WO2004113091A1 - Heat-sensitive recording material and benzenesulfonamide derivative - Google Patents

Abstract

A heat-sensitive recording material is disclosed which comprises a heat-sensitive color developing layer which is formed on a supporting body and contains a dye precursor and a developer which reacts with the dye precursor when heated and develops the dye precursor. The developer is composed of a compound having at least one substructure represented by the formula (I) below in a molecule. A specific benzenesulfonamide derivative having such a substructure is also disclosed. (I)

Description

 Description Thermal recording medium and benzenesulfonamide derivative Technical field

 The present invention relates to a thermosensitive recording medium and a novel benzenesulfonamide derivative.

 More specifically, the present invention relates to a thermosensitive recording medium having a thermosensitive coloring layer using a novel developer, which exhibits resistance to various environmental conditions, in particular, plastic plasticizers and enables long-term recording and storage. And a novel benzenesulfonamide derivative useful as the developer and the like. Background art

 Colorless or pale-coloring colorless dyes, for example, heat-sensitive recording materials utilizing the heat coloring phenomenon of leuco dyes with phenols and organic acids are described, for example, in JP-B-43-416, JP-B-4 It is described in Japanese Patent Application Laid-Open No. 5-14039 and Japanese Patent Application Laid-Open No. 48-277736, and is widely used.

Such a thermosensitive recording medium is generally called a chromogenic substance represented by a leuco dye and an ISP which is an organic acidic substance represented by a phenolic compound on paper or a plastic film as a support. The following formula

The developer represented by is dispersed finely and applied uniformly and thinly to form a heat-sensitive coloring layer.

When this heat-sensitive coloring layer is locally heated, the coloring material and the organic acid substance are removed. The developer is melted and mixed with each other, and color is generated by the transfer of protons.

 The technology for producing the thermal recording medium, that is, the coating technology itself, is not difficult, and the recording device is compact and inexpensive, and maintenance and inspection are easy. Therefore, these thermal recording media are nowadays not only used in conventional facsimile machines, but also in various applications such as prepaid cards, point cards, tickets, ski lift tickets, merchandise percode labels, and medical films. It is used. In recent years, thermal recording systems are not limited to conventional facsimile machines, but also prepaid cards, point cards, tickets, ski lift tickets, per-code labels for products, medical films, etc. Now used in

 Accordingly, there is a need for records to be preserved even when exposed to various environmental conditions.

 In particular, when used as a card or film, it is often compounded with plastic, and the problem is that recording is lost due to the plasticizer of the plastic. Colorants are required. As a plasticizer-resistant developer, for example, the following formula

Although the bissulfonylprea derivatives represented by the following formulas have been disclosed (for example, Japanese Patent Application Laid-Open No. 5-148220, this does not necessarily satisfy all of the requirements). .

Also, a developer having a sulfonamide phenol is disclosed as having a good storage stability of the ground color (for example, see Japanese Patent Application Laid-Open No. 2002-52835). This publication is not satisfactory in terms of plasticizer resistance and other properties as a color developer.

 As a developer having a pyrazole skeleton similar to the compound of the present invention, the following formula:

Are disclosed (for example, Japanese Patent Application Laid-Open No. 2000-239555), but they do not have sufficiently satisfactory performance. Disclosure of the invention

 Under such circumstances, the present invention has a thermosensitive coloring layer using a novel color developer, which exhibits resistance to various environmental conditions, especially plasticizers of plastics, and enables long-term recording and storage. It is an object of the present invention to provide a heat-sensitive recording medium and a novel compound useful as the developer.

 The present inventors have conducted intensive studies to achieve the above object, and as a result, using a compound having a specific partial structure as a developer that reacts with a dye precursor under heating to form a color. As a result, a thermosensitive recording medium suitable for the purpose can be obtained, and the specific benzenesulfonamide derivative having the above partial structure is a novel compound, and is extremely useful as the color developer and the like. Was.

 The present invention has been completed based on such findings.

 That is, the present invention

(1) A colorless or light-colored dye precursor on a support, and A heat-sensitive coloring layer containing a color developing agent that reacts with the precursor to develop the color; and the color developing agent is represented by the formula (I)

Is a compound having at least one partial structure represented by

Heat-sensitive recording medium,

(2) The partial structure is represented by the general formula (II)

[Wherein, R ² may be substituted with a hydrogen atom, a halogen atom, a 〇-〇 alkyl group, a C i C ₄ haloalkyl group, a C ₃ -C ₆ cycloalkyl group, a halogen atom or a C-dialkyl group. Shows a good phenyl group. ] The heat-sensitive recording material according to the above (1), which has a structure represented by the following formula:

(3) The developer is represented by the general formula (III)

[In the formula, R ¹ represents a halogen atom, C -C ₄ alkyl or C i~C ₄ Haroa alkyl group, 1 ³ or a hydrogen atom. ₁ to. _An alkyl group, n represents an integer of 0 to 3, and R ² is as defined in the formula (II). ]

The thermosensitive recording material according to (2), which is a benzenesulfonamide derivative represented by

(4) The developer is represented by the general formula (IV)

Wherein R ¹ is substituted with a halogen atom, a C alkyl group or a C ₁ -〇 ₄ haloalkyl group, R ⁴ is substituted with a hydrogen atom, a C 1 -C ₈ alkyl group or a halogen atom or a C i -C ₄ alkyl group. Or a general formula

(a)

(In the formula, Y represents a halogen atom or a C i -C ₄ alkyl group, and m represents 0, 1 or 2.)

And n represents an integer of 0 to 3, and R ² is as defined in the general formula (II). ]

The thermosensitive recording material according to (2), which is a benzenesulfonamide derivative represented by

 (5) The developer is represented by the general formula (V)

Wherein R ¹ is a halogen atom, a C i C alkyl group or a C i C ₄ haloalkyl group, and A is a C ₃ -C ₈ divalent optionally substituted by a C i -C ₄ alkyl group. A cycloalkyl ring, C _{7 to} C i which may be substituted with a C _{4 to} alkyl group; A divalent bicyclic alkyl ring, substituted with a C i -C ₄ alkyl group A divalent tricyclic alkyl ring of c _{10 to} c ₁₄ which may be substituted, a divalent aromatic ring which may be substituted with a halogen atom or a ci to c ₄ alkyl group, or a straight chain. Represents a C _{2 to} C ₂₂ divalent alkyl chain, which may be branched or branched; and a divalent aromatic ring and a C _{2 to} C ₂₂ divalent alkyl chain further include an oxygen atom, sulfur atoms, one S 0 ₂ -, -NHCO-, one NHCONH one, one NHC SNH-, divalent cycloalkyl ring C ₃ -C _8, Ji? ~ Ji divalent Bishiku port alkyl ring E 0 may contain divalent tricycloalkyl ring C ₁₀ -C ₁₄ as a partial structure. n represents an integer of 0 to 3, and R ² is as defined in formula (II). ]

The thermosensitive recording material according to (2), which is a benzenesulfonamide derivative represented by

(6) The partial structure is represented by the formula (VI)

The thermal recording medium according to the above (1), having a structure represented by:

 (7) The developer is represented by the general formula (VII)

[In the formula, R ¹ represents a halogen atom, an alkyl group or a lower alkyl group, X ¹ and Y ¹ are each independently an oxygen atom, a sulfur atom, one S 0 ₂ - one NR ⁵ - and - CR ⁶ R ⁷ — Is a divalent group selected from — Z is a single bond or an oxygen atom, a sulfur atom, one S〇 ₂ —, — NR ⁸ —, one (CR ⁹ R ¹⁰ ) _a —, one C (= O), and one It represents a divalent group selected from C (= S).

R ⁵ to R ^{1 G} are each independently a hydrogen atom, Ci C alkyl group, Ji To c ₄ haloalkyl group, c ₃ shows a to c ₆ consequent opening alkyl group or a halogen atom or a C i~C ₄ alkyl phenylene Le group may be substituted with a group, a and n are each 0-3 Indicates an integer.

When both of them are one NR ⁵ — or _CR ⁶ R ⁷ —, Z represents a single bond.

However, X ¹ or Y ¹ is an oxygen atom, a sulfur atom, one S 0 ₂ - or one NR ⁵ - in the case where, Z is one _{^{(CR 9 R 10) a -}} , -C (= 0) or one Indicates C (= S). ]

The thermosensitive recording material according to (6), which is a benzenesulfonamide derivative represented by

 (8) The developer is represented by the general formula (VIII)

[In the formula,! ^ ¹¹ to! ^ ¹⁶ are each independently substituted with a hydrogen atom, an alkyl group, a C i -C ₄ alkyl group, a C ₃ -C ₆ cycloalkyl group, a halogen atom or a C -dialkyl group. shows good phenylene Le group optionally, I ^{1 1,} R ^12, and R ¹⁵ or R ^16, may be R ¹³ or R ¹⁴ forms a together a connexion chemical bond or I ^{1 1,} R and ^{1 2,} R ¹⁵ or R ^16, R ^{1 3} or a together R ¹⁴ connexion, together with the carbon atom to which each is attached, may be substituted with halo gen atom or a C E ~ Ji alkyl group A benzene ring structure may be formed.

Scales ¹ and 11 are as defined in general formula (VII). ]

The thermosensitive recording material according to the above (7), which is a benzenesulfonamide derivative represented by (9) The developer has the general formula (IX)

[In the formula, R ¹ is a halogen atom, a C i -C ₄ alkyl group or a C i -C ₄ haloalkyl group, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a C ₁ -C ₄ alkyl group , C ₁ ~0 ₄ C port alkyl group, C ₃ -C ₆ shows a cycloalkyl group or a halogen atom or a C i~C ₄ alkyl a phenyl group which may be substituted with a group, n represents an integer of 0 to 3 Show. ]

The thermosensitive recording material according to (6), which is a benzenesulfonamide derivative represented by

 (10) The developer is represented by the general formula (X)

Wherein R ¹ represents a halogen atom, a C-alkyl group or a C haloalkyl group, R ¹⁹ represents a halogen atom, a C i C alkyl group or a C haloalkyl group, n represents an integer of 0 to 3, R ² is as defined in general formula (II). ]

The thermosensitive recording material according to (2), which is a benzenesulfonamide derivative represented by

 (1 1) General formula (III)

Wherein R ¹ is a halogen atom, a Ci-C ₄ alkyl group or a C-C ₄ haloalkyl group, R ² is a hydrogen atom, a halogen atom, a C-C ₄ alkyl group, a C-C ₄ haloalkyl group, ₃ -C ₆ Shikuroanorekiru group or a halogen atom or a C ~ Ji optionally substituted Fuweniru group with an alkyl group, R ³ is a hydrogen atom or a C i~C ₈ alkyl radical, n is an integer of 0 to 3. ]

A benzenesulfonamide derivative, having a structure represented by

(1 2) —General formula (IV)

Wherein R ¹ is a halogen atom, a C-C ₄ alkyl group or a C i-C ₄ haloalkyl group, R ² is a hydrogen atom, a halogen atom, a C-alkyl group, a C i-C

₄ C alkyl group, C ₃ -C ₆ alkyl group or halogen atom or

C -C ₄ alkyl which may be substituted phenyl group with a group, R ⁴ is a hydrogen atom,

A phenyl group which may be substituted by a C ₈ -C ₈ alkyl group, a halogen atom or a C 1 -C ₄ alkyl group, or a general formula (a)

(Wherein, Y represents a halogen atom or a C i -C ₄ alkyl group, m represents 0, 1 or 2), and n represents an integer of 0-3. ]

A benzenesulfonamide derivative, having a structure represented by

(13) General formula (V)

Wherein R ¹ is a halogen atom, a C i -C ₄ alkyl group or a C -C ₄ haloalkyl group, R ² is a hydrogen atom, a halogen atom, a Ci C alkyl group, a C i -C ₄ haloalkyl group, C ₃ -C ₆ consequent opening alkyl group or a halogen atom or a C ₁ -C ₄ alkyl a phenyl group which may be substituted with a group, A is C i~C ₄ alkyl C ₃ optionally substituted with -C ₈ divalent consequent opening alkyl ring, C ~ C ₄ good C ₇ substituted with an alkyl group ~ C. Divalent Bishiku port alkyl ring, a divalent tricycloalkyl ring Ci～c ₄ alkyl optionally substituted with one C ₁₀ -C _14, optionally substituted with a halogen atom or Ci～c ₄ alkyl group indicates also be a divalent aromatic ring or a divalent linear alkyl chain is a good C ₂ even those having branching also to c _22, divalent Kaoru aromatic ring and C ₂ ~ divalent alkyl chain of C ₂₂ is further oxygen atom, a sulfur atom, - S_〇 ₂ - one NHCO_, one -NHCONH- one NHC S NH-, C ₃

Divalent consequent opening alkyl ring ~c _8, c ₇ ~ci. And a divalent tricycloalkyl ring of c _{1C) to} ci ₄ as a partial structure. n shows the integer of 0-3. ]

A benzenesulfonamide derivative having a structure represented by

One CH2CH2CH2CH2CH2CH2

A benzenesulfonamide derivative according to the above (13), which has a structure represented by the following formula:

(1 5) —General formula (VII)

[In the formula, R ¹ represents a halogen atom, C i C alkyl group or 0 _{1-0 4} Haroa alkyl group, ¹及Pi丫¹ are each independently an oxygen atom, a sulfur atom, one S 0 ₂ -, - NR ⁵ _ and-a divalent group selected from CR ⁶ R ⁷ —, Z is a single bond or an oxygen atom, a sulfur atom, — S 0 ₂ —, — NR ⁸ _, — (CR ⁹ R ¹⁰ ) _a —, — It represents a divalent group selected from C (= 0) and 1 C (= S).

R ^{5 to} R ^{1 C)} are each independently a hydrogen atom; And an alkyl group, a C ₄ haloalkyl group, a C ₃ -C ₆ alkyl group or a phenyl group which may be substituted with a halogen atom or a C i C alkyl group, wherein a and n are respectively Indicates an integer from 0 to 3. When X ¹ and Y ¹ are both _NR ⁵ — or one CR ⁶ R ⁷ —, Z represents a single bond.

However, X ¹ or Y ¹ is an oxygen atom, a sulfur atom, _ S 0 ₂ - or one NR ⁵ - in the case of, Z is one _{^{(CR 9 R 10) a -}} , - C (= 0) or _C (= S). ]

A benzenesulfonamide derivative having a structure represented by the following formula (16):

[In the formula, R ¹ represents a halogen atom, a C i -C ₄ alkyl group or a C i -C ₄ halo phenol.

! ^ ¹¹ ~! ^ ¹⁶ each independently represents a hydrogen atom, an alkyl group, a C _{4 to} haloalkyl group, a C _{3 to} C ₆ cycloalkyl group, a halogen atom, or a phenyl which may be substituted with a C 1 to C ₄ alkyl group. R ¹ \ R ¹² , R ¹⁵ or R ¹⁶ and R ¹³ or R ¹⁴ may be combined together to form a chemical bond, and I ¹¹ , R ¹² , R ¹⁵ Or R ¹⁶ and R ¹³ or R ¹⁴ may be taken together to form a benzene ring structure which may be substituted with a halogen atom or a C i C alkyl group, together with the carbon atom to which each is bonded. . ]

A benzenesulfonamide derivative having a structure represented by the following formula (17):

Wherein R ¹ is a halogen atom, a C ₁ -C ₄ alkyl group or a C 1-ハ ロ₄ haloalkyl group, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, a C i C alkynole group, It represents a C i C-opening alkyl group, a C ₃ -C ₆ cycloalkyl group or a phenyl group which may be substituted with a halogen atom or a C i -C ₄ alkyl group, and n represents an integer of 0-3. ]

A benzenesulfonamide derivative having a structure represented by the following formula: BEST MODE FOR CARRYING OUT THE INVENTION

 The heat-sensitive recording material of the present invention has a heat-sensitive coloring layer containing a colorless or light-colored dye precursor, and a developer that reacts with the dye precursor under heating to develop the color on a support. I have.

 The colorless or light-colored dye precursor used in the thermosensitive coloring layer is not particularly limited, and may be any of known dye precursors conventionally used in the thermosensitive coloring layer of a thermosensitive recording medium. Can be selected and used.

Such dye precursors include, for example, triphenylmethane-based, diphenylmethane-based, fluoran-based, phenothiazine-based, auramine-based, and spiropyran-based compounds. Ethoxyphenyl) 1-3- (1-Ethyl-2-methylindole-3-yl) —4-azaphthalide; 3,3-bis (p-dimethylaminophenyl) monophthalide; 3,3- Bis (p-dimethylaminophenyl) -1-6-methylaminophthalide (common name: crystal violet lactone); 3: 3—Bis (p-dimethinoleaminopheninole) -1 6—Jetylaminophthalide; 3,3—Bis (p—dimethinoreaminopheninole) 16—Chronolephthalide; 3,3-bis (p-dibutyl) 3-amino-hexylamino-6-chlorofluorane; 3-dimethylamino-1,5,7-dimethylfluoran; 3-dimethylamino-7-methinolefluoran; 3-methylethylamino 6 3-Methyl-7-anilinofluoran; 3-Jetylamino-7-chlorofluoran; 3-Jetylamino7,8-Benzofuroran; 3-Jethylamino-6-methyl-17-chlorofluorane; 3- (N-p-to 6-methyl-1 7-anili-nof-noreolan; 3-piperidino-1 6-methinole 7-aeri-nofluoran 2— {N— (3′-Trifluoromethylphenyl) amino} -6-Jethylaminomethylfluoran; 2— {3,6-bis (Jethylamino) -1-9— (o-Chloranilino) Xanthine Benzo Acid lactam; 3-methylamino-6-methyl-7- (m-trichloromethylarino) fluoran; 3-ethylethylamino-7- (o-chloroanilino) fluoran; 3-dibutylamino-17- (o-chloroa- Rino) Fluoran; 3-N-methyl-1-N-amylamino_6-methyl-7-anilinofluoran; 3-N-Ethyl-N-isopentylamino-6-methyl-17-anilinofluoran; 3 — N-Methyl-1-N-cyclohexylamino _ 6-Methyl-7-anili-nofluorane; 3-Jetyl-6-methyl-1-7-anili-nofluoran; 3— (NN—Jetylamino) _ 5-Methyl-1 7- (N, N-dibenzylamino) phneoleane; Benzinolelecomene methylene phenolate; 6'-Chloro-8'-Methoxy-benzoindolinose pyropyran; 6'-Bromo-1 3'-Methoxy 1-Benzyndolinosepyropyran; 3- (2'-Hydroxy-1-4'-Dimethylaminoaminophenyl) -1-3- (2'-Methoxy-5'-Chlorophenyl) phthalide; 3- (2 ' -Hydroxy 4'-dimethylaminophenol 1) 3-(2'-Methoxy 1 5 '-2-Trophenyl) phthalide; 3-{2'-Hydroxy-1 4'-dimethylaminophenyl) 1 3-{2 '-Methoxy 5' 3-Methylphenyl) phthalide; 3- {2'-methoxy-1-4'-dimethylaminophenyl) -3- (2'-hydroxy-1-5'-chlorophenyl) phthalide; 3-morpholino-7- (N-propyl-1-trifluoromethylanilino) fluoran; 3-pyrrolidino_ 7-trifluoromethylanilynophnoleolane; 3-ethylaminoamino-5-chloro-7- (N-benzyltrifluoromethylol) Nilino) Fluoran; 3-piperidino-1 7- (di-p-chloro-mouth feninole) methinoleaminophnoleorane; 3- (N-ethinole_p-toluidino)-7-(a-phenylethylamino) Fluoran; 3 — Jech Amino 7— (o-Methoxycanolepoyulpheninoleamino) fluoran; 3-Jetylamino-1 5-methyl-7- (α-phenylethylamino) fluoran; 3-Jetylamino_7-pyridinofluoran; 2—Black mouth 3 _ (Ν-methyltoluidino) 1 7- (ρ- η-butylanilino) fluoran; 3-(Ν-benzinole 1 -cyclohexinoleamino) 1 5 6-benzo 1 7 _ 1-naphthinoleamino 1 4 '—promo Fluoran; 3-diethylenoamino 6_methyl_7—mesitidino 4,5'-benzofluoran, 3-—, Ν-di-η-butylylamino 6-methyl-17-anilinofluoroan, 3-Ν, Ν —Gee η—Pentylamino-1 6 _methyl-1 7—anilinofluoran, 2,2-bis (4- (6 "-(Ν-cyclohexyl Ν—methylamino) -1 3'-me Ruspiro (phthalid-1,3'9'-xanthen) _2'-ylamino) phenyl) propane etc. These dye precursors may be used alone or in combination of two or more. May be used.

On the other hand, in the present invention, as a developer which reacts with the dye precursor under heating to form a color, the following formula (I) is used in one molecule.

A compound having at least one partial structure represented by the following formula is used.

The partial structure represented by the formula (I) undergoes an interconversion called tautomerism as shown below.

 (I) (la) Accordingly, all compounds having a partial structure represented by the formula (I) used as a color developer in the present invention have an isomer based on this tautomerism. Is not limited to a specific isomer and may be any isomer or a mixture of isomers.

Note that the partial structure represented by the formula (Π) undergoes interconversion called tautomerism as shown below.

 (II) (Ha)

In addition, the partial structure represented by the formula (VI) causes interconversion called tautomerism as shown below.

The compound having at least one partial structure represented by the formula (I) includes a compound represented by the general formula (II)

(II)

Wherein R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₄ alkyl group,

4 haloalkyl group, a C ₃ -C ₆ cycloalkyl group, a halogen atom or a Ci～ C ₄ alkyl phenylene Le group may be substituted with a group. ]

And a compound having at least one partial structure represented by

In the general formula (Π), the halogen atom of R ² includes fluorine, chlorine, bromine and iodine atoms, and the C _{1 to} C ₄ alkyl group includes a methyl group, an ethyl group, an n-propyl group, Examples include an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. The haloalkyl group includes an alkyl group in which the hydrogen atom of the C04 alkyl group is appropriately substituted with a halogen atom as described above.

C ₃ -C ₆ cycloalkyl groups include cyclopropyl group, cyclobutyl group Group, consequent opening pentyl group, hexyl group and the like to the consequent opening, as the c ₁ to c ₄ Al kills a phenyl group which may be substituted with a group, for example, phenyl group a tolyl group, a xylyl group, Echirufuweeru group, Examples thereof include an n-propylphenyl group, an isopropynolepheninole group, an n-butynolephenyl group, a tert-butylphenyl group and the like.

 Further, the compound having at least one partial structure represented by the formula (I) includes a compound represented by the formula (VI)

And a compound having at least one partial structure represented by

In the present invention, the developer comprising a compound having at least one partial structure represented by the formula (I) in one molecule includes, for example, a general formula (in), a general formula (IV), a general formula (IV) Formula (V), Formula (VII), Formula (VIII), Formula (IX) and Formula (X)

61

600 contract zdf / e :) d ΐ6οεπ contract OA A benzenesulfonamide derivative represented by

In the general formula (III), R ¹ is a halogen atom, a Ci-C ₄ alkyl group or a C-C ₄ alkyl group, R ³ is a hydrogen atom or a C-C ₈ alkyl group, and n is 0-3. And R ² is the same as described above.

The halogen atom, alkyl group and dialkyl group in R ¹ are as described for R ² in the formula (II).

C E ~ Ji i ₈ alkyl groups are straight-chain of R ^3, may be either branched, and examples thereof include methyl group, Echiru group, n- propyl group, isopropoxy Ropinore group, various butyl Groups, various pentynole groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, and the like.

When R ¹ is a plurality, the plurality of R ¹ may be the same or different.

In the general formula (IV), R ⁴ represents a hydrogen atom, a di-to-dialkyl group, a halogen atom or a fuel group which may be substituted with a C i-C alkyl group, or the general formula (a)

(In the formula, Y represents a halogen atom or a C i -C ₄ alkyl group, and m represents 0, 1 or 2.)

Wherein R ¹ , R ² and n are the same as described above.

Halogen atom in R ^4, CC alkyl group, a halogen atom or

C ₁ -C ₄ alkyl a phenyl group which may be substituted with a group, C i~C ₄ Al kill group is as described above.

When there are a plurality of Ys, the plurality of Ys may be the same or different. In the general formula (V), A is substituted with a C, -C ₄ alkyl group. C ₇ to C ₈ which may be substituted by a C ₃ to C ₈ divalent cycloalkyl ring or a C to C ₄ alkyl group. Divalent Bishiku port alkyl ring, a divalent Torishikuroaru kill ring C I～c ₄ alkyl which may be substituted by a group c ₁₀ to c _4, may be substituted by Nono androgenic atom or a C alkyl group divalent aromatic ring or be linear represents a divalent alkyl chain optionally c ₂ to c ₂₂ be one having a branched, divalent aromatic ring及Pi c ₂ to c ₂₂ divalent alkyl chain of further oxygen atom, 'sulfur atom, _ S_〇 ₂ - one NHC O-one -NHCONH- one NHC S NH-, a divalent cycloalkyl ring C ₃ -C ₈ , C ₇ ~C. Divalent bicycloalkyl ring may contain divalent tricycloalkyl ring C ₁₀ -C ₁₄ as a partial structure. R ¹ , R ² and n are the same as described above. ,

The aromatic ring of C i~C ₄ alkyl or divalent optionally substituted with a halogen atom of A, for example,

And the like.

Further, the C _{2 to} C ₂₂ divalent alkyl chain may be linear or branched, and specific examples thereof include:

One CH ₂ CH ₂ One One CH ₂ CH ₂ CH ₂ CH ₂ — CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -One Hs ^ Hs ^ H H H ゥ Grl GH GHsGH i ^ Hs One ^ ri ゥ v ^ rlu OGHs

— CH ₂ CH ₂ SCH ₂ CH ₂ ^ — CH ₂ CH ₂ S0 ₂ CH ₂ CH ₂ — CH ₂ CH ₂ NHC (0) CH ₂ CH ₂ CH ₂ CH ₂ NHCONHCH ₂ CH ₂ z — CH CH ₂ NHCSNHCH ₂ CH ₂ one

And the like.

 A is

Those having a structure represented by In the general formula (VII), R ¹ is a halogen atom, Ci C alkyl group or C ₁ -C ₄ haloalkyl group, X ¹及Pi Y ¹ are each independently an oxygen atom, a sulfur atom, one S_〇 ₂ - , - NR ⁵ - and -CR ⁶ R ⁷ - divalent group selected from, Z is a single bond or an oxygen atom, a sulfur atom, one ^{_{S 0 2 -, -NR 8 -}} - (CR 9 R 10) a - , — Represents a divalent group selected from C (= 0) and 1 C (= S).

RSR ¹⁰ are each independently a hydrogen atom, CCA alkyl group, -C ₄ haloalkyl group, C ₃ -C ₆ consequent opening alkyl group or a halogen atom or a C _t -C ₄ optionally substituted with an alkyl group phenylene And a and n each represent an integer of 0-3.

When 1 and ¹ are both one NR ⁵ — or one CR ⁶ R ⁷ —, Z represents a single bond.

However, when X ¹ or Y ¹ is an oxygen atom, a sulfur atom, —S 0 ₂ — or —NR ⁵ —, Z is one (CR ⁹ R ¹⁰ ) _a —, -C (= 0) or — Indicates C (= S). '

A halogen atom for R ¹ , a 〇 to ア ル キ ル alkyl group, _{1-0 4} C port al kill group is as described by R ² in the general formula ([pi).

In the general formula (VIII), R ¹ is a halogen atom, a C ₁ -C ₄ alkyl group or a C i C alkyl group, R ¹ -R ¹⁶ are each independently a hydrogen atom, a 〇-〇 alkyl group, ₁ ～〇 ₄ C port alkyl group, C ₃ -C ₆ cycloalkyl group or a halogen atom or a C I～C ₄ alkyl a phenyl group which may be substituted with a group, scale ^{1 1,} R ^12, R ^{1 5,} or R ¹⁶ and R ¹³ or R ¹⁴ may together form a chemical bond, and R ¹ R ¹² , R ¹⁵ or R ¹⁶ and R ¹³ or R ¹⁴ may be bonded together to form a chemical bond. Together with the carbon atom, a benzene ring structure which may be substituted with a halogen atom or a C ₁ -C ₄ alkyl group may be formed. 1 ¹及Pi ₁ 1 is as defined in formula (VII).

In the general formula (IX), R ¹ is a halogen atom, a C i C alkyl group, or And R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group, a C _{4 to} C ₄ alkyl group, a C _{3 to} C ₆ cycloalkyl group or a halogen atom or Ci to It represents a phenyl group which may be substituted with a C ₄ alkyl group.

 Thank you! ! Is as defined in general formula (VII).

In the general formula (X), R ¹⁹ represents a halogen atom, an alkyl group, or a C ₄ -C ₄ haloalkyl group.

as well as! ! Is as defined in general formula (III). R ² is as defined in general formula (II).

Specific examples of the compound represented by the general formula (III) include N- (5-hydroxy-13-methyl-1H-pyrazole-4-1-carbonyl) -14-methylbenzenesulfonamide and the like. Specific examples of the compound represented by the general formula (IV) include: 5-hydroxy-13-methyl-41 (toluene-14-snorlehoninoleaminocanoleboninole) -pyrazonole-11 Acid butynoleamide, 5-hydroxy-3-methinole 4-1 (tonolene-14-snorlephoninoleaminocarbonyl) monopyrazole-1-carboxylate, 5-hydroxy-13-methinoleate 4-1 (toluene-14-norolephonyla) Minocarbyl) 1-pyrazole-1 O-octadecylamide rubonic acid, 5-hydroxy- 3-methinole 4 _ (toluene 4- 4-snolehoninoleamino) Specific examples of the compound represented by the general formula (V) include canoleponyl) -pyrazo / le 1-carboxylate phenylamide, and the like. 1,6-bis [5-hydroxy-3-methyl 4- (Toluene-1-4-sulfonylaminocarbonyl) 1-pyrazole-1-carbonylamido] hexamethylene, 4,4,1-bis [5-hydroxy-13-methyl-1-41 (toluene-4-sulfonylamino) Power report G) monopyrazole-1-carbonylamino] diphenylmethane and the like.

 Specific examples of the compound represented by the general formula (VII) include the following compounds.

LZ

llZ600 / ^ 00idf / X3d I60 £ ll / 00∑ OAV

In the compound represented by the general formula (VIII), and R ¹¹ R ^12, R ¹⁵ or R ^16, specific examples of compounds R ¹³ or R ¹⁴ forms a connexion chemical bonds such together May include the following compounds.

Further, in the compound represented by the general formula (VIII), R ¹¹ R ¹ R ¹⁵ or R ¹⁶ and R ¹³ or R ¹⁴ are taken together to form a halogen atom together with a carbon atom to which each is bonded. or specific examples of C i~C ₄ be substituted with an alkyl group is also optionally phenyl group compound include the following reduction compounds like.

 In the present invention, the above-mentioned general formula (III), general formula (IV), general formula (V), general formula (VII), general formula (VIII), general formula (IX) and One of the compounds represented by formula (X) may be selected and used alone, or two or more may be selected and used in combination.

 Further, the color developer of the present invention may further contain another color developer as an auxiliary color developer.

 Specific examples of the auxiliary color developer include the following compounds.

B i TU

 One of these auxiliary colors may be used alone, or two or more of them may be used in combination.

 The amount of the developer of the present invention is selected in the range of generally 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, per 1 part by mass of the colorless or pale color dye precursor. .

 The amount of the auxiliary color developer used is generally selected in the range of 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass with respect to 1 part by mass of the colorless or pale color dye precursor. .

 The thermosensitive coloring layer of the thermosensitive recording medium of the present invention contains, in addition to the dye precursor and the developer, a sensitizer and a binder such as a binder for binding various components on a support. Can be.

Examples of the sensitizer include stearic acid amide, 1-hydroxyl-2-naphthoic acid phenyl ester (Japanese Patent Application Laid-Open No. 57-191809), p-benzylbiphenyl (special Japanese Patent Application Laid-Open No. 60-82, 382, Japanese Patent Application Laid-Open No. 59-9092, p-Acetate Toluide (Japanese Patent Application Laid-Open No. 59-9902), 2-benzyloxynaphthalene (Japanese Patent Application Laid-Open No. 58-8) Japanese Patent Application Laid-Open (JP-A) No. 74904), oxalic diesters (JP-A-64-15883), benzyl p-benzyloxybenzoate (JP-A No. JP-A-57-148688, JP-A-2016691), 1,2_bis (m-tolyloxy) ethane (JP-A-60-56588), dibenzyl terephthalate (JP-A-58-98285), diphenyl carbonate, ditolyl carbonate (JP-A-58-136489), m-Tafel (JP-A-57-89994) ), 1,5-bis (p-methoxyphenoxy) -3-oxapentane (Japanese Patent Application Laid-Open No. Sho 62-181183), 1,4-bis (p'-tolyloxy) benzene (Japanese Patent Application Laid-Open No. 2-1535783), diphenylsulfone (Japanese Patent Publication No. 59-25673), p-toluenesulfonate phenyl ester (JP-A-59-73990) , Mesitylene sulfonic acid mono-p-tolyl ester (Japanese Patent Application Laid-Open No. 2-828085), 4,4′-diarinoleoxydiphenylsulfone, 4,4′-diisopene Noreoxydiphenylenoles / lephon, 4, 4'-Dimethoxydiphenylenolesnorefone (Japanese Patent Publication No. 2-9951), 4,4'-Di-n-pentyloxydiphenyl sulfone (Japanese Unexamined Patent Publication No. 60-47070) and p-toluenesulfonamide (Japanese Patent Publication No. 11-245524). These may be used alone or in a combination of two or more.

On the other hand, as the binder, for example, celluloses such as casein, gelatin, starch and derivatives thereof, methinoresenorelose, methoxycellulose, hydroxyshethylcellulose and carboxymethylcellulose, polyvinyl alcohol of various molecular weights andぴ Derivatives, sodium polyacrylate. Poly (vinylpyrrolidone), acrylamide (acrylic ester copolymer) .Acrylic acid amide (acrylic ester / methacrylic acid terpolymer, styrene / maleic anhydride) Acid copolymer alkali salt, water-soluble polymer materials such as polyacrylamide, sodium alginate, polybutyl acetate, polyurethane, styrene-butadiene copolymer, polyacrylic acid, polyacrylic ester Latex or solvent-soluble polymer materials such as ethylene chloride, vinyl chloride / butyl acetate copolymer, polybutyl methacrylate, ethylene / butyl acetate copolymer, styrene / butadiene / acrylic copolymer. .

 These may be used alone or in a combination of two or more.

 The heat-sensitive coloring layer of the heat-sensitive recording medium of the present invention may further contain various additives and auxiliaries as needed.

 Specifically, as a filler, calcium carbonate and surface-treated carbonic acid ruthenium, white carbon (silica), zinc oxide, titanium oxide, aluminum hydroxide, alumina, zinc hydroxide, barium sulfate, clay, calcined Examples thereof include inorganic fine powders or pigments such as talc, and organic fine powders such as urea-formalin resin, styrene-methacrylic acid copolymer, and polystyrene resin.

 In addition, higher fatty acid metal salts such as zinc stearate and calcium stearate are used to prevent thermal head abrasion and stateing, and are also used as antioxidants or ultraviolet absorbers. For this purpose, for example, a phenolic compound and a benzotriazole-based compound having the following structure can be added.

 1, 1, 3-tris (2-methinole _ 4-hydroxy-1-5-cyclohexyl fuinole) butane

4, 4 'butylidene-bis (6-t-butyl-3-methylpheno ^ " Nore)

 2, 2'-methylenebis (4-methinole-6-t-butynolephenol)

 OH OH

Me Me

2-—Methinolefeninole) benzotriazole

 -Methylenebis [4- (1,1,3,3-tetramethylbutyl (2H-benzotriazole-1-yl) phenol]]

The method for forming the heat-sensitive coloring layer in the heat-sensitive recording medium of the present invention is not particularly limited, and a conventionally known method, for example, the above-mentioned components constituting the heat-sensitive coloring layer are finely divided and mixed at an appropriate ratio. Disperse in water or solvent to generate heat A method of preparing a coating solution for forming a color layer, coating the solution on a support, and drying the solution can be used.

 The thickness of the heat-sensitive coloring layer thus formed is selected in the range of usually 0.1 to 100 μm, preferably 0.5 to 50 μm.

 Paper is mainly used as the support, but in addition to paper, various woven fabrics, non-woven fabrics, synthetic resin films, synthetic resin laminated paper, synthetic paper, metal foil, vapor-deposited sheets, or lamination of these materials The composite sheet combined with the above can be used arbitrarily according to the purpose.

 Further, if necessary, a protective layer and a coating layer such as a printing layer can be formed on the thus formed heat-sensitive coloring layer.

 The thus-prepared thermosensitive recording medium of the present invention, by using a novel color developer, exhibits resistance to plastic plasticizers in particular, and enables long-term recording and storage.

 Applications include facsimile paper and word processing paper, CRT image printer paper, recording paper and recording film for medical measuring instruments, thermal recording type tickets for automatic ticket vending machines, and coupons that require storage. It is also useful as cards, labels, receipts, etc., such as card and commuter pass or prepaid cards, point cards, tickets, ski lift tickets, barcode labels for products, and barcode system labels for POS.

 The present invention also provides a benzenesulfonamide derivative represented by the general formula (III), the general formula (IV), the general formula (V), the general formula (VII), the general formula (VIII) or the general formula (IX) Also provide.

 These benzenesulfonamide derivatives are novel compounds not described in the literature, and are useful as a developer or the like used in the thermosensitive coloring layer of the thermosensitive recording medium, as described above.

These compounds can be produced according to the following scheme. [Production of compound represented by general formula (I II)]

 Scheme 1: R is a lower alkyl group such as a methyl group or an ethyl group,

R ³ and n have the same meaning as described above.

R ³ NHNH

 O,, one

R _¾ ' ₂ ~ ^(ΧΙ) >

^W

 (III)

 First, an acetoacetic ester represented by the formula (X) is reacted with a hydrazine represented by the formula (XI) to produce a pyrazolone of the formula (XI I).

 It is preferable to react the compound represented by the formula (X) with an equivalent amount or more of (XI).

 This step is carried out in a solvent inert to the reaction, for example, an alcoholic solvent such as ethanol or methanol, an ethereal solvent such as tetrahedrofuran or dimethoxyethane, or a halo such as dimethylene chloride or dichloroethane. The reaction may be performed using an aromatic solvent such as a benzene-based solvent, toluene, or xylene, or may be performed without a solvent.

 The reaction temperature is not particularly limited, but usually the reaction proceeds smoothly from room temperature to about 80 ° C.

 Subsequently, the pyrazolone of the formula (XII) obtained in the step 1 is reacted with the sulfonylisocyanate of the formula (XIII) to obtain a compound of the general formula

The compound represented by (III) is obtained.

Here, with respect to the pyrazolones represented by the formula (XII), a sulfonyl isocyanate represented by the formula (XII I) is used in an equivalent amount or more, and a solvent inert to the reaction, for example, 1,4-dioxane, Solvents such as acetonitrile, tetrahydrofuran, tonolen, shiridani methylene, dichloroethane, and benzene The reaction is preferably performed in a medium.

 The reaction temperature is not particularly limited, but usually the reaction proceeds smoothly in the range of 0 ° C to 10 ° C.

 In addition, the reaction can proceed more smoothly by coexisting a weak base such as carbon dioxide, sodium carbonate or triethylamine depending on the solvent used.

 [Production of compounds represented by general formulas (IV) and (V)]

Scheme 2: R ¹ , R ² , R ⁴ , A and n have the same meaning as described above.

First, in Scheme 1, a compound represented by the formula (Ilia) is obtained by using a hydrazine represented by the formula (XI) in which R ³ is hydrogen.

 By reacting this (Ilia) with an isocyanate represented by the formula (XIV) in an equivalent amount or more, the compound represented by the general formula (IV) is converted to a diisocyanate represented by the formula (XV). Is reacted with 2 equivalents or more to obtain a compound of the general formula (V).

All are solvents inert to the reaction, for example, 1,4-dioxane, It is preferable to carry out the reaction in a solvent such as acetonitrile, tetrahydrofuran, toluene, methylene chloride, dichloroethane, and benzene. The reaction temperature is not particularly limited, but usually the reaction proceeds smoothly in the range of 0 ° C to 10 ° C.

 The reaction proceeds more smoothly by coexisting a weak base such as triethylamine.

 [Production of compound represented by general formula '(VII)]

Scheme 3: R ¹ , X ¹ , Y ¹ and n have the same meaning as described above.

 (XVI)

 (VII) When the 1,3-dicarbonyl compound represented by the formula (XVI) is reacted with the sulfonyl isocyanate represented by the formula (XVII), the compound represented by the general formula (VII) is obtained. Can be

 Here, a reaction inert solvent such as 1, The reaction is preferably carried out in a solvent such as 4-dioxane, acetonitrile, tetrahydrofuran, tonolene, methylene chloride, dichloroethane, and chlorobenzene.

 The reaction temperature is not particularly limited, but the reaction usually proceeds smoothly in the range of 0 ° C to 10 ° C.

Also, depending on the solvent used, for example, potassium carbonate, sodium carbonate, If a weak base such as triethylamine is used in an equivalent amount or more, the reaction proceeds more smoothly.

 In the same manner as described above, benzenesulfonamide derivatives represented by the general formulas (VIII), (IX) and (X) can also be produced.

Example

 Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

 Compound Production Example 1

 Production of N- (5-hydroxy-13-methyl-1H-pyrazole-4-carbon) _4-methyl-benzenesulfonamide (Compound No. 1)

Compound No. 1 At room temperature, 5-methyl-1-benzenepyrosazol-3-isone 0.50 _g Tonoleene 5 ml solution was added with 4-methyl-1-benzenesulfoninoleisocyanate 1.0 g, While stirring well, 0.50 g of triethylamine was gradually added dropwise.

 The reaction mixture was stirred at 80 ° C for 1 hour and separated into two layers.

The upper toluene layer was removed, a 5% by mass aqueous solution of hydrochloric acid was added, and the resulting crystals were separated by filtration and dried to obtain 1.35 _g (yield 90%) of the target compound.

 Melting point: 2 1 2. 4- 214.6 ° C

¹ H-NMR (acetone-d ₆ ): 2.40 (3 H, s) 2.44 (3 H, s) 7.42 (2 H, d) 7.98 (2 H, d)

 Compound Production Example 2 '

5-hydroxy-1 3-methyl-1 4-1 (toluene 4-sulfonylamino Preparation of carbonyl) -pyrazole-1-butyl carboxylate (Compound No. 2)

 3-Methinole-5-oxo-4,5-dihydropyrazolone 11-butynoleamide carboxylate 0.50 g and 4-methinolebenzenesnorehonyisocyanate 0.50 g acetonitrile 5 m 0.5 Og of triethylamine was gradually added dropwise to 1 solution while stirring well. .

 The reaction mixture was stirred at 80 ° C for 1 hour, 5 mass. /. An aqueous hydrochloric acid solution was added, and the resulting crystals were separated by filtration and dried to obtain 0.995 g (yield 95%) of the desired compound. Melting point: 2 1 0.6-2 13.8 ° C

¹ H-NMR (acetone— d ₆ ): 0.95 (3 H, s) 1.2-1.9 (4 H, m) 2.45 (3H, s) 2.5 1 (3 H , s) 3.40 (2H, q) 7.45 (2H, d) 7.98 (2H, d)

 Compound Production Example 3

Preparation of 1,6-bis (5-hydroxy-13-methyl-4-1 (tonolene-14-sulfonylaminocarbonyl) -pyrazole-11-carbonylamino) hexamethylene (Compound No. 3) ''

 Disperse 10 g of N- (5-hydroxy-3-methyl-1H-pyrazole-4-carbonyl) -14-methyl-1-benzenesulfonamide in 10 Oml of acetonitrile and mix well Triethylamine 5. Added lg. To this, a solution of 2.9 g of hexamethylene diisocyanate in 10 ml of acetonitrile was gradually added dropwise.

 The reaction mixture was stirred at room temperature for 1 hour and added to a 5% by mass aqueous hydrochloric acid solution. The resulting crystals were separated by filtration and dried to obtain 7.6 g (yield 59%) of the desired compound.

 Melting point: 1 88.6-192.1 ° C

'H-NMR (DMS O-d ₆ ): 1.1—1.7 (8 H, m) 2.40 (3 H, s) 2.61 (3 H, s) 3.0—3 . 4 (4H, m) 7.43 (2H, d) 7.91 (2H, d)

 Compound Production Example 4

 5-Hydroxy_3-methyl-4_ (toluene-4-sulfonylaminocarbonyl) -pyrazole-1 monoethyl rubonate (Compound No.

4) manufacture

 Compound No.4

N- (5-Hydroxy_3-methyl-1H-pyrazole-4-carbonyl) ― 4-Methyl-benzenesulfonamide 1 g is dispersed in acetonitrile 10 ml, and ethyl isocyanate is stirred well. 0.24 g was added. The reaction mixture was refluxed for 2 hours. After standing overnight, the crystals were separated by filtration and dried to obtain 0.94 g (yield: 75%) of the desired compound.

 Melting point: 221.8-223.9 ° C

H-NMR (DMS 0- d ₆ ): 1.16 (3 H t) 2.36 (3

H, s) 2.40 (3H, s) 3.2—3.5 (2Hm) 7.43 (2H, d) 7.90 (2H, d)

 Compound Production Example 5

5-Hydroxy-1-3-methinole 4- (toluene 4-s-norephonylaminoaminocanolepodinole) -Production of pyrazole-'octadecylamide carboxylate (Compound No. 5)

 Compound No.5

N- (5-hydroxy-3-methyl-1H-pyrazole-4-carbonyl) 100 mg of 1,4-methyl-benzenesulfonamide and 100 mg of octadecylisosocyanate 10 Omg of 5 mg of acetonitrile solution at 80 ° C The mixture was stirred for 1 hour, a 5% by mass aqueous solution of hydrochloric acid was added, and the resulting crystals were separated by filtration and dried to obtain 180 mg (yield: 90%) of the desired compound. Melting point: 143.1-148.3 ° C

 Compound Production Example 6

 5-Hydroxy-1-3-methylinole 4- (Tonolen-1-4-snolefo-noreaminocarbonyl) -pyrazole-1-carboxylic acid feramide (Compound No 6)

 Compound No.6

N— (5-Hydroxy-1-3-Methinole 1 H—Pyrazole 4—Norreboninole) —4-Methyl-1-benzenesnorrenamide 1 O Omg and Phenylisocyanate 4 Omg Acetonitrile 4 m 1 The solution was stirred at 80 ° C for 1 hour, a 5% by mass aqueous hydrochloric acid solution was added, and the formed crystals were separated by filtration and dried to obtain 129 mg (yield: 92%) of the desired compound.

 Melting point: 232.1-234.0 ° C

 Compound Production Example 7

Preparation of 4,4'-bis [5-hydroxy-3-methyl-4- (toluene-4-snolephoninoleaminocanoleboninole) -pyrazonole-carbonylamino] diphenylmethane (Compound No. 7)

N- (5-Hydroxy-1-3-methyl-1H-pyrazole-4_carbinole) Disperse 10 g of 14-methyl-1-benzenesnolephoneamide in 50 ml of acetonitrile and stir. A solution of 4,4′-diphenylmethane diisocyanate (4.2 g) in acetonitrile (25 ml) was gradually added dropwise to this solution in which 5.1 g of triethylamine was added and dissolved.

 The reaction mixture was stirred at room temperature for 1 hour, a 5% by mass aqueous solution of hydrochloric acid was added, and the resulting crystals were separated by filtration and dried to obtain 12.4 g of a crude product, which was washed with hot ethanol. 9.4 g (yield 33%) of the compound was obtained.

 Melting point: 241.3-246.8 ° C

'H-NMR (DMS O- d 6): 2. 3 5 (6 H, s) 2. 4 0 (6 H, s) 3. 9 1 (2 H, s) 7. 24 (4 H, d ) 7.3—7.8 (8 H, m) 7.9 1 (4H, d) 10.0.8 (2 H, s) 1 0.95 (2 H s)

 Compound Production Example 8

 Preparation of 5- (toluene-1-4-sulfonylaminopropyl) -barbituric acid (compound No. 8)

 Compound No.8

 A 300 ml three-necked flask was charged with 3.8 g (0.03 monole) of vanolevic acid, and 100 ml of acetonitrile and 3.0 g (0.03 mol) of triethylamine were added. Dissolved.

While stirring well at room temperature, 6.0 g (0.03 mol) of p-toluenesulfonyl isocyanate was added dropwise over 10 minutes, and the reaction was carried out for another 16 hours. After washing with acetonitrile, depressurize Dried.

 About 1 liter of distilled water was added to the crystals to dissolve them, and insolubles were removed by filtration. Then, a 5% by mass aqueous hydrochloric acid solution was added to adjust the pH to 1, and the resulting crystals were filtered off and dried. Thus, 8.4 g (0.026 mol, yield: 87%) of the target compound was obtained.

_{^{X H- NMR (DMS O- d 6}} ): 7. 4 2 (2 H, d) 7. 9 8 (2 H, d)

Compound Production Example 9

Preparation of 2- (toluene-1- 4-sulfoninoleaminocarbonyl) -1,3-cyclohexanedione (Compound No. 9)

 Compound No. 9

 In a 1-litre three-necked flask, 50 g (0.45 monole) of 1,3-cyclohexanedione was charged, and 300 ml of acetonitrile and 62 ml (0.45 mol) of triethylamine were added. In addition, it dissolved.

 At room temperature and with good stirring, 69 ml (0.45 mol) of p-toluenesulfonyl isocyanate was added dropwise over 1 hour, and the reaction was continued for another 48 hours. Acetonitrile was removed under reduced pressure, 300 ml of ethyl acetate and 1 liter of distilled water were added to the residue, and the aqueous layer was separated.

 5 mass in separated water layer. /. An aqueous hydrochloric acid solution was added to adjust the pH to 1, and the resulting crystals were separated by filtration and dried to obtain 107 g (0.35 mol, yield 77%) of the target compound.

 Melting point: 1 8 2. 9— 1 84.7 ° C

^ -NMR (DMS O— d ₆ ): 1.91 (2H, q) 2.41 (3 H, s) 2.57 (4H, t) 7.46 (2H, d) 7.91 (2H, d)

 Compound Production Example 10

 N- (5-Hydroxy-1,3-dimethyl-1H-pyrazole-4-force rubonyl) -14 Methylenolebenzenesnolephonamide (Compound No. 10)

 Compound No.10

 A 5-Om1 eggplant flask was charged with 5.0 g of 2,5-dimethyl-1,3,4-dihydroxypyrazol-3-one and 50 ml of toluene, and charged with 4-methyl-1-benzenesulfonyl isocyanate 8 .8 g was added, and 6.8 g of triethylamine was gradually added dropwise with good stirring.

 Further, the reaction mixture was stirred at 80 ° C. for 1 hour, and separated into two layers. The upper toluene layer was removed, a 5% aqueous hydrochloric acid solution was added, and the resulting crystals were separated by filtration and dried to obtain 11.7 g of the desired compound (yield 84%).

 Melting point: 2 16.1-2 22.1 ° C

^{X H -NMR (DMS O - d} 6): 2. 3 3 (3 H, s) 2. 4 0 (3 H, s) 3. 3 7 (3 H, s) 7. 3 8 (2 H, d) 7.90 (2 H, d)

 Compound Production Example 11

Production of N- (5-hydroxy-1-phenyl-3-methyl-1H-pyrazole-4-carbonyl) -14-methyl-1-benzenesulfonamide (Compound No. 11)

 Compound No.11

In a 300 ml eggplant flask, 5.0 g of 2-phenyl-5-methinole-3,4-dihydropyrazol-3-one and 50 ml of toluene were charged, and 4-methyl-benzenesulfonyl isocyanate was charged. "5.7 g of triethylamine was added, and 4.3 g of triethylamine was gradually added dropwise with good stirring.

 Further, the reaction mixture was stirred at 80 ° C. for 1 hour, and separated into two layers. The upper toluene layer was removed, a 5% aqueous hydrochloric acid solution was added, and the resulting crystals were separated by filtration and dried to obtain 9.9 g (yield 92%) of the desired compound.

 Melting point: 1 1 0.1-1 1 6.9 ° C

¹ H-NMR (acetone-d ₆ ): 2.43 (3 H, s) 3.32 (3 H, s) 7.23-7.72 (7 H, m) 7.98 (2 H, d) Compound Production Example 1 2

 Preparation of 2,4-bis [5-hydroxy 3-methynoleic 4- (tonolene _ 4 -sulfonylaminocarbol) pyrazole-11-carbo-lamino] toluene (compound No. 12)

 Compound Να12

In a 200 ml 1 eggplant flask, add N— (5-hydroxy-3-3-methyl-1 H-Pyrazono-l-canolepol) 4-Methyl-benzenesulfonamide (Compound No. 1) 10 g (0.034 M), trilene_2,4-diisocyanate 3 g (0.017M) and 50m1 of acetonitrile,

The mixture was heated and refluxed at 100 ° C for 3 hours.

 After cooling, the generated crystals were filtered out, washed with acetonitrile, and dried under reduced pressure to obtain 11.7 g (yield 90%) of the target compound.

 Melting point: 180-180 ° C '

 'H-NMR CDM SO-de): 2.33 (6H, s) 2.40 (6H, s) 2.51 (3H, s) 7.29-7.48 ( 7 H, m) 7.91 (4 H, d)

 Compound Production Example 13

 Production of N- (5-hydroxy-13-fuel-1H-pyrazole-4-hydroxyl) -14-methyl-1-benzenesulfonamide (Compound No. 13)

 Instead of 5-methyl-2,4-dihydro-pyrazol-13-one as a raw material, 5_phenyl-2,4-dihido-pyrazol-3-one 30 obtained in Production Reference Example 1 described below was used. Except for using g, 63.7 g (yield: 95%) of the target compound was obtained in the same manner as in Production Example 1 described above.

Compound No.13

 Melting point: 1 7 6 — 1 7 7 ° C

'H-NMR (DMS O-d ₆ ): 2.37 (3 H, s) 7.2-8.0 (7 H, m) 7.85 (2 H, d) 1 1.5 ( 3 H, bs) IR (cm ^-1 ): 1 6 9 6, 1 6 73, 1 1 6 1

Compound Production Example 14

 4,4,1-Bis (5-hydroxy-3-phenenole 4-1 (tonorenen 4- _snolehoninoleaminocanoleponyl) -pyrazono-le-1-1-carboninoleamino) diphthyl methane (compound No. 14) Manufacturing of

 Compound Ν 14

 Example 13 was repeated in the same manner as in Production Example 12 except that Compound No. 13 was used as a starting material instead of Compound No. 1, and methylene bisphenyl diisocyanate (MDI) was used as the isocyanate. Thus, the target compound (yield 92%) was obtained.

 Melting point: 226—2 28 ° C

— NMR (DMS O— d ₆ ): 2.36 (6 H, s) 3.92 (2 H, s) 6.7 (4 H, bs) 7.2—7.9 (26 H , m) 1 1.25 (1 H, d) 1 1.85 (1 H, bs)

IR (cm ^-1 ): 1 74 1, 1 6 90, 1 1 6 2

Compound Production Example 15

Preparation of 2,4_bis [5-hydroxy-3-phenyl-14- (tonolene-4-sulfonylaminocanolepol) pyrazole-11-carbonylamino] toluene (Compound No. 15)

 Compound Να15

 Production Example 12 except that Compound No. 13 was used as a raw material instead of Compound No. 1 and tolylene 1,4-diisocyanate (TDI) was used as an isocyanate. In the same manner as in the above, the desired compound (83% yield) was obtained.

 Melting point: 1 69-17 2 ° C

^ -NMR (DMS 0- d ₆ ): 2.37 (9 H, s) 6.7 (4 H, bs) 7.3-8.0 (2 1 H, m) 2 2.25 ( 1 H, d) 1 1.3 (1 H, d) 1 1.80 (1 H, d)

IR (cm ^-1 ): 1 7 6 0, 1 6 9 9, 1 1 6 6

Compound Production Example 16

1,6-bis (5-hydroxy_3-phenyl_4- (tonolene-1-4-sulfonylaminocarbonyl) -pyrazole-1-carbonylamino) hexamethylene (compound N o ,. 16) Manufacture

 Compound No. 13 was used in place of compound No. 1 as a raw material, and hexamethylene diisocyanate (HMD I) was used as the isocyanate in the same manner as in Production Example 12 above. The desired compound (90% yield) was obtained.

 Melting point: 16 3— 16 4 ° C

'H-NMR (DMS 0- d ₆ ): 1.2—1.9 (8 H, m) 2.35 (6 H, s) 3.2—3.6 (4 H, m) 7. 3—8.0 (1 8 H, m) 8.79 (2 H, t) 1 1.1 (2 H, bs) 1 1.8 (2 H, bs)

IR (cm ^-1 ): 1 70 5, 1 1 6 7

Compound Production Example 17

 Production of N- (5-hydroxy-3- (n-propynole) -11H-pyrazonole-14-carbonyl) -14-methylbenzenebenzenesulfonamide (Compound No. 17)

Compound Νο · 17 Instead of 5-methyl-2,4-dihydro-pyrazol-3-one as a raw material Instead, the same procedure as in Production Example 1 was performed except that 8.7 g of 5_ (n-propyl) -12,4-dihydro-pyrazol-13-one obtained in Production Reference Example 2 described later was used. Thus, 22.2 g (yield 100%) of the target compound was obtained.

 Melting point: 1 55—16 1 ° C

¹ H—NMR (acetone—d ₆ ): 0.90 (3H, t) 1.5—2.0 (2 H, m) 2.43 (3 H, s) 2.83 (2 H, t) ) 7.19 (1 H, s) 7.42 (2 H, d) 7.98 (2 H, d) 9.6 (2 H, bs)

IR (cm ^-1 ): 1 668, 1627, 1 1 68

Compound Production Example 18

 Production of 4,4,1-bis (5-hydroxy-13- (n-propynole) -14- (tonolene-14-snorolephonylaminocarbonyl) -pyrazole-1-carbonylamino) diphenylmethane

 Compound No.18

 Production Example 12 was repeated except that Compound No. 17 was used as the starting material instead of Compound No. 1 and methylene bisphenyl diisocyanate (MDI) was used as the isocyanate. Similarly, the target compound (yield 87%) was obtained.

 Melting point: 22 1—228 ° C

iH—NMR (DMS O— d ₆ ) .: 0.85 (6 H, t) 1.1—1.3 (4 H, m) 2.40 (6 H, s) 2.70 (4 H, t) t) 3.91 (2 H, s) 7.1-7.8 (16 H, m) 7.91 (4 H, d) 1 0.65 (1 H, s) 1 1. 0 (1 H, bs)

IR (cm " ¹ ): 1 6 9 8, 1 1 7 2

Compound Production Example 19

 Preparation of 2,4-bis [5-hydroxy-1- (n-propyl) -14- (tonolene-14-sulfonylaminocarbonyl) pyrazole-1-carbonylamino] toluene

 Compound No. 19

 The above production was carried out except that Compound No. 17 was used as the raw material instead of Compound No. 1 and tolylene-1,4-diisocyanate (TDI) was used as the isocyanate. In the same manner as in Example 12, the target compound (yield 46%) was obtained.

 Melting point: 1 7 6— 1 7 9 ° C

 'H-NMR CDMS O-dg): 2.36 (6H, s) 3.92 (2H, s) 6.7 (4H, bs) 7.2-7.9 (26H , m) 2 2.25 (1 H, d) 1 1.85 (1 H, bs)

IR (cm ^-1 ): 1 7 3 6, 1 6 9 7, 1 1 7 1

Compound Production Example 20

Production of 1,6-bis (5-hydroxy-1- (n-propyl) -14- (toluene-14-sulfonylaminocarbonyl) -pyrazole-1-carbonylamino) hexamethylene

 The same procedures as in Production Example 12 except that Compound No. 17 was used as the starting material instead of Compound No. 1 and hexamethylene diisocyanate (HMD I) was used as the isocyanate were used. In the same manner as in the above, the target compound (91% yield) was obtained.

 Melting point: 200-201 ° C

'H-NMR (DMS 0- d ₆ ): 0.83 (6 H, t) 1.2-1.9 (12 H, m) 2.39 (6 H, s) 2.69 (4 H, t) 3.1-3.5 (4 H, m) 7.43 (4 H, d) 7.88 (4 H, d) 8.50 (1 H, t) 1 0.0 (3 H, bs) 1 1.1 (2H, s)

IR (cm ^-1 ): 1 69 5, 1 1 7 3

Compound Production Example 21

Production of 4,4,1-bis [5-hydroxy-3- (n-propynole) -14- (tonoleene-4-sulfonylaminocarbonyl) pyrazole-1-1-carbonylamino] dicyclohexylmethane

 Compound No. 21

 Except that Compound No. 17 was used instead of Compound No. 1 as a raw material, and 4,4-methylenebiscyclohexyl isocyanate (hydrogenated MD I) was used as isocyanate. In the same manner as in Production Example 12 above, a target compound (yield: 91%) was obtained.

 Melting point: 1 78 -1 82 ° C

— NMR (DMS O— d ₆ ): 0.83 (6 H, t) 0.9—2.2 (24 H, m) 2.40 (6 H, s) 2.6—2.8 ( 4H, m) 4.00 (2 H, m) 7.42 (4 H, d) 7.90 (4 H, d) 8.1-8.8 (2 H, m) 1 1.0 (1 H, s)

IR (cm ^-1 ): 1 714, 1 703, 1 1 72

Manufacturing Reference Example 1

 Preparation of 5-phenyl-1-, 2,4-dihydro-pyrazol-3-one

 A 500 ml separable flask equipped with a mechanical stirrer is charged with 50 g (260 mmo1) of ethyl benzoyl acetate and 100 ml of methanol, and 14.3 g of hydrazine hydrate (286 mo 1) was added dropwise over 20 minutes.

After 2 hours, the formed white crystals are filtered out, dried and the target compound 37. 3 g (89% yield) were obtained.

^J H-NMR (DMS O-d ₆ ): 5.97 (1H, s) 7.2—7.9 (5H, m) 11.0 (2H, bs)

Manufacturing Reference Example 2

Production of 5- (n-propyl) -1,2,4-dihydro-pyrazol-3-one

 In the same manner as in Production Example 1 above, except that 50 g of 3-ethyl keto-n-ethyl hexanoate was used instead of benzoinole acetic acid ethyl acetate, 33.0 g of the target compound (yield Rate of 84%).

^ -NMR (acetone ~ d ₆ ): 0.94 (3 H, t) 1 '. 4—1.9 (2 H, m) 2.55 (2 H, t) 5.36 (1 H , s) 1 0.1 (1 H, bs)

 Thermal recording paper production example 1

 (1) Preparation of heat-sensitive coating solution

A dye precursor 3 Jechiruamino ⁶ - methyl-7- Aerinofuru Oran (trade name ODB, Yamamoto Chemicals Co., Ltd.) were dispersed in 5.0 ₂ 1. 25 wt% aqueous solution of polyvinyl alcohol 20 g, further using a sand grinder And pulverized to obtain a dispersion liquid A.

Then, the compound obtained in the above compound prepared in Example 1 N o. 1, 5. 0 g of likewise 1 dispersion was triturated with 2 5 mass _^0/0 aqueous solution of polyvinyl alcohol 20 g and Sandogurai Nda Liquid B was obtained.

Furthermore, benzyl naphthyl ether 5. 0 g, as in the above 1. using 2 5 mass _^0/0 Poly Bulle alcohol solution 20 g and a sand grinder and powder碎to obtain a dispersion liquid C. Further, 30 g of calcium carbonate was crushed with 70 g of water using a sand grinder to obtain a dispersion D.

 35 parts by weight of the dispersion A, 70 parts by weight of the dispersion B, 70 parts by weight of the dispersion C, 100 parts by weight of the dispersion D, and 57 parts by weight of 10% by weight polyvinyl alcohol , And 4 parts by mass of a 40% by mass zinc stearate dispersion were mixed to prepare a thermal coating solution.

 (2) Preparation of thermal recording paper

 The heat-sensitive coating solution obtained in the above (1) was applied to a high-quality paper with a thickness of 50 μπι using a bar coder and dried for 24 hours to obtain a heat-sensitive recording paper.

 Thermal recording paper production example 2

 Thermal recording paper was obtained in the same manner as in Example 1 except that Compound No. 2 was used instead of Compound 0.1 used in Example 1.

 Thermal recording paper production example 3

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 3 was used instead of Compound No. 1 used in Example 1.

 Thermal recording paper preparation example 4

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 7 was used instead of Compound No. 1 used in Example 1.

 Thermal recording paper production example 5

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 8 was used instead of Compound No. 1 used in Example 1.

 Example 6 of making thermal recording paper

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 10 was used instead of Compound No. 1 used in Example 1.

 Example 7 of making thermal recording paper

Compound No. 11 was used in place of compound N 0.1 used in Example 1. Except for the above, a thermal recording paper was obtained in the same manner as in Example 1.

 Comparative example of thermal recording paper production 1

 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was used instead of the compound No. 1 used in Example 1. Was.

 <Evaluation of color development and plasticizer resistance>

 The heat-sensitive recording papers obtained in Examples 1 to 7 and Comparative Example 1 were cut to a width of 1 cm, and heated on a hot plate heated to about 200 ° C. to develop color.

 The color density was measured using a Macbeth densitometer (RD 917).

 Further, the colored product was immersed in a plasticizer [di (2-ethylhexyl) phthalate], left at room temperature for 2 hours, pulled up to remove excess plasticizer, and again reduced the color density to Macbeth. It was measured with a densitometer.

 Table 1 shows the results thus obtained.

 Table 1

In Comparative Example 1, when immersed in a plasticizer, the color faded to the extent that it was difficult to recognize with the naked eye, whereas in Examples 1 to 7, color development remained at a level that was practically acceptable. I was

 As is clear from the results, the novel color developer of the present invention shows much better plasticizer resistance than the conventional color developer.

 Thermal recording paper preparation example 8

 The heat-sensitive coating liquid obtained in (1) of Example 1 of the above-mentioned heat-sensitive recording paper was subjected to fine coating with a coating thickness of 50 m using a basic applicator (BAP-03, manufactured by Imoto Seisakusho Co., Ltd.). It was coated on paper and dried for 24 hours to obtain a thermal recording paper. Thermal recording paper production example 9

 A thermosensitive recording paper was obtained in the same manner as in Example 8, except that Compound No. 7 was used instead of Compound N 0.1 used in Example 1.

 Comparative example 2 of thermal recording paper production

 A thermosensitive recording paper was obtained in the same manner as in Example 8, except that 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was used instead of the compound No. 1 used in Example 1. Was.

 <Heat resistance evaluation>

 The heat-sensitive recording paper obtained in Examples 8 and 9 and Comparative Example 2 was cut to a width of 1 cm, and passed between two rollers heated to about 230 ° C at a speed of 0.5 cmZ seconds. And developed the color.

 The color-developed thermal paper was stored in a thermostat at 80 ° C. for 24 hours, and the change in color density was measured.

 At the same time, thermal paper, which was not colored, was stored under the same conditions, and the color development of the white background (non-colored portion) was measured.

 The color density was measured using a Macbeth densitometer (RD 917).

The results thus obtained are shown in Table 2-1 (white area) and Table 2-2 (colored area). Table 2-1 (white background)

Table 2-2 (colored area)

In Comparative Example 2, the white background (non-colored portion) may be further colored by exposure to a high temperature, and it may be difficult to determine the record. On the other hand, in Examples 8 and 9, exposure to a high temperature was performed. No white background (non-colored portion) was developed even after the test, indicating that the recordability was excellent.

 There was no particularly large difference in the coloration between Examples 8 and 9 and Comparative Example 2. As is clear from the results, the novel color developer of the present invention shows much higher heat resistance than the conventional color developer.

 Light resistance evaluation>

 The heat-sensitive recording paper obtained in Examples 8 and 9 and Comparative Example 2 was cut to a width of 1 cm and passed between two rollers heated to about 230 ° C at a speed of 0.5 cm / sec. And developed the color.

Paste the colored thermal paper on the south-facing window and leave it for 3 days to change the color density. Was measured.

 The color density was measured using a Macbeth densitometer (RD 917).

 Table 3 shows the results.

 Table 3

In Comparative Example 2, fading of the color-developed portion was observed, whereas in Examples 8 and 9, no fading was observed, indicating that the recordability was excellent.

 As is evident from the results, the novel color developer of the present invention shows much better light fastness than conventional color developers.

 Thermal recording paper production example 10

 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that Compound No. 12 was used instead of Compound No. 1 used in Example 1.

 Example of thermal recording paper production 1 1

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 13 was used instead of Compound No. 1 used in Example 1.

 Thermal recording paper production example 1 2

 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that Compound No. 14 was used instead of Compound No. 1 used in Example 1.

 Thermal recording paper production example 13

A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 15 was used instead of Compound No. 1 used in Example 1. Thermal recording paper production example 14

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 16 was used instead of Compound No. 1 used in Example 1.

 Thermal recording paper production example 15

 A thermosensitive recording paper was obtained in the same manner as in Example 1 except that Compound No. 18 was used instead of Compound No. 1 used in Example 1.

 Thermal recording paper production example 16

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 19 was used instead of Compound No. 1 used in Example 1.

 Thermal recording paper production example 17

 A thermosensitive recording paper was obtained in the same manner as in Example 1, except that Compound No. 21 was used instead of Compound No. 1 used in Example 1.

 Comparative example 3 of thermal recording paper production

 Instead of the compound No. 1 used in Example 1, a commercial color developer (Nippon Soda Co., Ltd., D-8; ISP)

A thermosensitive recording paper was obtained in the same manner as in Example 1 except for using.

 Comparative example of thermal recording paper production 4

 Instead of the compound No. 1 used in Example 1, a commercially available color developer (Nippon Soda Co., Ltd., D_90)

A thermosensitive recording paper was obtained in the same manner as in Example 1 except for using. <Evaluation of color development and plasticizer resistance>

 The heat-sensitive recording papers obtained in Examples 10 to 17 and Comparative Examples 3 and 4 were cut to a width of 1 cm, and heated on a hot plate heated to about 200 ° C. to develop color. The color density was measured using a Macbeth densitometer (RD 917).

 Further, the colored product was immersed in a plasticizer [di (2-ethylhexyl) phthalate], allowed to stand at room temperature for 2 hours, pulled up, wiped off excess plasticizer, and reduced the color density to Macbeth. It was measured with a densitometer.

 In addition, the color development density after immersion and the color development initial density were defined as the retention rates.

 Table 4 shows the results thus obtained.

 Table 4

In Comparative Example 3, when immersed in a plasticizer, the color faded to the extent that it was difficult to identify with the naked eye, whereas in Examples 10 to 17, the color development remained practically unproblematic.

Further, the compound (D-90) of Comparative Example 4 has plasticizer resistance. The compounds of 10, 12, 14, and 16 were found to exhibit even more sufficiently high plasticizer resistance.

 As is clear from the results, the novel color developer of the present invention shows much better plasticizer resistance than the conventional color developer.

 Heat resistance evaluation>

 The heat-sensitive recording papers obtained in Examples 10 to 17 and Comparative Example 2 were cut to a width of 1 cm, and heated on a hot plate heated to about 200 ° C. to develop color. The colored thermal paper and the uncolored thermal paper (white background) were stored in a thermostat at 95 ° C for 24 hours. It was measured using a densitometer (RD 917).

 Table 5 shows the results thus obtained.

 Table 5

Control after storage at 95 ° C for 24 hours

 Thermal recording paper

Colored area density White background Colored area density White background Example 1 1 1.0.8 0.07 1.05 0.14 Example 1 1 0.85 0.08 0.75 0.12 Example 1 2 1.01 0 10 0.96 0.14 Example 1 3 0.98 0.10 1.03 0.16 Example 1 4 0.88 0.06 0.88 0.12 Example 1 5 0.80 0.07 0.74 0.13 Example 1 6 0.57 0.09 0.72 0.14 Example 1 7 0.68 0.08 0.82 0.14 Comparative example 3 0.59 0.06 0.33 0.31 Comparative Example 4 0.58 0.06 0.51 0.25 In Comparative Examples 3 and 4, the white background (non-colored portion) was clearly colored by exposure to high temperature, and it was difficult to determine the record. On the other hand, in Examples 10 to 17, Even when exposed to high temperatures, the coloration of the white background (non-colored portion) was slight, and the storage stability of the record was excellent, and was at a level with no practical problems.

 As is clear from these results, the novel color developer of the present invention shows remarkably superior heat resistance than the conventional color developer. Industrial applicability

 According to the present invention, there is provided a thermosensitive recording medium having a thermosensitive coloring layer using a novel developer, which exhibits resistance to various environmental conditions, in particular, plastic plasticizers and enables long-term recording and storage. And a novel benzenesulfonamide derivative useful as the developer and the like can be provided.

Claims

The scope of the claims

1. On a support, there is provided a colorless or pale-colored dye precursor, and a thermosensitive coloring layer containing a coloring agent that reacts with the dye precursor under heating to develop the color, and wherein the coloring agent is In one molecule, the formula (I)

A thermosensitive recording medium, characterized in that it is a compound having at least one partial structure represented by the formula:

2. The partial structure has the general formula (II)

[In the formula, R ² is substituted with a hydrogen atom, a halogen atom, a di-alkyl group, a Ci-C ₄ haloalkyl group, a C ₃ -C ₆ cycloalkyl group or a halogen atom or a C-dialkyl group. Represents a phenyl group which may be substituted. The thermal recording medium according to claim 1, having a structure represented by the following formula:

3. The developer has the general formula (III)

Wherein R ¹ is a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -〇 ₄ haloalkyl group, R ³ is a hydrogen atom or a C i -C ₈ alkyl group, n is an integer of 0-3, R ² is as defined in general formula (II). ]

3. The thermal recording according to claim 2, which is a benzenesulfonamide derivative represented by the formula: body.

 4. The developer is represented by the general formula (IV)

[Wherein, R ¹ is a halogen atom, a Ci C alkyl group or a C i C haloalkyl group, R ⁴ is a hydrogen atom,

A phenyl group which may be substituted with an alkyl group, a halogen atom, or a C i -C ₄ alkyl group, or a general formula (a)

(In the formula, Y represents a halogen atom or a C i -C ₄ alkyl group, and m represents 0, 1 or 2.)

And n represents an integer of 0 to 3, and R ² is as defined in the general formula (II). ]

The thermosensitive recording material according to claim 2, which is a benzenesulfonamide derivative represented by the following formula:

 5. The developer is represented by the general formula (V)

[In the formula, R ¹ is a halogen atom, a C ^{1 to} C ₄ alkyl group or C i to C ^, a lower alkyl group, and A is C optionally substituted with a C _{1 to} C ₄ alkyl group. ~ C ₈ Divalent consequent opening alkyl ring, C ₁ to c ₄ Good c ₇ ~ci be substituted with an alkyl group. Substituted divalent Bishiku port alkyl ring, a divalent tricycloalkyl ring, a halogen atom or a C E ～〇 ₄ alkyl C ～〇 ₄ alkyl optionally substituted by a group c ₁₀ ~ci ₄ of A divalent aromatic ring which may be substituted, or a C ₂ to C ₂₂ divalent alkyl chain which may be linear or branched; The divalent alkyl chain of c _{2 to} c ₂₂ further includes an oxygen atom, a sulfur atom, one S〇 ₂ —, — NHCO—, — NHCONH—, one NHC SNH—, and a C _{3 to} C ₈ divalent alkyl chain. A cycloalkyl ring,

. Divalent Bishiku port alkyl ring may comprise a divalent tricycloalkyl ring C ₁₀ -C i ₄ as a partial structure. n represents an integer of 0 to 3, and R ² is as defined in formula (II). ]

The thermosensitive recording material according to claim 2, which is a benzenesulfonamide derivative represented by the following formula:

 6. The partial structure is represented by the formula (VI)

2. The thermal recording medium according to claim 1, having a structure represented by:

7. The developer is represented by the general formula (VII)

[In the formula, R ¹ represents a halogen atom, C i C alkyl group or C ₁ ~ Ji ₄ Haroa alkyl group, ¹及Pi丫¹ are each independently an oxygen atom, a sulfur atom, - S 0 ₂ -, one NR ⁵ - and a single CR ⁶ R ⁷ - divalent group selected from, Z is a single bond or an oxygen atom, a sulfur atom, - S0 ₂ -, one ^{NR 8 -, - (CR 9} R 10) a -, It represents a divalent group selected from one c (= o) and one c (= s).

R ⁵ to R ^{1 Q} is substituted with independently hydrogen atom, Ji E-alkyl group, Ji E -C ₄ haloalkyl groups, C ₃ -C ₆ cycloalkyl group or a halogen atom or a C ～〇 ₄ alkyl group And a and n each represent an integer of 0 to 3.

When both the values are one NR ⁵ — or one CR ⁶ R ⁷ —, Z represents a single bond.

However, the oxygen source X ¹ or Y ¹ is a sulfur atom, _ S 0 ₂ - or one NR ⁵ - in the case of, Z is one _{^{(CR 9 R 10) a -}} , one C (= 0) or one Indicates C (= S). ]

7. The thermosensitive recording material according to claim 6, which is a benzenesulfonamide derivative represented by the following formula:

 8. The developer has the general formula (VIII)

Wherein, Rn～R ¹⁶ are each independently a hydrogen atom, Ci C alkyl groups, C ～〇 ₄ Ha port alkyl groups, C ₃ -C ₆ there cycloalkyl group Rere halo gen atom or a C ₁ -C _{4 represents a} phenyl group which may be substituted with an alkyl group, and may form a chemical bond with I ¹¹ , R ¹² , R ¹⁵ or R ¹⁶ and R ¹³ or R ¹⁴ together. and a scale ^{1 1, R 1 2, R} 1 5 , or R ^16, R ^{1 3} or an R ¹⁴ together form connexion, together with the carbon atom to which each is attached, halo gen atom or a C i C alkyl group May form a benzene ring structure which may be substituted.

The length is as defined in the general formula (VII). ] The thermosensitive recording material according to claim 7, which is a benzenesulfonamide derivative represented by the following formula:

 9. The developer has the general formula (IX)

[Wherein, R ¹ is a halogen atom; ₄ alkyl or C I～C ₄ Haroa alkyl group, R ^{1 7} and R ¹⁸ are each independently a hydrogen atom, Ci C Al kill group, 0 ₁ ～〇 ₄ C port alkyl group, C ₃ -C ₆ cycloalkyl It represents an alkyl group or a phenyl group which may be substituted with a halogen atom or a C to C ₄ alkyl group, and n represents an integer of 0 to 3. ]

7. The thermosensitive recording material according to claim 6, which is a benzenesulfonamide derivative represented by the following formula:

 10 0. The developer is represented by the general formula (X)

[Wherein, R ¹ represents a halogen atom, C ₁ -C ₄ alkyl or C ～〇, lower alkyl group, R ^{1 9} is halogen atom, C ~ Ji alkyl group or a C I～C ₄ haloalkyl group, n represents an integer of 0 to 3, and R ² is as defined in the general formula (II). ]

The thermosensitive recording material according to claim 2, which is a benzenesulfonamide derivative represented by the following formula:

1 1. General formula (III)

Wherein R ¹ is a halogen atom, a C alkyl group or a C 1 to C ₄ haloalkyl group, R ² is a hydrogen atom, a halogen atom, a C _{1 to} C ₄ alkyl group,

4 haloalkyl group, C ₃ -C ₆ cycloalkyl group or halogen atom or phenyl group optionally substituted with C ₁ -C ₄ alkyl group, R ³ is hydrogen atom or C i -C ₈ alkyl group, n is Indicates an integer from 0 to 3. ]

A benzene sulfonamide derivative having a structure represented by the following formula:

1 2. General formula (IV)

[In the formula, R ¹ represents a halogen atom, C ～◦ ₄ alkyl or C ~0 ₄ Haroa alkyl group, R ² is a hydrogen atom, a halogen atom, Ji _{1-0 4} Arukiru group, 〇 ₁ ~ Ji ₄ haloalkyl group, C ₃ -C ₆ consequent opening alkyl group or a halogen atom or a C i~C ₄ alkyl a phenyl group which may be substituted with a group, R ⁴ is a hydrogen atom, C ~ Ji i ₈ alkyl group or a halogen atom or a C i to A phenyl group which may be substituted with a C ₄ alkyl group, or a compound represented by the general formula (a):

 (Wherein, Y represents a halogen atom or a C alkyl group, m represents 0, 1 or 2), and n represents an integer of 0 to 3. ]

A benzenesulfonamide derivative having a structure represented by the following formula:

1 3. General formula (V)

[In the formula, R ¹ represents a halogen atom, C ～〇 ₄ alkyl group or a C -C ₄ Haroa alkyl group, R ² is a hydrogen atom, a halogen atom, C I～C ₄ alkyl groups, C -C ₄ haloalkyl groups, C ₃ -C ₆ consequent opening alkyl group or a halogen atom or a C I～C ₄ alkyl a phenyl group which may be substituted with a group, a is a divalent optionally substituted with C alkyl C ₃ -C ₈ Sik port alkyl ring, C ~ Ji ₄ alkyl C ₇ may be substituted by a group -C. Divalent Bishiku port alkyl ring, C ~◦ ₄ divalent tricycloalkyl ring alkyl group C ₁₀ optionally substituted with -C _14, optionally substituted with a halogen atom or a C i~C ₄ alkyl group aromatic ring of may divalent be, or straight-chain and even represents a divalent alkyl chain optionally C ₂ -C ₂₂ even those with branched, divalent Kaoru aromatic ring and C ₂ divalent alkyl chain -C ₂₂ further oxygen atom, a sulfur atom, one S_〇 ₂ - one NHCO-, one -NHCONH-, one NHC SNH-, divalent consequent opening Anorekinore of C ₃ -C ₈ ring, C ₇ ~C a. Divalent Bishiku port Anorekinore ring, a divalent tricycloalkyl ring c ₁₀ to c ₁₄ may include as a partial structure. n shows the integer of 0-3. ]

A benzenesulfonamide derivative having a structure represented by the following formula: 14 · A is

14. The benzene sulfonamide derivative according to claim 13, having a structure represented by the following formula:

 1 5. General formula (VII)

[Wherein, R ¹ is a halogen atom, a Ci C alkyl group or a 0 _{1 to} 〇 ₄ haloalkyl group, ¹ and 丫¹ are each independently an oxygen atom, a sulfur atom, —S 0 ₂ —, 1 NR ⁵ — And a divalent group selected from CR ⁶ R ⁷ —, Z is a single bond or an oxygen atom, a sulfur atom, one S〇 ₂ —, — NR ⁸ —,-(CR ⁹ R ¹⁰ ) _a —, one C ( = 0), 'and 1 C (= S).

R ^{5 to} R ^{1 Q} are each independently substituted with a hydrogen atom, a CCA alkyl group, a C _{1 to} C ₄ haloalkyl group, a C _{3 to} C ₆ cycloalkyl group, a halogen atom, or a C _{1 to} C ₄ alkyl group. And a and n each represent an integer of 0 to 3. In the case where both R and R are 1 NR ⁵ — or 1 CR ⁶ R ⁷ —, Z represents a single bond.

However, when X ¹ or Y ¹ is an oxygen atom, a sulfur atom, — S 0 ₂ — or one NR ⁵ —, Z is one (CR ⁹ R ¹⁰ ) _a —, — C (= 0) or one Indicates C (= S). ]

A benzenesulfonamide derivative having a structure represented by the following formula:

 1 6. The developer is of the general formula (VIII)

[In the formula, R ¹ represents a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -〇 ₄ haloalkyl group.

Shaku ¹¹ to! ^ ¹⁶ are each independently a hydrogen atom, a di-to-dialkyl group, a C _{1 to} C ₄ haloalkyl group, a C _{3 to} C ₆ cycloalkyl group or a halogen atom or a C i to C ₄ alkyl Represents a phenyl group which may be substituted with a group,

_{R ll,} and R _12, R 1 5, or R _16, may be R 1 3 or R 1 4 forms a connexion chemical bonds such together, also with ^{I 1 1, R 12, R} 15 or R ^16, R ¹³ or R ¹⁴ are together a connexion, together with the carbon atom to which each is attached, it may form a benzene ring structure which may be substituted with a halogen atom or a C ₁ -C ₄ alkyl group. ]

A benzene sulfonamide derivative having a structure represented by the following formula:

1 7. The developer has the general formula (IX)

[Wherein, R ¹ is a halogen atom, a CC alkyl group or a C ₁ -C ₄ haloalkyl group, R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkynole group, _A phenyl group which may be substituted with a _{1 to 4} haloanoalkyl group, a C _{3 to} C ₆ cycloalkyl group, a halogen atom or a C i to C ₄ alkyl group, and n represents an integer of 0 to 3. ]

A benzenesulfonamide derivative having a structure represented by the following formula: