JP2003171368A - Cinnoline derivative compound, pigment and heat- sensitive recording material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new cinnoline derivative compound suitable as a diazo compound component for forming a pigment, or the like, the pigment produced by the reaction of the cinnoline derivative compound with a coupler compound, and a heat-sensitive recording material containing the cinnoline derivative compound and having high storage stability. <P>SOLUTION: The cinnoline derivative compound is expressed by formula (1) (R<SP>1</SP>to R<SP>4</SP>are each H, an alkyl, an aryl, OR<SP>5</SP>, SR<SP>6</SP>, NR<SP>7</SP>R<SP>8</SP>, COR<SP>10</SP>, a halogen atom or SO<SB>2</SB>R<SP>10</SP>; and B is H, COR<SP>10</SP>, SO<SB>2</SB>R<SP>11</SP>or POR<SP>12</SP>R<SP>13</SP>). The cinnoline derivative compound is preferably included in a microcapsule. This invention further provides the pigment produced by the reaction of the cinnoline compound with the coupler compound and the heat-sensitive recording material containing the cinnoline compound as a diazo compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a cinnoline derivative compound, a dye, and a heat-sensitive recording material, and more specifically,
As a diazo compound component, a novel cinnoline derivative compound that is suitably used for forming a dye, a dye formed by the reaction of the cinnoline derivative compound with a coupler compound, and the cinnoline derivative compound are contained, and excellent photofixability Thermal recording material.

[0002]

2. Description of the Related Art Diazo compounds are compounds having extremely high chemical activity, and easily react with a coupling component such as a phenol derivative or a compound having an active methylene group to form an azo dye, and also have photosensitivity. It has the property of decomposing upon irradiation with light and losing its activity. Therefore, diazo compounds have been used for a long time as an optical recording material represented by diazo copy (edited by The Photographic Society of Japan, "Basics of Photographic Engineering-
Non-silver salt photo edition- "Corona Publishing (1982) P89-P11
7, P182-P201).

Further, by utilizing the property of decomposing by light and losing activity, it has been applied to a recording material which is required to fix an image recently, and a typical example thereof is a diazo compound and a coupling component (coupler compound). A light-fixing type heat-sensitive recording material has been proposed which heats and reacts with an image signal to form an image, and then irradiates the light to fix the image (Koji Sato et al., The Institute of Image Electronics Engineers, Vol. 11, Vol. No. 4 (19
82) P290-296).

In general, the diazo compound has a very high activity, and the diazo compound gradually decomposes into heat even in a dark place to lose its reactivity. Therefore, when it is used as a recording material, the shelf life is short. there were. Further, the heat-sensitive recording material has a problem that after forming an image, discoloration occurs due to heat or chemicals.

Therefore, the characteristics of the heat-sensitive recording material can be utilized, and a highly stable diazo compound, a dye formed by the reaction of the diazo compound and a coupler compound, and a stable image formation containing the diazo compound are formed. There has been a demand for the development of a heat-sensitive recording material capable of achieving the above.

[0006]

SUMMARY OF THE INVENTION The present invention aims to solve the above-mentioned problems in the prior art and achieve the following objects, that is, the present invention forms a dye as a diazo compound component together with a coupler component. , A highly stable novel cinnoline derivative compound, a dye formed by the reaction of the cinnoline derivative compound with a coupler compound, and a thermosensitive recording containing the cinnoline derivative compound and having good raw storage stability Intended to provide material.

[0007]

Means for solving the above-mentioned problems are as follows. That is, <1> A cinnoline derivative compound represented by the following general formula (1).

[0008]

[Chemical 4]

In the general formula (1), R¹, R², R
³, And R^FourAre each independently a hydrogen atom, an alkyl group,
Reel base, -OR^Five, -SR⁶, -NR⁷R⁸, -CO
R^Ten, Halogen atom, -SO₂R^TenRepresents R^FiveAnd R⁶
Are a hydrogen atom, an alkyl group, an aryl group, and
Represents an acyl group. R⁷And R⁸Are independently hydrogen
Child, alkyl group, aryl group, acyl group, alkyl group
It represents a sulfonyl group and an arylsulfonyl group. Furthermore R
⁷And R⁸Are linked to each other by -O-, -S-, -SO ₂
-, -NR⁹Represents an alkylene group which may include-
You R⁹Is a hydrogen atom, an alkyl group, an aryl group, an acyl group
Group, alkylsulfonyl group, arylsulfonyl group,
Alkoxycarbonyl group, and aryloxycarboni
Represents a radical. R^TenIs a hydrogen atom, hydroxyl group, alkyl group,
Lucoxy group, aryloxy group, and -NR ⁷R⁸The table
You Where R⁷And R⁸Is the above R⁷And R⁸Same as
is there. B is a hydrogen atom, -COR^Ten, -SO₂R¹¹,-
POR¹²R¹³Represents R¹¹Is an alkyl group, aryl
Group, heterocyclic group, and -NR⁷R⁸Represents Where R⁷Over
And R⁸Is the above R⁷And R⁸Is the same as. R¹²And R
¹³Are each independently an alkyl group, an aryl group, an alkoxy group.
Represents a Si group and an aryloxy group.

<2> A dye characterized by being formed by reacting a cinnoline derivative compound represented by the following general formula (1) with a coupler compound.

[0011]

[Chemical 5]

In the general formula (1), R¹, R², R
³, And R^FourAre each independently a hydrogen atom, an alkyl group,
Reel base, -OR^Five, -SR⁶, -NR⁷R⁸, -CO
R^Ten, Halogen atom, -SO₂R^TenRepresents R^FiveAnd R⁶
Are a hydrogen atom, an alkyl group, an aryl group, and
Represents an acyl group. R⁷And R⁸Are independently hydrogen
Child, alkyl group, aryl group, acyl group, alkyl group
It represents a sulfonyl group and an arylsulfonyl group. Furthermore R
⁷And R⁸Are linked to each other by -O-, -S-, -SO ₂
-, -NR⁹Represents an alkylene group which may include-
You R⁹Is a hydrogen atom, an alkyl group, an aryl group, an acyl group
Group, alkylsulfonyl group, arylsulfonyl group,
Alkoxycarbonyl group, and aryloxycarboni
Represents a radical. R^TenIs a hydrogen atom, hydroxyl group, alkyl group,
Lucoxy group, aryloxy group, and -NR ⁷R⁸The table
You Where R⁷And R⁸Is the above R⁷And R⁸Same as
is there. B is a hydrogen atom, -COR^Ten, -SO₂R¹¹,-
POR¹²R¹³Represents R¹¹Is an alkyl group, aryl
Group, heterocyclic group, and -NR⁷R⁸Represents R¹²And R
¹³Are each independently an alkyl group, an aryl group, an alkoxy group.
Represents a Si group and an aryloxy group.

<3> A heat-sensitive recording material comprising a support and a heat-sensitive recording layer containing a diazo compound and a coupler compound which is colored by reacting with the diazo compound.
A heat-sensitive recording material comprising a cinnoline derivative compound represented by the following general formula (1) as the diazo compound.

[0014]

[Chemical 6]

In the general formula (1), R¹, R², R
³, And R^FourAre each independently a hydrogen atom, an alkyl group,
Reel base, -OR^Five, -SR⁶, -NR⁷R⁸, -CO
R^Ten, Halogen atom, -SO₂R^TenRepresents R^FiveAnd R⁶
Are a hydrogen atom, an alkyl group, an aryl group, and
Represents an acyl group. R⁷And R⁸Are independently hydrogen
Child, alkyl group, aryl group, acyl group, alkyl group
It represents a sulfonyl group and an arylsulfonyl group. Furthermore R
⁷And R⁸Are linked to each other by -O-, -S-, -SO ₂
-, -NR⁹Represents an alkylene group which may include-
You R⁹Is a hydrogen atom, an alkyl group, an aryl group, an acyl group
Group, alkylsulfonyl group, arylsulfonyl group,
Alkoxycarbonyl group, and aryloxycarboni
Represents a radical. R^TenIs a hydrogen atom, hydroxyl group, alkyl group,
Lucoxy group, aryloxy group, and -NR ⁷R⁸The table
You Where R⁷And R⁸Is the above R⁷And R⁸Same as
is there. B is a hydrogen atom, -COR^Ten, -SO₂R¹¹,-
POR¹²R¹³Represents R¹¹Is an alkyl group, aryl
Group, heterocyclic group, and -NR⁷R⁸Represents Where R⁷Over
And R⁸Is the above R⁷And R⁸Is the same as. R¹²And R
¹³Are each independently an alkyl group, an aryl group, an alkoxy group.
Represents a Si group and an aryloxy group.

<4> The thermosensitive recording material according to <3>, wherein the cinnoline derivative compound represented by the general formula (1) is encapsulated in microcapsules.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The cinnoline derivative compound, dye and heat-sensitive recording material of the present invention will be described in detail below.

(Cinnoline derivative compound) The cinnoline derivative compound of the present invention is characterized by being represented by the following general formula (1).

[0019]

[Chemical 7]

In the general formula (1), R¹, R², R
³, And R^FourAre each independently a hydrogen atom, an alkyl group,
Reel base, -OR^Five, -SR⁶, -NR⁷R⁸, -CO
R^Ten, Halogen atom, -SO₂R^TenRepresents R^FiveAnd R⁶
Are a hydrogen atom, an alkyl group, an aryl group, and
Represents an acyl group. R⁷And R⁸Are independently hydrogen
Child, alkyl group, aryl group, acyl group, alkyl group
It represents a sulfonyl group and an arylsulfonyl group. Furthermore R
⁷And R⁸Are linked to each other by -O-, -S-, -SO ₂
-, -NR⁹Represents an alkylene group which may include-
You R⁹Is a hydrogen atom, an alkyl group, an aryl group, an acyl group
Group, alkylsulfonyl group, arylsulfonyl group,
Alkoxycarbonyl group, and aryloxycarboni
Represents a radical. R^TenIs a hydrogen atom, hydroxyl group, alkyl group,
Lucoxy group, aryloxy group, and -NR ⁷R⁸The table
You Where R⁷And R⁸Is the above R⁷And R⁸Same as
is there. B is a hydrogen atom, -COR^Ten, -SO₂R¹¹,-
POR¹²R¹³Represents R¹¹Is an alkyl group, aryl
Group, heterocyclic group, and -NR⁷R⁸Represents Where R⁷Over
And R⁸Is the above R⁷And R⁸Is the same as. R¹²And R
¹³Are each independently an alkyl group, an aryl group, an alkoxy group.
Represents a Si group and an aryloxy group.

The compound represented by the general formula (1) is a compound having a cinnoline skeleton as is clear from the structure, but it is a cyclic derivative obtained by a diazotization reaction, and is a coupler similar to the diazonium salt compound. It has not been known so far that a dye can be formed together with a compound, and that when the dye is used in a heat-sensitive recording material, the background coloring is small.

Among the substituents in the above general formula (1),
The alkyl group may be linear or branched and may have an unsaturated bond. The alkyl group is an alkoxy group,
It may be further substituted with an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aryl group, a hydroxy group, a halogen atom or the like. The aryl group is an alkyl group, an alkoxy group, a nitro group, a cyano group, a hydroxy group or a halogen atom,
It may be further substituted.

In the general formula (1), R ¹ , R ² , R
^3, and R ⁴ are each independently a hydrogen atom, an alkyl group, an aryl ^{group, -OR 5, -SR 6, -NR} 7 R 8, -CO
R ^10, a halogen atom, a -SO ₂ R ^10. Among the substituents represented by R ^{1 to} R ⁴ , a hydrogen atom; a carbon atom number of 1 to 1
An alkyl group having 8; an aryl group having 6 to 18 carbon atoms; R
⁵ is an alkyl group having 1 to 22 carbon atoms, 6 to 6 carbon atoms
22 aryl group, -OR ⁵ which is an acyl group having 2 to 22 carbon atoms; R ⁶ is an alkyl group having 1 to 22 carbon atoms,
Aryl group having 6 to 22 carbon atoms, 2 to 22 carbon atoms
-SR ⁶ acyl group; R ⁷ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an aryl group having a carbon number of 6 to 22, R ⁸ is an alkyl group having 1 to 22 carbon atoms,
Aryl group having 6 to 22 carbon atoms, 2 to 22 carbon atoms
Is an acyl group of R ⁷ and R ⁸ are linked to each other to form —O—, —
_{S -, - SO 2 -,} - NR 9 - a which may contain an alkylene group having 4 to 10 carbon atoms, (wherein, R ⁹ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon atoms Number 6
R ¹⁰ is 1 to carbon atoms; ~ 18 aryl group, -NR ⁷ R ⁸ acyl group having 2 to 18 carbon atoms is preferred)
An alkyl group having 18 carbon atoms, an aryl group having 6 to 18 carbon atoms,
Alkoxy group having 1 to 18 carbon atoms, 6 to 1 carbon atoms
-COR ¹⁰ which is an aryloxy group of 8; a fluorine atom,
A halogen atom such as a chlorine atom or a bromine atom; R ¹⁰ is an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkyl group having 6 to 18 carbon atoms. -SO ₂ R ¹⁰ or an aryloxy group; are preferred.

Among the above preferred substituents, a hydrogen atom;
An alkyl group having 1 to 12 carbon atoms; 6 to 12 carbon atoms
An aryl group of R^Five Is alkyl having 1 to 16 carbon atoms
Group, an -OR having 6 to 16 carbon atoms^Five ;
R⁶ Is an alkyl group having 1 to 16 carbon atoms, having 6 carbon atoms
~ SR which is an aryl group of ~ 16⁶ ; R⁷ Is a hydrogen atom,
Alkyl group having 1 to 16 carbon atoms, 6 to 16 carbon atoms
Is an aryl group of R ⁸ Is an alkane having 1 to 16 carbon atoms
Kill group, aryl group having 6 to 16 carbon atoms, number of carbon atoms
2 to 16 acyl groups, R⁷ And R⁸ Are connected to -O
-, -S-, -SO₂ -, -NR⁹ -May be included
-NR is an alkylene group having 4 to 6 carbon atoms.⁷ R
⁸ ; R^TenIs an alkyl group having 1 to 12 carbon atoms, a carbon atom
An aryl group having 6 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms,
Coxy group, aryloxy group having 6 to 12 carbon atoms
-COR^TenFluorine atom, chlorine atom; R^TenIs a carbon atom
Alkyl group having 1 to 12 carbon atoms and aryl having 6 to 12 carbon atoms
Group, alkoxy group having 1 to 12 carbon atoms, number of carbon atoms
-SO, which is an aryloxy group of 6 to 12₂R^TenIs special
Is preferred.

From the viewpoint of further improving the efficiency of light fixing property, among R ^{1 to} R ⁴ in the general formula (1),
One at least ^is, -OR ^5, -SR ^6, and -NR ⁷ R
It is preferably any of ⁸ .

In the general formula (1), B is a hydrogen source.
Child, -COR^Ten, -SO₂R¹¹, -POR¹²R¹³The table
You R¹¹Is an alkyl group, an aryl group, a heterocyclic group, and
-NR ⁷R⁸Represents Where R⁷And R⁸Is the above R⁷
And R⁸Is the same as. R¹²And R¹³Are each independently
Alkyl group, aryl group, alkoxy group, and aryl
Represents an oxy group. Among the substituents represented by B, R¹¹
Is an alkyl group having 1 to 22 carbon atoms, 2 to 2 carbon atoms
-NR of 2⁷ R⁸An aryl group having 6 to 22 carbon atoms,
-SO which is a heterocyclic group containing N, O or S₂ R¹¹; R
¹², R¹³Is an alkyl group having 1 to 18 carbon atoms, alkoxy
Si group, aryl group having 6 to 18 carbon atoms, aryloxy
Is -POR¹²R¹³Is preferred.

Of the above-mentioned preferred substituents, R ¹¹ is an alkyl group having 1 to 16 carbon atoms, or an aryl group having 6 to 16 carbon atoms, —SO ₂ R ¹¹ , R ¹² and R ¹³ are 1 carbon atoms. It is more preferable to use -POR ¹² R ¹³ which is an alkoxy group having 12 to 12 or an aryloxy group having 6 to 12 carbon atoms. Of these, —SO ₂ R ¹¹ having 6 to 14 carbon atoms is particularly preferable from the viewpoint of reactivity with the coupler compound.

Specific examples of the substituents represented by R ^{1 to} R ⁴ are shown below, but the present invention is not limited thereto.

R ^{1 to} R ⁴ are each independently a hydrogen atom, phenyl group, tolyl group, methyl group, ethyl group, n-
Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group,
Hexyl group, octyl group, decyl group, dodecyl group, allyl group, 2-butenyl group, benzyl group, α-dimethylbenzyl group, methoxy group, ethoxy group, propyloxy group,
Butyloxy group, octyloxy group, dodecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, methoxyethoxy group, phenoxyethoxy group, 4-
Methoxyphenoxyethoxy group, phenoxy group, chlorophenoxy group, 4-octyloxyphenoxy group, acetyloxy group, butyryloxy group, benzoyloxy group, methylthio group, ethylthio group, butylthio group, hexylthio group, octylthio group, dodecylthio group, octadecylthio group. Group, benzylthio group, phenethylthio group, phenylthio group, tolylthio group, chlorophenylthio group,
Methoxyphenylthio group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dioctylamino group, N-methyl-N-cyclohexylamino group, diphenylamino group, N-ethyl-N-tolylamino group, acetylamino Group, a propionylamino group,
Isobutyrylamino group, pivaloylamino group, myristoylamino group, stearoylamino group, acryloylamino group, benzoylamino group, cinnamoylamino group,
Morpholino group, piperidino group, pyrrolidino group, N-butyrylpiperazino group, ethoxycarbonyl group, phenyloxycarbonyl group, carbamoyl group, fluorine atom, chlorine atom, bromine atom, sulfamoyl group, methanesulfonylamino group, benzenesulfonylamino group , Octylaminosulfonyl group, phenylaminosulfonyl group, trifluoromethyl group, octylaminocarbonylmethyloxy group, di (butyloxycarbonylmethyl) amino group,
Di (dibutylaminocarbonylmethyl) amino group, dicyanoethylamino group, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, octylsulfonyl group, phenylsulfonyl group, tolylsulfonyl group, chlorophenylsulfonyl group, butyloxyphenylsulfonyl group, sulfo A group, a methoxysulfonyl group, a phenoxysulfonyl group and the like are preferable.

The substituent represented by B includes a methanesulfonyl group, an ethanesulfonyl group, a butanesulfonyl group,
Benzenesulfonyl group, 4-methylbenzenesulfonyl group, 2-mesitylenesulfonyl group, 4-methoxybenzenesulfonyl group, 4-octyloxybenzenesulfonyl group, 2,4,6-triisopropylbenzenesulfonyl group, β-styrenesulfonyl group, Vinylbenzenesulfonyl group, 4-chlorobenzenesulfonyl group, 2,5-
Dichlorobenzenesulfonyl group, 2,4,5-trichlorobenzenesulfonyl group, 1-naphthalenesulfonyl group, 2-naphthalenesulfonyl group, quinolinesulfonyl group, thiophenesulfonyl group, nitrobenzenesulfonyl group, cyanobenzenesulfonyl group, acetylaminobenzenesulfonyl group , Butoxycarbonylbenzenesulfonyl group, pentafluorobenzenesulfonyl group, trifluoromethanesulfonyl group, perfluorobutanesulfonyl group, camphorsulfonyl group, dimethylaminosulfonyl group, diphenylphosphoryl group, diethylphosphoryl group and the like.

The method for producing the compound represented by the general formula (1) includes diazotization of the compound represented by the following general formula (2) and subsequent intramolecular cyclization,

[0032]

[Chemical 8]

Alternatively, XB (where X represents a halogen atom) is added to the diazo compound represented by the following general formula (3), if necessary, pyridine, triethylamine,
The presence of a base such as potassium carbonate or sodium hydroxide, a method of reacting, and the like can be mentioned.

[0034]

[Chemical 9]

R ^{1 to} R ⁴ , B in each of the above general formulas
Is as defined in the above general formula (1).

Specific examples of the cinnoline derivative compound represented by the general formula (1) [(1-1) to (1-2) will be given below.
9)], but the present invention is not limited thereto.

[0037]

[Chemical 10]

[0038]

[Chemical 11]

[0039]

[Chemical 12]

[0040]

[Chemical 13]

[0041]

[Chemical 14]

[0042]

[Chemical 15]

(Dye) Next, the dye of the present invention will be described. The dye of the present invention is characterized by being formed by reacting the cinnoline derivative compound represented by the general formula (1) with a coupler compound. The cinnoline derivative compound represented by the general formula (1) of the present invention is a compound having a cinnoline skeleton as is clear from the structure, but it is a cyclic derivative obtained by a diazotization reaction and is similar to the diazonium salt compound. A dye can be formed by reacting with a coupler compound.

As the coupler compound to be reacted with the cinnoline derivative compound represented by the general formula (1), known naphthol derivatives, hydroxynaphthoic acid derivatives, phenol derivatives, pyrazolone derivatives, 1,3-diketone derivatives, ketocarboxamide derivatives are known. , Pyrazolotriazole derivatives, hydrazone derivatives, hydroxycoumarin derivatives, barbituric acid derivatives and the like can be used. For example, US Pat. Nos. 1,969,479 and 3,26.
No. 5,506, No. 4,486,527, No. 4,6
No. 59,644, British Patent No. 2,196,141, JP-A-61-273986, JP-A-64-67379, JP-A-59-160136 and the like are preferable. Specific examples include resorcin, flurglucin, sodium 2,3-dihydroxynaphthalene-6-sulfonate, 1-hydroxy-2-naphthoic acid morpholinopropylamide, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2, 3-dihydroxy-6-sulfanylnaphthalene, 2-hydroxy-3-naphthoic acid anilide, 2-hydroxy-3-naphthoic acid ethanolamide, 2-hydroxy-3-naphthoic acid octylamide, 2-hydroxy-3-naphthoic acid- N-dodecyloxypurupyramide, 2-hydroxy-3-naphthoic acid tetradecylamide, acetanilide, acetoacetanilide, benzoylacetanilide, 2-chloro-5-octylacetoacetanilide,
1-phenyl-3-methyl-5-pyrazolone, 1-
(2'-octylphenyl) -3-methyl-5-pyrazolone, 1- (2 ', 4', 6'-trichlorophenyl)
-3-benzamido-5-pyrazolone, 1- (2 ',
4 ', 6'-trichlorophenyl) -3-anilino-5
-Pyrazolone, 1-phenyl-3-phenylacetamido-5-pyrazolone, and further C-1 to C-6 shown below
And the like. These coupler compounds are 2
It is also possible to obtain a desired coloring hue by combining two or more kinds.

[0045]

[Chemical 16]

(Thermal Recording Material) The thermal recording material of the present invention will be described below. In the heat-sensitive recording material containing the cinnoline derivative compound represented by the general formula (1), in order to apply this compound, (1) a solid dispersion method is used and (2) an emulsion dispersion method is used. Method,
(3) Polymer dispersion method, (4) latex dispersion method, (5) microencapsulation method, and the like. Among them, microcapsulation method is particularly preferable. .

The content of the cinnoline derivative compound represented by the general formula (1), it is preferably 0.02~3.0g / m ^2, is 0.1 to 2.0 g / m ² Is more preferable. In this case, the content is 0.02 g / m
^When it is less than ² , the color density is insufficient, while when it is more than 3.0 g / m ² , coloring of the background after light irradiation becomes a problem.

Next, the method for incorporating the cinnoline derivative compound represented by the general formula (1) into the heat-sensitive recording material will be described in detail.

As a method of emulsifying and dispersing, first, the cinnoline derivative compound represented by the general formula (1) is dissolved in oil. This oil may be solid or liquid at room temperature,
It may be a polymer, for example, a low boiling auxiliary solvent such as acetic acid ester, methylene chloride, cyclohexanone and /
Or phosphoric acid ester, phthalic acid ester, acrylic acid ester, methacrylic acid ester, other carboxylic acid ethesul, fatty acid amide, alkylated biphenyl, alkylated terphenyl, alkylated naphthalene, diarylethane, chlorinated paraffin, alcohol system, phenol Examples include oils of a system type, an ether type, a monoolefin type and an epoxy type. Specific examples include tricresyl phosphate, trioctyl phosphate, octyl diphenyl phosphate, tricyclohexyl phosphate, dibutyl phthalate, dioctyl phthalate, dilaurate phthalate, dicyclohexyl phthalate, butyl oleate, diethylene glycol benzoate, dioctyl sebacate, Dibutyl sebacate, dioctyl adipate, trioctyl trimellitate, acetyltriethyl citrate, octyl maleate, dibutyl maleate, isoamyl biphenyl, chlorinated paraffin, diisopropyl naphthalene,
1,1'-ditolylethane, 2,4-di-t-amylphenol, N, N-dibutyl-2-butoxy-5-t-
High boiling oils such as octylaniline, hydroxybenzoic acid 2-ethylhexyl ester, polyethylene glycol and α-methylstyrene dimer can be mentioned. Among them, alcohol-based, phosphoric acid ester-based, carboxylic acid ester-based, alkylated biphenyl, Alkylated terphenyls, alkylated naphthalenes, diarylethanes are preferred. Further, an antioxidant such as hindered phenol or hindered amine may be added to the high boiling point oil.

An oil solution containing the cinnoline derivative compound represented by the general formula (1) is added to an aqueous solution of a water-soluble polymer, and emulsified and dispersed by a colloid mill, a homogenizer or ultrasonic waves. As the water-soluble polymer used at that time, a water-soluble polymer such as polyvinyl alcohol is used, but an emulsion or latex of a hydrophobic polymer can also be used together. As the water-soluble polymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, carboxy modified polyvinyl alcohol, amino modified polyvinyl alcohol, itaconic acid modified polyvinyl alcohol, styrene-maleic anhydride copolymer,
Butadiene-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, polyacrylamide, polystyrene sulfonic acid, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, gelatin and the like. Of these, carboxy-modified polyvinyl alcohol is particularly preferable. Examples of the emulsion or latex of the hydrophobic polymer include styrene-butadiene copolymer, carboxy-modified styrene-
Examples thereof include a butadiene copolymer and an acrylonitrile-butadiene copolymer. At this time, a conventionally known surfactant or the like may be added, if necessary, for the purpose of improving the emulsion stability.

As a method for microencapsulating the cinnoline derivative compound represented by the general formula (1), a conventionally known microencapsulation method can be used. That is, the cinnoline derivative compound represented by the general formula (1) and the microcapsule wall precursor are dissolved in an organic solvent that is sparingly or insoluble in water and added to an aqueous solution of a water-soluble polymer, and a homogenizer or the like is used. Can be emulsified and dispersed, and the temperature can be raised to prepare a polymer substance that becomes the microcapsule wall by forming a wall film at the oil / water interface. Specific examples of the polymer material that becomes the wall film of the microcapsule include, for example, polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin,
Amino aldehyde resin, melamine resin, polystyrene resin, styrene-acrylate copolymer resin, styrene-
Methacrylate copolymer resins, gelatin, polyvinyl alcohol and the like and mixtures thereof can be mentioned. Particularly preferable among these are microcapsules having a wall film made of a polyurethane-polyurea resin.

Microcapsules having a wall film made of polyurethane / polyurea resin are prepared by mixing a microcapsule wall precursor such as polyisocyanate with a core substance to be encapsulated and emulsifying it in an aqueous solution of a water-soluble polymer such as polyvinyl alcohol. It is manufactured by dispersing and raising the liquid temperature to cause a polymer formation reaction at the oil drop interface.

Here, some of the specific examples of the polyisocyanate compound as the microcapsule wall precursor are shown below. For example, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, naphthalene-1,4-diisocyanate, diphenylmethane-
4,4'-diisocyanate, 3,3'-diphenylmethane-4,4'-diisocyanate, xylene-1,4
-Diisocyanate, 4,4'-diphenylpropane diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, propylene-1,2-diisocyanate, butylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, cyclohexylene-1, Diisocyanates such as 4-diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, triisocyanates such as toluene-2,4,6-triisocyanate, 4,4′-dimethyldiphenylmethane-2,2 ′ , 5,5'-Tetraisocyanate and other tetraisocyanates, addition product of hexamethylene diisocyanate and trimethylolpropane, addition of 2,4-tolylene diisocyanate and trimethylolpropane , An isocyanate prepolymer such as an adduct of xylylene diisocyanate and trimethylolpropane, an adduct of tolylene diisocyanate and hexanetriol, etc. In addition, two or more kinds of them may be used in combination, if necessary. Particularly preferred is one having three or more isocyanate groups in the molecule.

In the method of microencapsulation, as the organic solvent for dissolving the cinnoline derivative compound represented by the general formula (1), the oil exemplified in the method of emulsifying and dispersing can be used. The same applies to water-soluble polymers.

The particle size of the microcapsules is 0.1.
1.0 μm is preferable, and more preferably 0.2 to 0.7.
It is in the range of μm.

The heat-sensitive recording layer containing the cinnoline derivative compound represented by the general formula (1) used in the present invention and the coupler compound which reacts with the compound to develop a color further accelerates the color reaction. Including a basic substance, a sensitizer for improving thermal sensitivity, an antioxidant for improving fastness, a UV absorber, a metal salt capable of chelating the formed dye and a metal complex, or a precursor thereof You may stay.

The basic substance includes not only inorganic or organic basic compounds, but also compounds capable of decomposing upon heating to release an alkaline substance. Typical examples include organic ammonium salts, organic amines, amides, urea and thiourea, and their derivatives, thiazoles, pyrroles, pyrimidines, piperazines, guanidines, indoles, imidazoles, imidazolines, Examples thereof include nitrogen-containing compounds such as triazoles, morpholines, piperidines, amidines, formazines and pyridines. Specific examples thereof include tricyclohexylamine, tribenzylamine, octadecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl. -4-methylimidazole, 2-
Undecyl imidazoline, 2,4,5-trifuryl-2
-Imidazoline, 1,2-diphenyl-4,4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1,2,3- Tricyclohexylguanidine, guanidine trichloroacetate, N,
There are N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenzothiazole, 2-benzoylhydrazinobenzothiazole and the like. These can be used in combination of two or more.

The sensitizers usable in the present invention include phenols, ethers, esters, sulfonamides,
Examples thereof include amides, ureas, urethanes, alcohols and the like. Specific examples thereof include 1,1- (4-hydroxyphenyl) -2-2-ethylhexane, benzyloxynaphthalene, toluenesulfonamide, butoxybenzenesulfonamide, 1,2-phenoxyethane, diphenylurea, benzamide, stearin. Acid amide and the like can be mentioned. These may be used alone,
It is also possible to use two or more types in combination.

In the present invention, the cinnoline derivative compound represented by the above general formula (1), the coupler that reacts with the compound to produce a color when heated, a basic substance, and optionally a sensitizer are used. Is not particularly limited. That is, as in the case of the cinnoline derivative compound represented by the general formula (1), (1) a method of using by solid dispersion,
There are (2) a method of emulsifying and dispersing, (3) a method of dispersing and using a polymer, (4) a method of dispersing and using a latex, and (5) a method of encapsulating and using. However, from the viewpoint of storability, the method of microencapsulating and using the microcapsules is preferable, and the case of microencapsulating the cinnoline derivative compound represented by the general formula (1) is particularly preferable.

In the present invention, in order to further improve the light resistance, the following known antioxidants can be used, for example, European Patent Publication No. 310,551 and German Patent Publication No. 3,435,443. Japanese Patent Publication, European Patent Publication No. 310,552, Japanese Patent Laid-Open No. 3-1
21449, European Published Patent No. 459,41
6, JP-A-2-262654, JP-A-2-
71262, JP-A-63-163351,
U.S. Pat. No. 4,814,262, JP-A-54-485.
35, JP-A-5-61166, and 5-11.
9449, U.S. Pat. No. 4,980,275, Japanese Patent Laid-Open No. 63-113536, 62-262047.
Publication, European patent publication 223,739 publication,
Examples thereof include those disclosed in European Patent Publication No. 309,402 and European Patent Publication No. 309,401.

Further, it is also effective to use various additives which are already known in heat-sensitive recording materials and pressure-sensitive recording materials. Some of these antioxidants are shown in JP-A-60-125470 and JP-A-60-125471.
JP, JP-A-60-125472, JP-A-60
-287485, JP-A-60-287486, JP-A-60-287487, and JP-A-62-1.
46680, JP-A-60-287488,
JP-A-62-282885, JP-A-63-898
77, JP-A-63-88380, JP-A-6.
3-088831, JP 01-239282, JP 04-291685, JP 04-
291684, JP 05-1888687, JP 05-188686, and JP 05-1.
No. 10490, No. 05-1108437, No. 05-170361, No. 63-2.
No. 03372, JP-A-63-224989,
JP-A-63-267594, JP-A-63-182
484, JP-A-60-107384, JP-A-60-107383, and JP-A-61-162828.
No. 7, JP-A-61-185483, JP-A-Sho 6
1-211079, JP-A-63-251282, JP-A-63-051174, JP-B-48-
The compounds described in JP-A-043294, JP-B-48-033212 and the like can be mentioned.

Specific examples include 6-ethoxy-1-phenyl-2,2,4-trimethyl-1,2-dihydroquinoline, 6-ethoxy-1-octyl-2,2,4-trimethyl-1,2. -Dihydroquinoline, 6-ethoxy-1-
Phenyl-2,2,4-trimethyl-1,2,3,4-
Tetrahydroquinoline, 6-ethoxy-1-octyl-
2,2,4-trimethyl-1,2,3,4-tetrahydroquinoline, nickel cyclohexanoate, 2,2-bis-4-hydroxyphenylpropane, 1,1-bis-4
-Hydroxyphenyl-2-ethylhexane, 2-methyl-4-methoxy-diphenylamine, 1-methyl-2
-Phenylindole and the compounds shown below (Q-1 to Q
-73).

[0063]

[Chemical 17]

[0064]

[Chemical 18]

[0065]

[Chemical 19]

[0066]

[Chemical 20]

[0067]

[Chemical 21]

[0068]

[Chemical formula 22]

[0069]

[Chemical formula 23]

[0070]

[Chemical formula 24]

These antioxidants can be added to the heat-sensitive recording layer, the intermediate layer or the protective layer in the heat-sensitive recording material of the present invention. When these antioxidants and the like are used in combination, for example, specific examples (Q-7), (Q-45),
(Q-46) or compound (Q-10) and compound (Q-1)
The combination of 3) is mentioned.

Examples of the UV absorber or its precursor include conventionally known hydroxybenzophenones, cinnamic acid esters, salicylic acid esters, benzotriazoles and triazines. Specific examples thereof include the compounds (E-1 to E-9) shown below, but the invention is not limited thereto.

[0073]

[Chemical 25]

The UV absorber or its precursor can be added to the protective layer, the heat-sensitive recording layer or the intermediate layer by emulsification dispersion, polymer dispersion, latex dispersion, solid dispersion or microencapsulation.

As the binder in the present invention, conventionally known binders can be used, and examples thereof include water-soluble polymers such as polyvinyl alcohol and gelatin, and polymer latex.

As the support in the present invention, plastic film, paper, plastic resin laminated paper, synthetic paper and the like can be used.

In the present invention, when heat-sensitive recording layers having different hues are laminated, an intermediate layer can be provided to prevent color mixing. A water-soluble polymer compound is used for the intermediate layer. Examples thereof include polyvinyl alcohol, modified polyvinyl alcohol, methyl cellulose, sodium polystyrene sulfonate, styrene-maleic acid copolymer, gelatin and the like.

In the protective layer in the present invention, various pigments, release agents and the like can be added in addition to the same water-soluble polymer compound as that of the intermediate layer.

The constitution of the heat-sensitive recording material to which the present invention is applied is not particularly limited, and two or more kinds of the cinnoline derivative compounds represented by the general formula (1) having different maximum absorption wavelengths are used, and multi-color heat-sensitive recording is carried out. The material can be obtained. Also,
Along with the cinnoline derivative compound represented by the general formula (1), another coloring system, for example, a coloring system of an electron-donating colorless dye and an electron-accepting compound, a diazonium salt compound and the diazonium salt compound are reacted with each other under heat. Even if combined with a color development system with a coupler compound that develops color, a base development system that develops a color by contact with a basic compound, a chelate development system, and a color development system that develops a color by reacting with a nucleophile to cause an elimination reaction. A multicolor thermosensitive recording material can be obtained. These may exist in the same layer or may be laminated in different layers. Examples of the multicolor heat-sensitive recording material include, for example, (i) a cinnoline derivative compound represented by the above general formula (1) having a maximum absorption wavelength of 360 ± 20 nm, which is reacted with the compound to give a color on a support. A heat-sensitive recording layer containing a coupler, a heat-sensitive recording layer containing a cinnoline derivative compound represented by the general formula (1) having a maximum absorption wavelength of 400 ± 20 nm, and a coupler that reacts with the compound to develop a color. A heat-sensitive recording material provided in sequence, (ii) a heat-sensitive material containing, on a support, a cinnoline derivative compound represented by the general formula (1) having a maximum absorption wavelength of less than 340 nm, and a coupler which reacts with the compound to develop a color. A recording layer, a thermosensitive recording layer containing a cinnoline derivative compound represented by the general formula (1) having a maximum absorption wavelength of more than 400 nm, and a coupler that reacts with the compound to develop a color. A recording material, (iii) a heat-sensitive recording layer containing a diazonium salt compound having a maximum absorption wavelength of 360 ± 20 nm and a coupler which reacts with the compound to develop a color on a support, and a maximum absorption wavelength of 400 ± 20 nm A heat-sensitive recording material in which a heat-sensitive recording layer containing a cinnoline derivative compound represented by the general formula (1) and a coupler which reacts with the compound to develop a color is sequentially provided, and (iv) a maximum absorption wavelength of 360 on a support. A thermosensitive recording layer containing a cinnoline derivative compound represented by the general formula (1) having a wavelength of ± 20 nm and a coupler that reacts with the compound to develop a color, and a maximum absorption wavelength of 400.
A thermosensitive recording material in which a thermosensitive recording layer containing a diazonium salt compound having a wavelength of ± 20 nm and a coupler that reacts with the compound to produce a color is sequentially provided is mentioned.

The maximum absorption wavelengths of the cinnoline derivative compound represented by the general formula (1) or the cinnoline derivative compound represented by the general formula (1) and the diazonium salt compound having two or more different photosensitizing wavelengths are exemplified above. Although not limited to the wavelength, it is preferable that the maximum absorption wavelengths are separated from each other by at least 20 nm or more from the viewpoint of sequentially performing optical fixing.

In the present invention, the maximum absorption wavelength of the cinnoline derivative compound or diazonium salt compound represented by the general formula (1) is 0.1 g / m 2 for each compound.
The coating film of ² to 1.0 g / m ² was measured by a spectrophotometer (MPS-2000 manufactured by Shimadzu Corporation).

The heat-sensitive recording material of the present invention may be applied by laminating the heat-sensitive recording layers, and a multicolor heat-sensitive recording material can be obtained by changing the hue of each heat-sensitive recording layer.

The layer structure is not particularly limited, but for example, two kinds of the general formula (1) having different photosensitizing wavelengths can be used.
2 layers of a thermosensitive recording layer in which a cinnoline derivative compound represented by the following and a coupler which reacts with each of the compounds under heat to form different hues are combined, and a thermosensitive layer in which an electron-donating colorless dye and an electron-accepting compound are combined A multicolor thermosensitive recording material having a recording layer laminated thereon can be used. That is, a first heat-sensitive recording layer containing an electron-donating colorless dye and an electron-accepting compound on a support, a cinnoline derivative compound represented by the general formula (1) having a maximum absorption wavelength of 360 ± 20 nm, and the compound. Second containing a coupler that develops color when reacted with heat
A heat-sensitive recording layer, and a third heat-sensitive recording layer containing a cinnoline derivative compound represented by the general formula (1) having a maximum absorption wavelength of 400 ± 20 nm, and a coupler that develops a color when reacted with the compound. To do. In this example, full-color image recording is possible by selecting the hues of the heat-sensitive recording layers to be the three primary colors in subtractive color mixing, yellow, magenta, and cyan.

In the recording method of this multicolor heat-sensitive recording material, first, the third heat-sensitive recording layer is heated to cause the cinnoline derivative compound represented by the general formula (1) and the coupler contained in the third layer to develop color. Next, irradiate with light of 400 ± 20 nm and
After decomposing the unreacted compound contained in the heat-sensitive recording layer, sufficient heat is applied so that the second heat-sensitive recording layer develops a color, and the general formula (1) contained in the layer is added. The cinnoline derivative compound represented by and the coupler are colored. At this time, the third thermosensitive recording layer is also heated strongly at the same time, but the cinnoline derivative compound represented by the general formula (1) has already been decomposed and the coloring ability is lost, so that no color is produced. Further, the compound contained in the second thermosensitive recording layer is decomposed by irradiating with light of 360 ± 20 nm, and finally, sufficient heat for the first thermosensitive recording layer to develop color is applied to develop the color. At this time, the third and second thermosensitive recording layers are also strongly heated at the same time, but since each compound represented by the general formula (1) has already been decomposed and the coloring ability has been lost, no coloring occurs.

Specific examples of the diazonium salt compound which can be used in the heat-sensitive recording material of the present invention include 4- (N
-(2- (2,4-di-tert-amylphenoxy)
Butyryl) piperazino) benzenediazonium, 4-dioctylaminobenzenediazonium, 4- (N- (2
-Ethylhexanoyl) piperazino) benzenediazonium, 4-dihexylamino-2-hexyloxybenzenediazonium, 4-N-ethyl-N-hexadecylamino-2-ethoxybenzodiazonium, 3-chloro-4-dioctylamino-2 -Octyloxyobenzenediazonium, 2,5-dibutoxy-4-morpholinobenzenediazonium, 2,5-octoxy-4-morpholinobenzenediazonium, 2,5-dibutoxy-4
-(N- (2-ethylhexanoyl) piperazino) benzenediazonium, 2,5-diethoxy-4- (N-
(2- (2,4-di-tert-amylphenoxy) butyryl) piperazino) benzenediazonium, 2,5-
Dibutoxy-4-tolylthiobenzenediazonium, 3
Examples thereof include acid anion salts such as-(2-octyloxyethoxy) -4-morpholinobenzenediazonium and the following diazonium salt compounds D-1 to D-5. Particularly, hexafluorophosphate salt, tetrafluoroborate salt and 1,5-naphthalene sulfonate salt are preferable.

[0086]

[Chemical formula 26]

In the present invention, as the color-forming component used in the heat-sensitive recording layer, a cinnoline derivative compound represented by the general formula (1), a compound utilizing the reaction of the diazonium salt compound with a coupler, and an electron donor are used. Examples of the electron-donating colorless dye used in the heat-sensitive recording material of the present invention include triarylmethane compounds, diphenylmethane compounds, and thiazine. Compounds, xanthene compounds, spiropyran compounds, and the like. Triarylmethane compounds and xanthene compounds are particularly useful because of their high color density. For example, 3,3-bis (p-dimethylaminophenyl)-
6-dimethylaminophthalide (that is, crystal violet lactone), 3,3-bis (p-dimethylamino)
Phthalide, 3- (p-dimethylaminophenyl) -3-
(1,2-dimethylindol-3-yl) phthalide,
3- (p-dimethylaminophenyl) -3- (1-octyl-2-methylindol-3-yl) phthalide, 3
-(O-methyl-p-diethylaminophenyl) -3-
(1-Ethyl-2-methylindol-3-yl) -4
-Azaphthalide, 4,4'-bis (dimethylamino) benzhydrin benzyl ether, N-halophenyl leuco auramine, N-2,4,5-trichlorophenyl leuco auramine, rhodamine-B-anilinolactam,
Rhodamine (p-nitroanilino) lactam, Rhodamine-B- (p-chloroanilino) lactam, 2-benzylamino-6-diethylaminofluorane, 2-anilino-6-diethylaminofluorane, 2-anilino-3
-Methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-cyclohexylmethylaminofluorane, 2-anilino-3-methyl-6-isoamylethylaminofluorane, 2- (o-chloroanilino)-
6-diethylaminofluorane, 2-octylamino-
6-diethylaminofluorane, 2-ethoxyethylamino-3-chloro-2-diethylaminofluorane, 2
-Anilino-3-chloro-6-diethylaminofluorane, benzoyl leuco methylene blue, p-nitrobenzyl leuco methylene blue, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran,
3,3′-dichloro-spiro-dinaphthopyran, 3-benzylspirodinaphthopyran, 3-propyl-spiro-
Dibenzopyran etc. are mentioned.

Examples of the electron-accepting compound include phenol derivatives, salicylic acid derivatives, hydroxybenzoic acid esters and the like. Particularly, bisphenols and hydroxybenzoic acid esters are preferable. Examples of some of these are 2,2-bis (p-hydroxyphenyl) propane (ie, bisphenol A), 4,4′-
(P-Phenylenediisopropylidene) diphenol (ie, bisphenol P), 2,2-bis (p-hydroxyphenyl) pentane, 2,2-bis (p-hydroxyphenyl) ethane, 2,2-bis (p -Hydroxyphenyl) butane, 2,2-bis (4'-hydroxy-
3 ', 5'-dichlorophenyl) propane, 1,1-
(P-Hydroxyphenyl) cyclohexane, 1,1-
(P-Hydroxyphenyl) propane, 1,1- (p-
Hydroxyphenyl) pentane, 1,1- (p-hydroxyphenyl) -2-ethylhexane, 3,5-di (α
-Methylbenzyl) salicylic acid and its polyvalent metal salts,
3,5-di (tert-butyl) salicylic acid and its polyvalent metal salt, 3-α, α-dimethylbenzylsalicylic acid and its polyvalent metal salt, butyl p-hydroxybenzoate, p
-Benzyl hydroxybenzoate, 2-ethylhexyl p-hydroxybenzoate, p-phenylphenol, p
-Cumylphenol and the like.

[0089]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition, all "parts" in this example represent "parts by mass".

-Synthesis of Cinnoline Derivative Compound- <Example 1; Synthesis of Exemplified Compound (1-6)> To a mixed solution of 15 ml of methanol and 6.2 ml of concentrated hydrochloric acid, 4.9 g of the corresponding aniline was added. Next, a solution prepared by dissolving 1.7 g of sodium nitrite in 10 ml of water was added at a reaction temperature of 1
The solution was added dropwise while keeping the temperature below 0 ° C. After heating to room temperature 3
After stirring for 0 minutes, water was added to filter the resulting crystals,
3.1 g of the exemplary compound (1-6) of the present invention (yield 60
%)Obtained. The compound was identified by using 1 H-NMR. The results are as follows. 1 H-NMR (CDCl ₃ ) δ; 8.05 (1H), 7.
25 (1H), 6.85 (1H), 3.80 (2H),
3.64 (2H), 2.70 (1H)

Example 2 Synthesis of Exemplified Compound (1-7) 6.5 g of the corresponding aniline was added to a mixed solution of 50 ml of methanol and 4.2 ml of concentrated hydrochloric acid. Next, a solution prepared by dissolving 1.2 g of sodium nitrite in 30 ml of water,
The solution was added dropwise while maintaining the reaction temperature at 10 ° C or lower. After warming to room temperature and stirring for 30 minutes, water was added and the resulting crystals were filtered to give 3.1 g of the exemplary compound (1-7) of the present invention.
(Yield 60%) was obtained. The compound was identified by using 1 H-NMR. The results are as follows. 1 H-NMR (CDCl ₃ ) δ; 7.90 (1H), 7.
43-7.58 (3H), 3.81 (1H), 3.64
(1H), 3.30 (4H), 2.98 (2H), 1.
65 (2H), 1.20-1.40 (18H), 0.8
5 (3H)

-Synthesis of Dye- <Example 3; Synthesis of Dye> 0.44 g of coupler compound 1 represented by the following structural formula and 0.11 of triethylamine.
g was dissolved in 10 ml of ethyl acetate, and 0.2 parts of the exemplified compound (1-6) of the present invention was added to the mixture while stirring.
1 g was added. The resulting dye was purified on a silica gel column. The λmax of the dye in ethyl acetate was measured and found to be 541.4 nm.

[0093]

[Chemical 27]

Example 4 Synthesis of Dye> Example 3
In the above, except that 0.43 g of the coupler compound 1 was used and 0.53 g of the following coupler compound 2 was used,
Dyes were synthesized in the same manner as the dyes of Example 3. Λmax of the dye in ethyl acetate was 51
It was 5.4 nm.

[0095]

[Chemical 28]

Example 5: Synthesis of dye> Example 3
In the above, except that 0.45 g of the coupler compound 1 was used and 0.75 g of the following coupler compound 3 was used,
Dyes were synthesized in the same manner as the dyes of Example 3. Λmax of the dye in ethyl acetate is 48
It was 8.2 nm.

[0097]

[Chemical 29]

<Example 6; Synthesis of dye> Example 3
In the above, except that 0.46 g of the following coupler compound 4 was used instead of 0.44 g of the coupler compound 1,
Dyes were synthesized in the same manner as the dyes of Example 3. Λmax of the dye in ethyl acetate was 51
It was 9.0 nm.

[0099]

[Chemical 30]

From the results of Examples 3 to 6 above, the cinnoline derivative compound of the present invention reacted with the coupler compound,
It was confirmed to have a function of forming a dye.

-Preparation and Evaluation of Thermosensitive Recording Material- <Example 7> [Preparation of Thermosensitive Recording Layer Liquid] Preparation of Diazo Compound Capsule Liquid As the diazo compound (cinnoline derivative compound), the exemplified compound (1- 7) 2.8 parts, dibutyl sulfate 2.
8 parts and 0.52 parts of 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE 651, trade name, manufactured by Ciba Geigy) were dissolved in 19.0 parts of ethyl acetate. Furthermore, 5.9 parts of isopropyl biphenyl, which is a high boiling point solvent, and 2.5 parts of tricresyl phosphate were added to the above liquid, and heated to uniformly mix. As a capsule wall agent, xylylene diisocyanate / trimethylolpropane adduct (75 mass% ethyl acetate solution Takenate D
(110 N: manufactured by Takeda Pharmaceutical Co., Ltd.) (7.6 parts) was further added to this solution and stirred uniformly. Separately, 64 parts of a 6 mass% gelatin (MGP-9066: trade name, manufactured by Nippi Gelatin Industry Co., Ltd.) aqueous solution containing 2.0 parts of a 10 mass% sodium dodecylsulfonate aqueous solution was prepared, and the diazo compound (cinnoline derivative compound) was prepared. ) The solution was added, and the mixture was emulsified and dispersed with a homogenizer. After 20 parts of water was added to the obtained emulsion to homogenize it, the temperature was raised to 40 ° C. with stirring and the encapsulation reaction was carried out for 3 hours. After that, the liquid temperature is lowered to 35 ° C., 6.5 parts of an ion exchange resin Amberlite IRA68 (manufactured by Organo) and 13 parts of Amberlite IRC50 (manufactured by Organo) are added, and the mixture is further stirred for 1 hour. Then, the ion exchange resin was filtered to obtain the target capsule liquid.

Preparation of Coupler Emulsion Dispersion As a coupler, 3.0 parts of compound b-1 shown below, 4.0 parts of triphenylguanidine, and 4 parts of 1,1- (p-hydroxyphenyl) -2-ethylhexane were used. 0.0 copies, 4,
8.0 parts of 4 '-(p-phenylenediisopropylidene) diphenol, 8.0 parts of 2-ethylhexyl-4-hydroxybenzoate, 2.0 parts of b-2 as an antioxidant, 1,1, 2.0 parts of 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
Dissolved in 10.5 parts of ethyl acetate, 0.48 parts of tricresyl phosphate, which is a high boiling point solvent, 0.24 parts of diethyl maleate, Pionin A41C (manufactured by Takemoto Yushi Co., Ltd.)
After adding 27 parts, it heated and mixed uniformly. Separately 8% by weight gelatin (# 750 gelatin: manufactured by Nitta Gelatin Co., Ltd.)
The mixture was added to 93 parts of the aqueous solution and emulsified and dispersed by a homogenizer. The remaining ethyl acetate was evaporated from this emulsion to obtain the target emulsion dispersion.

[0103]

[Chemical 31]

Preparation of coating liquid The above diazo compound (cinnoline derivative compound) capsule liquid, coupler emulsion dispersion liquid, and styrene-butadiene rubber (SBR: SN307: trade name, manufactured by Sumitomo Nogatak Co., Ltd.) were each used as a diazo compound / coupler. Ratio of 1
And a diazo compound / styrene-butadiene rubber ratio of 1 / 6.4 were mixed to prepare a desired coating liquid.

[Preparation of Protective Layer] 20.5% by mass zinc stearate dispersion liquid (Hydrin F115: trade name) in 61 parts of 5.0% by mass carboxy-modified polyvinyl alcohol (KL-318: manufactured by Kuraray Co., Ltd.) aqueous solution. , Chukyo Yushi Co., Ltd.), and 2 parts of the compound represented by the following formula c-1:
8.4 parts by mass aqueous solution, ME-3 which is a fluorine-based release agent
8.0 (manufactured by Daikin), K, which is a wheat starch
0.5 part of F-4 (made by Kagoshima Starch Co., Ltd.) was added and stirred uniformly. This is called mother liquor. Separately, ion-exchanged 20% by mass aqueous solution of kaogros (manufactured by Shiraishi Industry Co., Ltd.) 12.
5 parts, Poise 532A (manufactured by Kao) 0.06 parts, Hydrin Z-7 (manufactured by Chukyo Yushi Co., Ltd.) 1.87 parts, 10 mass% polyvinyl alcohol (PVA105: manufactured by Kuraray Co., Ltd.)
25 parts and 0.39 part of a 2% by mass sodium dodecyl sulfonate aqueous solution were mixed and finely dispersed with a dyno mill. This liquid is called a pigment liquid. To 80 parts of the above mother liquor, 4.4 parts of the pigment liquid is added and stirred for 30 minutes or more. After that, Wetmaster500 (manufactured by Toho Kagaku) 2.8
Parts were added, and the mixture was further stirred for 30 minutes or more to obtain the target coating liquid.

[0106]

[Chemical 32]

[Preparation of Thermosensitive Recording Material] A thermosensitive recording layer containing a cinnoline derivative compound with a Meyer bar on a photographic paper support obtained by laminating polyethylene on high-quality paper,
The desired heat-sensitive recording material was obtained by sequentially coating and drying the protective layers. The coating amount as the solid content 1 m ² per each 8.
It was 4 g and 1.2 g.

[Thermal recording and evaluation] Using a Kyocera thermal head KST type, (1) the applied power and pulse width to the thermal head were determined so that the recording energy per unit area was 62 mJ / mm ^2, and the thermal recording was performed. When the material was printed, it developed red. When the thermosensitive recording material before printing was left at a temperature of 60 ° C. and a humidity of 30% for 24 hours and then printed, no decrease in density was observed.

As a result, it was confirmed that the heat-sensitive recording material using the cinnoline derivative compound of the present invention as a diazo compound did not deteriorate in color development due to storage before printing.

[0110]

INDUSTRIAL APPLICABILITY According to the present invention, a novel cinnoline derivative compound, which is preferably used together with a coupler component as a diazo compound component in the formation of a dye and has high stability, is formed by the reaction of the cinnoline derivative compound with the coupler compound. It is possible to provide a heat-sensitive recording material containing a dye and a cinnoline derivative compound, which is excellent in raw storage stability.

Claims (4)

[Claims] 1. A structure represented by the following general formula (1):
And a cinnoline derivative compound. [Chemical 1] In the general formula (1), R¹, R², R³, And R
^FourAre each independently a hydrogen atom, an alkyl group, an aryl
Group, -OR^Five, -SR⁶, -NR⁷R⁸, -COR^Ten,Halo
Gen atom, -SO₂R^TenRepresents R^FiveAnd R⁶Is that
Hydrogen atom, alkyl group, aryl group, and acyl group
Represent R⁷And R⁸Are each independently a hydrogen atom or alkyl
Group, aryl group, acyl group, alkylsulfonyl group, and
And an arylsulfonyl group. Furthermore R⁷And R⁸Is
Connected to each other by -O-, -S-, -SO ₂-, -NR⁹−
Represents an alkylene group which may contain. R⁹Is hydrogen
Atom, alkyl group, aryl group, acyl group, alkyls
Rufonyl group, arylsulfonyl group, alkoxycarbo
It represents a nyl group and an aryloxycarbonyl group. R^Ten
Is a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, ant
Group and -NR ⁷R⁸Represents Where R⁷Over
And R⁸Is the above R⁷And R⁸Is the same as. B is hydrogen
Atom, -COR^Ten, -SO₂R¹¹, -POR¹²R¹³The table
You R¹¹Is an alkyl group, an aryl group, a heterocyclic group, and
-NR⁷R⁸Represents R¹²And R¹³Are each independently
Kill group, aryl group, alkoxy group, and aryl group
Represents a group. 2. A cinnoline represented by the following general formula (1):
Due to the reaction between the derivative compound and the coupler compound
A dye characterized by being formed by [Chemical 2] In the general formula (1), R¹, R², R³, And R
^FourAre each independently a hydrogen atom, an alkyl group, an aryl
Group, -OR^Five, -SR⁶, -NR⁷R⁸, -COR^Ten,Halo
Gen atom, -SO₂R^TenRepresents R^FiveAnd R⁶Is that
Hydrogen atom, alkyl group, aryl group, and acyl group
Represent R⁷And R⁸Are each independently a hydrogen atom or alkyl
Group, aryl group, acyl group, alkylsulfonyl group, and
And an arylsulfonyl group. Furthermore R⁷And R⁸Is
Connected to each other by -O-, -S-, -SO ₂-, -NR⁹−
Represents an alkylene group which may contain. R⁹Is hydrogen
Atom, alkyl group, aryl group, acyl group, alkyls
Rufonyl group, arylsulfonyl group, alkoxycarbo
It represents a nyl group and an aryloxycarbonyl group. R^Ten
Is a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, ant
Group and -NR ⁷R⁸Represents Where R⁷Over
And R⁸Is the above R⁷And R⁸Is the same as. B is hydrogen
Atom, -COR^Ten, -SO₂R¹¹, -POR¹²R¹³The table
You R¹¹Is an alkyl group, an aryl group, a heterocyclic group, and
-NR⁷R⁸Represents R¹²And R¹³Are each independently
Kill group, aryl group, alkoxy group, and aryl group
Represents a group. 3. A diazo compound and the dia compound on a support.
Contains a coupler compound that develops a color when reacted with a zo compound
A heat-sensitive recording material provided with a heat-sensitive recording layer, comprising:
Cinnoline represented by the following general formula (1) as a zo compound
Thermal recording material containing a derivative compound
Fee. [Chemical 3] In the general formula (1), R¹, R², R³, And R
^FourAre each independently a hydrogen atom, an alkyl group, an aryl
Group, -OR^Five, -SR⁶, -NR⁷R⁸, -COR^Ten,Halo
Gen atom, -SO₂R^TenRepresents R^FiveAnd R⁶Is that
Hydrogen atom, alkyl group, aryl group, and acyl group
Represent R⁷And R⁸Are each independently a hydrogen atom or alkyl
Group, aryl group, acyl group, alkylsulfonyl group, and
And an arylsulfonyl group. Furthermore R⁷And R⁸Is
Connected to each other by -O-, -S-, -SO ₂-, -NR⁹−
Represents an alkylene group which may contain. R⁹Is hydrogen
Atom, alkyl group, aryl group, acyl group, alkyls
Rufonyl group, arylsulfonyl group, alkoxycarbo
It represents a nyl group and an aryloxycarbonyl group. R^Ten
Is a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, ant
Group and -NR ⁷R⁸Represents Where R⁷Over
And R⁸Is the above R⁷And R⁸Is the same as. B is hydrogen
Atom, -COR^Ten, -SO₂R¹¹, -POR¹²R¹³The table
You R¹¹Is an alkyl group, an aryl group, a heterocyclic group, and
-NR⁷R⁸Represents R¹²And R¹³Are each independently
Kill group, aryl group, alkoxy group, and aryl group
Represents a group. 4. The heat-sensitive recording material according to claim 3, wherein the cinnoline derivative compound represented by the general formula (1) is encapsulated in microcapsules.