. An electron-donating color-forming compound represented by formula (1), wherein R ₁ is an alkyl group having 1 to 6 carbon atoms;
₂ is an alkoxyalkyl group having 3 to 5 carbon atoms, R ₃
Is a fluoran compound wherein is a hydrogen atom or a methyl group. 6. An electron-donating color-forming compound represented by formula (1), wherein R ₁ is an alkyl group having 1 to 6 carbon atoms;
_2. The recording material according to claim 1, wherein ₂ is a cyclohexyl group, and R ₃ is a fluoran compound having a hydrogen atom or a methyl group.