JPH05278325A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material enhanced in raw preservability and the storage stability of a developed color image by providing a recording layer containing a specific fluorane compd. (electron donating color forming compd.) and an electron acceptive compd. on a support. CONSTITUTION:A predetermined amount of a fluorane compd. represented by formula I (wherein R1 and R2 are a 1-12C alkyl group, a 3-12C alkyl group or a 5-12C cycloalkyl group and R3 is a hydrogen atom or a 1-4C alkyl group) and a predetermined amount of an electron acceptive compd. such as a phenol derivative are ground along with a water-soluble binder by a ball mill to be dispersed in and mixed with the binder to prepare a coating solution for a recording layer. This coating solution is applied to a support such as paper, a plastic sheet or synthetic paper and dried to form the recording layer to obtain a thermal recording material. Pigment, a water-insoluble binder, a surfactant, an ultraviolet absorber or hindered phenol can be added to the recording layer if necessary.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a recording material. More specifically, it relates to a recording material having improved storage stability.

[0002]

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

However, when the compound is used as a color-forming compound for a recording material, for example, a pressure-sensitive recording material, the microcapsule surface (CB surface) is very unstable with respect to light, and it turns red when irradiated with light. In addition, there is a problem that after the light irradiation, even if the compound is brought into contact with the electron-accepting compound (developing agent), it no longer develops a green color. Furthermore, there is a drawback that the color image is also unstable to light. Also, for example, 3-
N, N-diethylamino-6-methyl-7-chlorofluorane is a chromogenic compound that develops a vermilion or red color, and is known to be useful as a chromogenic compound for recording materials (Japanese Patent Publication No. S45-45). -4701). However, when the compound is used as a recording material, for example, a color-forming compound for a heat-sensitive recording material, the color-forming sensitivity is low and a heat-sensitive recording material suitable for high-speed recording cannot be obtained, and further improvement is strongly desired. It is the current situation.

[0004]

In view of the above-mentioned problems, an object of the present invention is to provide a recording material having improved raw storability and storage stability of a color image.

[0005]

The present inventors have arrived at the present invention as a result of extensive studies on recording materials, particularly electron donative color forming compounds. That is, the present invention relates to a recording material utilizing color formation by contact between an electron-donating color forming compound and an electron-accepting compound, wherein the fluorane represented by the general formula (1) or (Chem. 2) is used as the electron-donating color forming compound. The present invention relates to a recording material using at least one compound.

[0006]

[Chemical 2] (In the formula, 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 , R ₂
May form a 5-membered or 6-membered heterocyclic ring with N atom, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

Further, the fluorane compound represented by the general formula (1) used as the electron-donating color-forming compound has a R ₁ and R ₂ alkyl group having 1 to 6 carbon atoms and an alkoxyalkyl group having 3 to 5 carbon atoms. or cyclohexyl group, fluoran compounds R ₃ is a hydrogen atom or a methyl group, -NR ₁ R ₂ is pyrrolidino, piperidino group or morpholino group, fluoran compounds R ₃ is a hydrogen atom or a methyl radical, R Fluoran compounds in which ₁ and R ₂ are alkyl groups having 1 to 6 carbon atoms, R ₃ is a hydrogen atom or a methyl group, R ₁ is an alkyl group having 1 to 6 carbon atoms, and R ₂ is 3 to 3 carbon atoms.
5 is an alkoxyalkyl group, 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 which 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 thereof include nonyl group, n-decyl group, n-undecyl group, n-dodecyl group and the like. In particular, methyl group, ethyl group,
An alkyl group having 1 to 6 carbon atoms such as an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, an n-pentyl group, an isopentyl group and an n-hexyl group is preferable.

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 Examples thereof include -n-hexyloxypropyl group. In particular, 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 preferable. Further, R ₁ and R ₂ have 5 carbon atoms
When the cycloalkyl group of 1 to 12 is represented, examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group. A cyclohexyl group is particularly preferred.

In the compound represented by the general formula (1),
When R ₁ and R ₂ together with the N atom form a 5-membered or 6-membered heterocycle, preferred examples of the 5-membered or 6-membered heterocycle include, for example, pyrrolidino group, piperidino group and morpholino group. Groups 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, particularly a hydrogen atom,
A methyl group is preferred.

The following compounds may be mentioned as specific examples of the compound represented by the general formula (1) according to the present invention, 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-phenylaminofluorane 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-phenylaminofluorane 7.3-N, N-di-isopentylamino-7-N-cyclohexyl-N-phenylaminofluorane 8.3-N , N-di-n-hexylamino-7-N-cyclohexyl-N-phenylaminofluorane 9.3-N, N-di-n-heptylamino-7-N-cyclohexyl-N-phenylaminofluorane 10 .3-N, N-Di-n-octylamino-7-N-cyclohexyl-N-phenylaminofluorane

11.3-N, N-Di-n-nonylamino-7-N-cyclohexyl-N-phenylaminofluorane 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-phenylaminofluorane 15.3-N, N-di- (2'-methoxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluorane 16.3-N, N-di- (2'-ethoxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluorane 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-phenylaminofluorane 20.3-piperidino-7-N-cyclohexyl-N-phenylaminofluorane 21.3-morpholino-7-N-cyclohexyl-N-phenylaminofluorane 22.3 -N-methyl-N-ethylamino-7-N-cyclohexyl-N-phenylaminofluorane 23.3-N-methyl-N-n-propylamino-7-N-cyclohexyl-N-phenylaminofluorane 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-phenylaminofluorane 27.3-N-methyl-N-sec-butylamino-7-N-cyclohexyl-N -Phenylaminofluorane 28.3-N-ethyl-N-n-propylamino-7-N-cyclohexyl- -N-phenylaminofluorane 29.3-N-ethyl-N-isopropylamino-7-N- Cyclohexyl-N-phenylaminofluorane 30.3-N-ethyl-N-n-butylamino-7-N-cyclohexyl-N-phenylaminofluorane 31.3-N-ethyl-N-isobutylamino-7- N-cyclohexyl-N-phenylaminofluorane 32.3-N-ethyl-N-sec-butylamino-7-N-cycl Lohexyl-N-phenylaminofluorane 33.3-Nn-propyl-N-isopropylamino-7-N-cyclohexyl-N-phenylaminofluorane 34.3-Nn-propyl-Nn- Butylamino-7-N-cyclohexyl-N-phenylaminofluorane 35.3-N-n-propyl-N-isobutylamino-7-N-cyclohexyl-N-phenylaminofluorane 36.3-N- n-Propyl-N-sec-butylamino-7-N-cyclohexyl-N-phenylaminofluorane 37.3-N-isopropyl-N-n-butylamino-7-N-cyclohexyl-N-phenylamino Fluoran 38.3-N-isopropyl-N-isobutylamino-7-N-cyclohexyl-N-phenylaminofluorane 39.3-N-n-butyl-N-isobutylamino-7-N-cyclohexyl-N-phenylaminofluorane 40.3-N-methyl-N-n-pentylamino-7-N-cyclohexyl-N- Phenylaminofluorane

41.3-N-ethyl-N-isopentylamino-7-N-cyclohexyl-N-phenylaminofluorane 42.3-N-ethyl-Nn-hexylamino-7-N-cyclohexyl- N-phenylaminofluorane 43.3-N-ethyl-Nn-octylamino-7-N-cyclohexyl-N-phenylaminofluorane 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-phenylaminofluorane 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-phenylaminofluorane 48.3-N-ethyl-N- (3'-methoxypropyl) amino- 7-N-Cyclohexyl-N-phenylaminofluorane 49.3-N-ethyl-N- (3'-ethoxypropyl) amino-7-N-cyclohexyl-N-phenylaminofluorane 50.3-N -Ethyl-N- (3'-n-hexyloxypropyl) amino-7-N-cyclohexyl-N-phenylaminofluorane 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-phenylaminofluorane 54.3-N-n-propyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylamino Fluoran 55.3-N-n-butyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluorane

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-n-hexyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluorane 59.3-Nn-decyl-N-cyclohexylamino- 7-N-cyclohexyl-N-phenylaminofluorane 60.3-N-ethyl-N-cycloheptylamino-7-N-cyclohexyl-N-phenylaminofluorane 61.3-N-ethyl-N-cyclo Octylamino-7-N-cyclohexyl-N-phenylaminofluorane 62.3-N-ethyl-N- Cyclodecylamino-7-N-cyclohexyl-N-phenylaminofluorane 63.3-N-ethyl-N-cyclododecylamino-7-N-cyclohexyl-N-phenylaminofluorane 64.3-N, N- Dimethylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 65.3-N, N-diethylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 66.3-N , N-di-n-propylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 67.3-N, N-di-n-butylamino-6-methyl-7-N- Cyclohexyl-N-phenylaminofluorane 68.3-N, N-di-isobutylamino-6-methyl-7-N-cyclohexyl-N- Phenylaminofluorane 69.3-N, N-di-n-pentylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 70.3-N, N-di-isopentylamino- 6-methyl-7-N-cyclohexyl-N-phenylaminofluorane

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

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

101.3-N-isopropyl-N-isobutylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 102.3-N-n-butyl-N-isobutylamino-6-methyl -7-N-Cyclohexyl-N-phenylaminofluorane 103.3-N-methyl-N-n-pentylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 104.3- N-Ethyl-N-isopentylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 105.3-N-ethyl-Nn-hexylamino-6-methyl-7-N- Cyclohexyl-N-phenylaminofluorane 106.3-N-ethyl-Nn-octylamino-6-methyl-7-N-cyclohexyl -N-phenylaminofluorane 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-phenylaminofluorane 110.3-N-methyl-N- (2'-n-decyloxyethyl) amino-6-methyl-7- N-cyclohexyl-N-phenylaminofluorane 111.3-N-ethyl-N- (3'-methoxypropyl) amino-6-methyl-7-N-cyclohexyl-N -Phenylaminofluorane 112.3-N-ethyl-N- (3'-ethoxypropyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 113.3-N-ethyl-N- (3′-n-Hexyloxypropyl) amino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane 114.3-N-ethyl-N-cyclopentylamino-6-methyl-7-N-si Chlohexyl-N-phenylaminofluorane 115.3-N-methyl-N-cyclohexylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane

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

The fluorane 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) (chemical formula 3) and a general formula (3) ( The N-cyclohexyldiphenylamine derivative represented by Chemical formula 4) is preferably added in the presence of a dehydration condensation agent such as concentrated sulfuric acid, concentrated sulfuric acid to which fuming sulfuric acid is added, polyphosphoric acid, phosphorus pentoxide, and anhydrous aluminum chloride. It can be produced by reacting in concentrated sulfuric acid, discharging to ice water after the reaction, and subjecting the obtained cake to alkali treatment.

[0021]

[Chemical 3] (In the formula, R ₁ and R ₂ have the same meanings as in the case of the general formula (1))

[0022]

[Chemical 4] (In the formula, 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 at a temperature range of about 0 to 100 ° C. for several hours to several tens hours. The reaction temperature is particularly preferably in the range of about 0 to 50 ° C. when the reaction is carried out in concentrated sulfuric acid. Since the reaction time depends on the reaction temperature, it is necessary to carry out a sufficient time. The alkali treatment carried out after the dehydration condensation is preferably carried out in a temperature range of about 0 to 100 ° C., preferably about 40 to 100 ° C., with a pH of about 9 to 13 using an aqueous solution of potassium hydroxide, sodium hydroxide or the like. Although the reaction time depends on the reaction temperature, it usually takes several tens of minutes to several hours. The alkali treatment may be carried out in the coexistence of an organic solvent such as benzene, toluene, xylene and chlorobenzene, and in this case, the fluorane compound formed can be extracted into the organic solvent. The fluoran compound thus produced can be purified by a known purification method such as recrystallization or column chromatography, if necessary, to increase its 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 effect of the present invention is not impaired,
It is also possible to use various known electron-donating color-forming compounds in mixture with the fluorane compound represented by the general formula (1). The use ratio of the fluorane compound represented by the general formula (1) and various known electron donative color forming compounds varies depending on the kind 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 40% by weight in order to adjust the color tone of the color image. % Or more is particularly preferable.

Examples of the electron-donating color-forming compound other than the fluorane compound represented by the general formula (1) used in the present invention include triarylmethane compounds, diarylmethane compounds, rhodamine-lactam compounds, and fluorane compounds. , 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-methylpyrrol-3-yl) -6-dimethylaminophthalide, 3,3-bis [2,2-bis (4-
Dimethylaminophenyl) ethenyl] -4,5,6,7
-Such as tetrachlorophthalide.

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

Examples of fluorane compounds include 3,6-dimethoxyfluorane, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, and 3-diethylamino-7-methoxyfluorane. Diethylamino-7-chlorofluorane, 3-
Diethylamino-6-methyl-7-chlorofluorane,
3-diethylamino-6,7-dimethylfluorane, 3
-N-cyclohexyl-N-n-butylamino-7-methylfluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-di-n −
Hexylaminofluorane, 3-diethylamino-7-
Anilinofluorane, 3-diethylamino-7- (2-
Chloroanilino) fluorane, 3-diethylamino-7
-(3-chloroanilino) fluorane, 3-diethylamino-7- (2,3-dichloroanilino) fluorane,
3-diethylamino-7- (3-trifluoromethylanilino) fluorane, 3-di-n-butylamino-7-
(2-chloroanilino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-di-n
-Butylamino-6-chloro-7-anilinofluorane,

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

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

3-N-2'-methoxyethyl-N-methylamino-6-methyl-7-anilinofluorane, 3-
N-2'-methoxyethyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-2'-ethoxyethyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-2'-ethoxyethyl-N-ethylamino-6-methyl-7-anilinofluorane, 3
-N-3'-methoxypropyl-N-methylamino-6
-Methyl-7-anilinofluorane, 3-N-3'-ethoxypropyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-2'-methoxyethyl-N
-Isobutylamino-6-methyl-7-anilinofluorane, 3-N-2'-tetrahydrofurfuryl-N-ethylamino-6-methyl-7-anilinofluorane, 3
-N- (4'-methylphenyl) -N-ethylamino-6
-Methyl-7-anilinofluorane, 3-diethylamino-6-ethyl-7-anilinofluorane, 3-di-ethylamino-6-methyl-7- (2 ', 6'-dimethylphenylamino) fluorane , 3-di-n-butylamino-6-methyl-7- (2 ', 6'-dimethylphenylamino) fluorane, 3-di-n-butylamino-7-
(2 ', 6'-dimethylphenylamino) fluorane,
2,2-bis [4 '-(3-N-cyclohexyl-N-
Methylamino-6-methylfluorane) -7-ylaminophenyl] propane and the like.

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 and 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 and the like.

As the spiro compound, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-
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 '
-Fluorene) -3-one, 3 ', 6'-bisdiethylamino-7-diethylamino-2-methylspiro (1,
3-benzoxazine-4,9'-fluorene) and the like. These electron-donating color forming compounds may be used alone or in admixture of two or more kinds for the purpose of adjusting the color tone of a color 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 a metal salt or complex thereof, a urea derivative, or an inorganic electron-accepting compound such as acid clay. Can be mentioned. 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 [alias, 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- Propoxydiphenyl sulfone, 4-hydroxy-4'-
Isopropoxydiphenyl sulfone, 4-hydroxy-4′-n-butoxydiphenyl sulfone, 3,4-
Dihydroxy-4'-methyldiphenyl sulfone, 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,
A phenol derivative 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, 2-hydroxy-3-naphthoic acid, 2-hydroxy-6-naphthoic acid, phthalic acid monobenzyl ester, phthalic acid monophenyl ester, and other organic acids or metals thereof. Salts (eg, metal salts of nickel, zinc, aluminum, calcium, etc.), zinc thiocyanate antipyrine complex, complexes such as molybdate acetylacetone complex, phenylthiourea, di (3-trifluoromethylphenyl) thiourea, 1,4- Preferred are 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. 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 energization heat-sensitive recording material, a light-sensitive pressure-sensitive recording material, and a heat-sensitive recording transfer recording material, preferably a heat-sensitive recording material, A pressure-sensitive recording material, an electrically heat-sensitive recording material and a light and pressure-sensitive recording material, particularly preferably a heat-sensitive recording material and a pressure-sensitive recording material. Examples of pressure-sensitive recording materials include US Pat. Nos. 2,505,470 and 2,505,471.
No. 2505489, No. 2548366, No. 27
No. 12507, No. 2730456, No. 2730457
No. 3, No. 3103404, No. 3418250, No. 39
There are various forms described in No. 24027, No. 4010038, etc., and the present invention can be applied to pressure-sensitive recording materials of these various forms. In general,
It comprises at least one pair of sheets containing separately an electron-donating color-forming compound and an electron-accepting compound on a suitable support such as paper, plastic sheet, synthetic paper and the like.

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

Of course, a so-called intermediate sheet in which the above-mentioned electron-donating color-forming compound dispersion liquid or the capsule dispersion liquid is coated on one surface of the support and the electron-accepting compound dispersion liquid is coated on the other surface, Is a mixed dispersion of a capsule dispersion of an electron-donating color forming compound and a dispersion of an electron-accepting compound or a capsule dispersion of an electron-donating color-forming compound on the same surface of the support, and A form such as a so-called single copying sheet in which an electron-donating color-forming compound capsule and an electron-accepting compound are made to coexist on the same surface of a support by applying a dispersion liquid is also included. The use ratio of the electron-donating color forming compound and the electron-accepting compound is various conditions such as a desired coating amount, the form of the pressure-sensitive recording material, the encapsulation method, the composition of the coating liquid including various auxiliary agents, and the coating method. It depends on the condition, so it may be selected appropriately. It is easy for a person skilled in the art to determine this usage amount.

As the heat-sensitive recording material, for example, Japanese Patent Publication No.
No. 4-3680, No. 44-27880, and No. 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 these various forms of heat-sensitive recording materials.
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 50 to 100 parts by weight of the electron-donating color-forming compound.
It is 700 parts by weight, preferably 100 to 500 parts by weight. In addition to the electron-donating color-forming compound and the electron-accepting compound that are directly involved in the color development, a heat-fusible compound (melting point of about 70 to 150) is used for the purpose of improving the color-developing sensitivity.
C., more preferably a compound having a melting point of about 80 to 130.degree. C.) is further 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, the electron-donating color forming compound 10 is usually used.
10 to 700 parts by weight of the heat-fusible compound with respect to 0 parts by weight,
It is preferable to use 20 to 500 parts by weight.

Examples of such heat-fusible compounds include stearic acid amide, palmitic acid amide, stearyl urea, N-ethylcarbazole, nitrogen-containing compounds such as 4-methoxydiphenylamine, 4-benzyloxybenzoic acid benzyl ester. , 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 terephthalic acid dibenzyl ester, 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, 1 , 2-diphenoxybenzene, 1,4-bis (3'-methylphenyloxymethyl) benzene, 4-chlorobenzyloxy- (4'-
Examples thereof include 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, etc. are each added in a water-soluble binder in a ball mill,
A coating liquid can be prepared by pulverizing and dispersing to a particle size of 3 μm or less, preferably 1.5 μm or less by a means such as a sand mill and mixing them. As the 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 derivative, casein, gelatin, methyl cellulose, carboxymethyl cellulose,
Examples thereof include gum arabic and carboxyl group-modified polyvinyl alcohol.

Further, in the recording layer of the heat-sensitive recording material of the present invention, a pigment, a water-insoluble binder, a metal soap, a wax, a surfactant, an ultraviolet absorber, a hindered phenol, an antifoaming agent, etc. may be added, if necessary. Added. As the pigment, zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, titanium oxide, talc, wax, 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 ester. Examples of the surfactant include sulfosuccinic acid-based alkali metal salts and fluorine-containing surfactants.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, and benzotriazolylphenol derivatives.

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, an air knife coater on a support,
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. As the support, paper, plastic sheet, synthetic paper or the like is used. If necessary, a protective layer may be provided on the front surface and / or the back surface of the thermosensitive recording layer, or an undercoat layer may be provided between the support and the thermosensitive recording layer. Various known techniques in the manufacturing method of the recording material can be applied.

An electrothermal recording material is disclosed in, for example, JP-A-49 / 49
It is manufactured by the method described in JP-A-11344, JP-A-50-48390 and the like. Generally, a conductive compound,
An electron-donating color-forming compound, an electron-accepting compound and a coating liquid in which a binder is dispersed are applied onto a suitable support such as paper, or a conductive compound is applied onto the support to form a conductive layer. It is manufactured by applying a coating liquid in which an electron-donating color-forming compound and an electron-accepting compound are dispersed in a binder. The sensitivity can be improved by using the above-mentioned heat-fusible compound in combination.

The light and pressure sensitive recording material is described in, for example, JP-A-57 / 57.
It is manufactured by the method described in JP-A-179836. Generally, a photopolymerization initiator such as silver bromide, silver behenate, Michler's ketone, a benzoin derivative or a benzophenone derivative is crosslinked with a polyfunctional monomer such as a polyallyl compound, poly (meth) acrylate or poly (meth) acrylamide. An agent, an electron-donating color-forming compound, and, if necessary, a solvent together enclosed in a synthetic resin capsule such as polyether urethane or polyurea,
And at least a pair of sheets separately containing an electron-accepting compound. After imagewise exposure, the difference between curing and uncuring of the capsule by light is used to develop the color by contacting with the electron-accepting compound coated on the support by using the electron-donating color-forming compound in the unexposed area. It is what makes them.

[0050]

EXAMPLES The present invention will be described in more detail below 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 3-5.5 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)
Wherein R ₃ is a hydrogen atom and R ₄ is a methyl group,
Melting point 89-91 ° C.] 24 g at the same temperature, 10-25
The mixture was stirred at 0 ° C for 30 hours. The reaction mixture was discharged into 1000 ml of ice water, and the precipitated solid was collected and washed with water, and the wet cake was added to 10% NaOH water (400 ml), and toluene (500 ml) was further added, and the mixture was heated at 60 to 70 ° C. for 3 hours. It was stirred. The toluene layer was separated, washed with warm water until it became neutral, the toluene layer was separated, and the toluene was distilled off under reduced pressure. 200 ml of methanol was added to the residue, and the mixture was allowed to stand at room temperature, and the precipitated crystals were separated by filtration. Then, the crystals were recrystallized from isopropanol to give almost the desired crystals of 3-N, N-diethylamino-7-
30 g of N-cyclohexyl-N-phenylaminofluorane compound was obtained. Melting point 152-154 ° C. This fluorane compound is 4% in 95% acetic acid aqueous solution.
Absorption maximums were shown at 40 nm, 470 nm and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and rapidly developed a green color on silica gel.

Production Example 2 Production of Compound of Exemplified Compound No. 4 In Production Example 1, 2- (4′-N was used instead of 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. , N-di-n-butylamino-2 '
-Hydroxybenzoyl) benzoic acid was used, and a 3-N, N-di-n-butylamino-7-N-cyclohexyl-N-phenylaminofluorane compound was produced according to the method described in Production Example 1. .. Melting point 167-169 [deg.] C. This fluorane compound is 4% in 95% acetic acid aqueous solution.
Absorption maximums were shown at 40 nm, 470 nm and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and rapidly developed a green color on silica gel.

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

Production Example 4 Production of Compound of Exemplified Compound No. 44 In Production Example 1, 2- [4′-N was used instead of 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. 3-N- (2'-ethoxyethyl) amino-2'-hydroxybenzoyl] benzoic acid was used according to the method described in Preparation Example 1 except that 3-N was used.
-Ethyl-N- (2'-ethoxyethyl) amino-7-
An N-cyclohexyl-N-phenylaminofluorane compound was prepared. Melting point 117 to 120 ° C. This fluorane compound is 4% in 95% acetic acid aqueous solution.
Absorption maximums were shown at 40 nm, 470 nm and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and rapidly 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 used instead of 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. -Isobutyl-N- (2'-methoxyethyl) amino-2'-hydroxybenzoyl] benzoic acid was used according to the method described in Preparation Example 1 except that 3
A -N-isobutyl-N- (2'-methoxyethyl) amino-7-N-cyclohexyl-N-phenylaminofluorane compound was prepared. Melting point 185 to 187 ° C. This fluorane compound is 4% in 95% acetic acid aqueous solution.
Absorption maximums were shown at 40 nm, 470 nm and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and rapidly developed a green color on silica gel.

Production Example 6 Production of Compound of Exemplified Compound No. 54 In Production Example 1, 2- (4′-N was replaced with 2- (4′-N, N-diethylamino-2′-hydroxybenzoyl) benzoic acid. -N-Propyl-N-cyclohexylamino-2'-hydroxybenzoyl) benzoic acid was used according to the method described in Preparation Example 1 except that 3-N-n was used.
A -propyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluorane compound was prepared. Melting point 229-231 ° C. This fluorane compound is 4% in 95% acetic acid aqueous solution.
Absorption maximums were shown at 40 nm, 470 nm and 625 nm. The toluene solution of this fluoran compound was colorless and transparent, and rapidly 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 the benzoic acid derivative was used. The color hues of each fluoran compound on silica gel are also shown in the table.

[0057]

[Table 1]

[0058]

[Table 2]

Production Example 18 Production of Compound of Exemplified Compound No. 67 25.5 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. And then dissolved in N- (4-methoxy-2-methylphenyl) -N-cyclohexyl-N-phenylamine [a compound of the general formula (3) in which R ₃ is a methyl group, R ₄ is a methyl group, melting point 118 to 120 ° C] 29 g was added at the same temperature, and the mixture was stirred at 10 to 25 ° C for 30 hours. The reaction mixture was discharged into 1000 ml of ice water, and the precipitated solid was collected, washed with water, added with 10% NaOH water (400 ml), and added with 500 ml of toluene, and then stirred at 60 to 70 ° C for 3 hours. did. The toluene layer was separated, washed with warm water until it became neutral, the toluene layer was separated, and the toluene was distilled off under reduced pressure. Methanol 2 in the residue
After adding 00 ml and leaving it at room temperature, the precipitated crystals were separated by filtration. Further, the crystals were recrystallized from n-butanol to give almost the desired crystals of 3-N, N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofur. 41 g of an oran compound was obtained. Melting point 197-199 ° C. This fluorane compound is 49% in 95% acetic acid aqueous solution.
It showed an absorption maximum at 5 nm. The toluene solution of this fluoran compound was colorless and transparent, and rapidly developed a vermillion color on silica gel.

Production Examples 19-30 Instead of 2- (4'-N, N-di-n-butylamino-2'-hydroxybenzoyl) benzoic acid in Production Example 18, Table 2 (Table 3, Table 3) was used. 4, each fluorane 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 prepared by the following pressure sensitive recording material preparation method, and evaluated by the following evaluation methods. The results are shown in Table 3 (Table 6) and Table 4 (Table 7). [Method for producing 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-based solvent (5% by weight of an electron-donating color-forming compound) (SAS-2 manufactured by Nippon Petrochemical Co., Ltd.)
96) After mixing 200 g and emulsifying with a homomixer,
60 g of a methylol melamine aqueous solution (manufactured by Mitsui Toatsu Chemicals, Euramine T-30) having a solid content of 50% is added, and the mixture is stirred and held at 55 ° C. for 3 hours to obtain a microcapsule dispersion liquid having an average particle diameter of 5.0 μm. To 100 g of this dispersion, 4.0 g of wheat starch granules, 20 g of 20% oxidized starch paste and 11 parts of water.
6 g was added to disperse and coated on a paper having a basis weight of 40 g / m ^{2 so} that the coating amount was 5 g / m ² in terms of solid content.
Get a sheet. On the other hand, zinc salt of a co-condensation resin of salicylic acid and styrene was used as an electron-accepting compound (developing agent). 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.
Is coated on the above paper at a dry coating amount of 5.5 g / m ² to prepare a lower (CF) sheet.

Composition of water-based paint 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 as follows. Indicated. Example 1: 3-N, N-diethylamino-7-N-cyclohexyl-N-phenylaminofluorane (Compound of Exemplified Compound No. 2) Example 2: 3-N, N-di-n-butylamino-7 -N
-Cyclohexyl-N-phenylaminofluorane (Compound of Exemplified Compound No. 4) Example 3: 3-N-methyl-N-isobutylamino-7
-N-Cyclohexyl-N-phenylaminofluorane (Compound of Exemplified Compound No. 26) Example 4: 3-N-ethyl-N- (2'-ethoxyethyl) amino-7-N-cyclohexyl-N-phenylamino Fluoran (Compound of Exemplified Compound No. 44) Example 5: 3-N-isobutyl-N- (2'-methoxyethyl) amino-7-N chlorhexyl-N-phenylaminofluorane (Compound of Exemplified Compound No. 45) Example 6: 3-N-n-propyl-N-cyclohexylamino-7-N-cyclohexyl-N-phenylaminofluorane (Compound of Exemplified Compound No. 54)

[Evaluation Method of Pressure Sensitive Recording Paper] (Light Resistance Test of Upper Sheet) Upper Pressure Sensitive Recording Paper (CB)
Regarding the microcapsule surface of the sheet, the change in color of each microcapsule surface before sunlight irradiation and after 2 hours of sunlight irradiation is examined. Furthermore, the microcapsule surface of the upper (CB) sheet is irradiated with sunlight for 2 hours and after the sunlight is irradiated for 2 hours, the upper (CB) sheet and the lower (CF) sheet are superposed so as to face each other, and pressed. A color image is formed by passing through the roll, and the color tone of the color image is visually observed. (Lightfastness test of colored image) The upper (CB) sheet and the lower (CF) sheet of pressure-sensitive recording paper are superposed and passed through a pressure roll to form a colored image, and the light stability of the colored image is formed. Find out. The color tone of the color image formed on each lower sheet is visually observed after irradiation with sunlight for 5 hours and 10 hours.

Comparative Example 1 The same procedure as described in Example 1 was repeated except that 3-N, N-diethylamino-7-N, N-dibenzylaminofluorane 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 clear from Table 3, the pressure-sensitive recording material using the fluorane compound represented by the general formula (1) as the electron-donating color-forming compound is better than the existing pressure-sensitive recording material using the fluorane compound. It was found that the light stability of the microcapsule surface was very good, and the light stability in the microcapsule was also very good.

[0069]

[Table 7] As is clear from Table 4, the pressure-sensitive recording material using the fluorane compound represented by the general formula (1) as the electron-donating color-forming compound is better than the existing pressure-sensitive recording material using the fluorane compound. 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-phenylaminofluorane (Compound of Exemplified Compound No. 67), an upper (CB) sheet and a lower (CF) sheet were produced by the above-mentioned production method of the pressure-sensitive recording material.
When the microcapsule-coated surface of the CB sheet and the developer-coated surface of the CF sheet were superposed so as to face each other and pressure-written, a vermilion colored image was obtained on the developer-coated surface.
This color image was excellent in light resistance, wet heat resistance and NOx resistance, and was a practically useful pressure-sensitive recording material.

Example 8 Pressure Sensitive Recording Material 70% by weight of 3-N, N-diethylamino-7-N-cyclohexyl-N-phenylaminofluorane, 3-N, N-diethylamino-as an electron-donating color-forming compound.
6-Methyl-7-chlorofluorane A mixture of 30% by weight was used in the above method for producing a pressure-sensitive recording material.
A sheet and a bottom (CF) sheet were prepared. When the microcapsule-coated surface of the CB sheet and the developer-coated surface of the CF sheet were superposed so as to face each other and pressure-written, a black color image was obtained on the developer-coated surface. This color image has excellent light resistance, wet heat resistance and NO _x resistance,
It was a practically useful pressure-sensitive recording material.

Example 9 Thermosensitive recording material 100 g of solution A and 250 solution B prepared by the following preparation method
g, each dispersion of C liquid 250 g, and 23 g of 30% paraffin wax were mixed, and this was coated on a high-quality paper so that the dry coating amount was 5.0 ± 0.5 g / m ² , dried, and heat-sensitive. A recording paper was prepared. The obtained thermal 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 the liquid A, 3-N,
N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenylaminofluorane was used. The color tone of the thermosensitive recording paper was vermilion.

[Preparation Method of Dispersion] (Liquid A Composition) Electron-donating color-forming compound 10 g 10% aqueous polyvinyl alcohol solution (Kuraray-117) 10 g Water 80 g Total 100 g (Liquid B composition) Electron-accepting compound (bisphenol A) ) 20 g Light calcium carbonate (Okutama industry, TP-123) 40 g 10% Polyvinyl alcohol aqueous solution (Kuraray-117) 60 g Water 130 g Total 250 g (C liquid 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 liquids A, B, and C are dispersed by a sand grinding mill so that the average particle diameter is 1.5 μm or less, to prepare a dispersion liquid. [Evaluation Method of Thermal Recording Paper] (Coloring Performance Test against 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). To measure. The larger the value is, the deeper the color is developed.

Comparative Example 2 3-N, N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenyl used as the electron-donating color-forming compound in solution A in Example 9 3-N, N-diethylamino-6 instead of aminofluorane
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 thermosensitive recording paper was vermilion.

[0075]

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

Example 10 3-N, N-di-n-butylamino-6-methyl-7-N-cyclohexyl-N-phenyl used as the electron-donating color-forming compound in solution A in Example 9 Instead of aminofluorane, 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 phenylaminofluorane was used. When this thermosensitive recording paper was brought into contact with a metal block heated to 130 ° C., a green colored image was instantaneously obtained. This color image is excellent in heat resistance, moist heat resistance and oil resistance and is a practically useful heat-sensitive recording material.

[0077]

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

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kayoshi Yoshikawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (6)

[Claims] 1. A recording material utilizing color formation by contact between an electron-donating color-forming compound and an electron-accepting compound, wherein the electron-donating color-forming compound is a fluoran compound represented by the general formula (1) A recording material comprising at least one of: [Chemical 1] (In the formula, 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 , R ₂
May form a 5-membered or 6-membered heterocyclic ring with 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, wherein in the general formula (1), 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, The recording material according to claim 1, wherein R ₃ is a fluorane compound in which a hydrogen atom or a methyl group is present. 3. An electron-donating color-forming compound is a fluoran compound represented by 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 present. 4. The electron-donating color-forming compound is a fluoran compound represented by the general formula (1), wherein 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. The recording material according to claim 1, wherein 5. An electron-donating color-forming compound, wherein R ₁ is an alkyl group having 1 to 6 carbon atoms, R _1
2 is an alkoxyalkyl group having 3 to 5 carbon atoms, and R ₃
The recording material according to claim 1, wherein is a fluoran compound in which is a hydrogen atom or a methyl group. 6. The electron-donating color-forming compound has the formula (1), wherein R ₁ is an alkyl group having 1 to 6 carbon atoms, and R is
The recording material according to claim 1, wherein ₂ is a cyclohexyl group, and R ₃ is a fluorane compound in which a hydrogen atom or a methyl group is present.