JP2016182773A - Heat-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-sensitive recording material which has excellent heat resistance of its skin and good water resistance.SOLUTION: A heat-sensitive recording material contains at least one specific compound represented by the general formula (1) in the figure as a developing compound. [In the formula, X is a divalent crosslinking group, and Rto Rare each independently a hydrogen atom, alkyl group, arylalkyl group, aryl group, alkoxy group, aryloxy group, alkylcarbonylamino group, arylcarbonylamino group, alkylsulfonyl group, arylsulfonyl group, arylthio group, cyano group, nitro group, amino group, arylamino group (monoarylamino group or diarylamino group), halogen atom, or the like.]SELECTED DRAWING: None

Description

  The present invention relates to a heat-sensitive recording material having good water resistance and excellent background heat resistance.

  In general, heat-sensitive recording materials are obtained by dispersing a leuco dye and a developing compound such as a phenolic compound into fine particles separately, and then mixing both of them together with a binder, sensitizer, filler, lubricant, etc. A chemical reaction that occurs when one or both of the leuco dye and the color developing compound is melted and brought into contact with heat by applying the coating liquid obtained by adding the additive to the paper, film, synthetic paper, etc. Thus, color recording is obtained. For the color development of such a heat-sensitive recording material, a thermal printer or the like with a built-in thermal head is used. Compared with other recording methods, this thermal recording method is (1) no noise during recording, (2) no need for development and fixing, (3) maintenance-free, (4) machine is relatively Due to its low cost, it is widely used in the facsimile field, the output of computers, the field of printers such as calculators, the field of recorders for medical measurement, the field of automatic ticket machines, the field of thermal recording labels, and the like.

  In recent years, the use of heat-sensitive recording materials has been expanded, and the demand for high-speed recording has further increased in order to further improve productivity, and development of heat-sensitive recording materials that can sufficiently cope with high-speed recording has been strongly desired. In this case, a color developing compound with a low melting point and a low heat of fusion is required, but this property is likely to cause deterioration of the unrecorded part (background) of the heat-sensitive recording material during manufacture, use or storage. Therefore, not only high whiteness but also improvement in stability is strongly desired.

  In general, a color developing compound having a phenolic hydroxyl group has a high color developing ability. Among them, a bisphenol-based color developing compound has, for example, 2,2-bis (4-hydroxy) disclosed in Patent Document 1 because of its high color density. Many reports have been reported, including phenylpropane) (bisphenol A) and 4,4′-dihydroxydiphenylsulfone (bisphenol S) disclosed in Patent Document 2. However, they are inferior in water resistance and have drawbacks such as deterioration of the background (background fogging).

US Pat. No. 3,539,375 Japanese Patent Laid-Open No. 57-11088

  As a result of intensive studies to achieve the above object, the present inventor has a heat-sensitive recording material using a specific compound represented by the following general formula (1) as a color developing compound, which has excellent water resistance, In addition, the present inventors have newly found that the background is excellent in heat resistance and completed the present invention.

［式（１）中、Ｘは２価の架橋基を、Ｒ^１〜Ｒ^１０はそれぞれ独立に、水素原子、アルキル基、アリールアルキル基、アリール基、環構成原子として窒素原子、酸素原子、硫黄原子から選択される１乃至３つの原子を含む、５又は６員環の複素環基、環構成原子として窒素原子、酸素原子、硫黄原子から選択される１乃至３つの原子を含む、５又は６員環の複素環アミノ基、環構成原子として窒素原子、酸素原子、硫黄原子から選択される１乃至３つの原子を含む、５又は６員環の複素環基に、１つのベンゼン環が縮環した縮環型５又は６員環の複素環アミノ基、アルコキシ基、アリールオキシ基、アルキルカルボニルアミノ基、アリールカルボニルアミノ基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルカルボニル基、アリールカルボニル基、カルバモイル基、モノアルキルカルバモイル基、ジアルキルカルバモイル基、モノアリールカルバモイル基、ジアリールカルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、スルファモイル基、モノアルキルスルファモイル基、ジアルキルスルファモイル基、モノアリールスルファモイル基、ジアリールスルファモイル基、ヒドロキシ基、アルキルスルホニル基、アリールスルホニル基、アルキルチオ基、アリールチオ基、ウレイド基、ジアルキルウレイド基、モノアリールウレイド基、ジアリールウレイド基、アルコキシカルボニルアミノ基、シアノ基、ニトロ基、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、アリールアミノ基（モノアリールアミノ基又はジアリールアミノ基）、メルカプト基、カルボキシ基、スルホン基、ハロゲン原子を表す。］
（２）一般式（１）において、Ｒ^１〜Ｒ^１０がそれぞれ独立に、水素原子、アルキル基、アリールアルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルカルボニルアミノ基、アリールカルボニルアミノ基、アルキルスルホニル基、アリールスルホニル基、アリールチオ基、シアノ基、ニトロ基、アミノ基、アリールアミノ基（モノアリールアミノ基又はジアリールアミノ基）、ハロゲン原子；よりなる群から選択される基であることを特徴とする（１）に記載の感熱記録材料、
（３）一般式（１）において、Ｒ^１〜Ｒ^１０がそれぞれ独立に、水素原子又はアルキル基であることを特徴とする（１）又は（２）に記載の感熱記録材料、
（４）一般式（１）において、Ｒ^１〜Ｒ^１０がすべて水素原子であることを特徴とする（１）乃至（３）のいずれか一つに記載の感熱記録材料、
（５）一般式（１）において、Ｘが脂肪族炭化水素残基又は芳香族残基であることを特徴とする（１）乃至（４）のいずれか一つに記載の感熱記録材料、
（６）一般式（１）において、Ｘがベンゼン環であることを特徴とする（１）乃至（５）のいずれか一つに記載の感熱記録材料、
（７）（１）乃至（６）のいずれか一つに記載の感熱記録材料を含む感熱記録層、
（８）一般式（１）が下記式（２）又は式（３）で表される化合物、

に関する。 That is, the present invention
(1) A heat-sensitive recording material comprising at least one compound represented by the following general formula (1):

[In the formula (1), X represents a divalent bridging group, and R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, an alkyl group, an arylalkyl group, an aryl group, or a ring atom as a nitrogen atom, oxygen atom, sulfur. 5 or 6-membered heterocyclic group containing 1 to 3 atoms selected from atoms, 1 to 3 atoms selected from nitrogen atom, oxygen atom, sulfur atom as ring constituting atoms, 5 or 6 One benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a heterocyclic amino group as a ring member, a nitrogen atom, an oxygen atom, and a sulfur atom as ring constituent atoms Condensed 5- or 6-membered heterocyclic amino group, alkoxy group, aryloxy group, alkylcarbonylamino group, arylcarbonylamino group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylcarbo Group, arylcarbonyl group, carbamoyl group, monoalkylcarbamoyl group, dialkylcarbamoyl group, monoarylcarbamoyl group, diarylcarbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, Monoalkylsulfamoyl group, dialkylsulfamoyl group, monoarylsulfamoyl group, diarylsulfamoyl group, hydroxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, ureido group, dialkylureido group, Monoarylureido group, diarylureido group, alkoxycarbonylamino group, cyano group, nitro group, amino group, monoalkylamino group, dialkylamino group Arylamino group (mono-arylamino group or diarylamino group), a mercapto group, a carboxyl group, a sulfonic group, a halogen atom. ]
(2) In the general formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, alkyl group, arylalkyl group, aryl group, alkoxy group, aryloxy group, alkylcarbonylamino group, arylcarbonylamino group, It is a group selected from the group consisting of alkylsulfonyl group, arylsulfonyl group, arylthio group, cyano group, nitro group, amino group, arylamino group (monoarylamino group or diarylamino group), halogen atom; The heat-sensitive recording material according to (1),
(3) In the general formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom or an alkyl group, The heat-sensitive recording material according to (1) or (2),
(4) In the general formula (1), R ^{1 to} R ¹⁰ are all hydrogen atoms, The heat-sensitive recording material according to any one of (1) to (3),
(5) In the general formula (1), X is an aliphatic hydrocarbon residue or an aromatic residue, The heat-sensitive recording material according to any one of (1) to (4),
(6) The heat-sensitive recording material according to any one of (1) to (5), wherein in the general formula (1), X is a benzene ring,
(7) a thermal recording layer comprising the thermal recording material according to any one of (1) to (6),
(8) A compound in which the general formula (1) is represented by the following formula (2) or formula (3),

About.

  The present invention provides a heat-sensitive recording material that is excellent in water resistance and has a high stability against heat by using the specific compound represented by the general formula (1) as a color developing compound. it can.

The present invention will be described in detail.
The present invention usually uses a colorless or light-coloring compound and a specific compound represented by the above general formula (1), and, if necessary, other color developing compounds, sensitizers and storages shown below. The present invention relates to a heat-sensitive recording material containing a property improver, a binder, a filler, and other additives.

Specific examples of the aliphatic hydrocarbon residue and the aromatic residue of the divalent bridging group X in the general formula (1) are shown below, but are not limited thereto.
That is,
The aliphatic hydrocarbon residue means a group obtained by removing two hydrogen atoms from a linear, branched or cyclic aliphatic hydrocarbon. Specific examples of the aliphatic hydrocarbon residue include methane, ethane, n-propane, n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane. Chains; branched chains such as isopropane, isobutane, sec-butane, t-butane, isohexane, t-hexane, isoheptane, t-heptane, isooctane, t-octane, 2-ethylhexane, isononane, isodecane (preferably C3-C10); cyclic (preferably C3-C7) such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, etc .; preferably C1-C10 linear or branched, preferably linear Is more preferable. ;

  Further, examples of the cyclic aliphatic hydrocarbon include 5- or 6-membered alicyclic heterocycles having 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring constituent atoms. Specific examples Examples thereof include the following formulas (4-1) to (4-5). “*” In each formula represents a binding site. ;

  The aromatic residue in the bridging group X means a group obtained by removing two hydrogen atoms from an aromatic ring, a condensed ring containing an aromatic ring, an aromatic heterocyclic ring, or the like. Specific examples of the aromatic ring include benzene rings of the following formulas (5-1) to (5-3), naphthyl rings of the formulas (6-1) to (6-9), and formulas (7-1) to (7-1). Examples thereof include a biphenyl ring of the formula (7-5), and a C6-C12 aromatic residue is preferred. In each formula, “*” represents a binding site. ;

  Specific examples of the aromatic heterocyclic ring containing a 5- or 6-membered ring structure containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring-constituting atoms include the following formulas (8-1) to (8-1) Formula (8-12) etc. are mentioned, Furthermore, polycyclic aromatic heterocycles, such as following formula (9-1)-formula (9-6), are mentioned. In each formula, “*” represents a binding site. ;

Specific examples of R ^{1 to} R ¹⁰ in general formula (1) include, but are not limited to, the following.

That is,
A linear, branched or cyclic alkyl group, preferably a C1-C10 alkyl group (specific examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n- Straight chain such as octyl, n-nonyl, n-decyl; isopropyl, isobutyl, sec-butyl, t-butyl, isoamyl, t-amyl, isohexyl, t-hexyl, isoheptyl, t-heptyl, isooctyl, t-octyl , 2-ethylhexyl, isononyl, isodecyl and the like (preferably C3 to C10); cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like (preferably C3 to C7); preferably linear Or a branched chain, more preferably a straight chain.);

  An arylalkyl group, preferably a C6-C12 aryl C1-C10 alkyl group, more preferably a phenyl C1-C6 alkyl group, and even more preferably a phenyl C1-C4 alkyl group (specific examples include phenylmethyl, 2-phenylethyl, 3- The alkyl moiety such as phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl and the like is linear; the alkyl moiety such as α-methylbenzyl is branched; and the like.

An aryl group, preferably a C6-C12 aryl group (specific examples include phenyl, naphthyl, biphenyl, etc.);
A 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-constituting atom (preferably an aromatic heterocyclic moiety. Specific examples include: 5-membered cycloaliphatic such as pyrrolidinyl, tetrahydrofuryl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl; 6-membered cycloaliphatic such as piperidinyl, piperazinyl, dioxan-2-yl, morpholinyl, thiomorpholinyl Aromatic 5-membered rings such as pyrrole, pyrazole, imidazole, triazole, furyl, thiophen-2-yl, thiophen-3-yl, oxazole, thiazole, etc .; Aromatic 6-membered rings such as pyridine, pyrazine, pyridazine, triazine In the above, the ring-constituting atom is a nitrogen atom, and Those selected from the sulfur atom is preferred;

  A 5- or 6-membered heterocyclic amino group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom as a ring-constituting atom (preferably an aromatic heterocyclic moiety. Specific examples include , Pyrrolidinylamino, tetrahydrofurylamino, tetrahydrothiophen-2-ylamino, tetrahydrothiophen-3-ylamino and the like; piperidinylamino, piperazinylamino, dioxan-2-ylamino, mol 6-membered alicyclic compounds such as folinylamino, thiomorpholinylamino; pyrroleamino, pyrazoleamino, imidazolamino, triazoleamino, furylamino, thiophen-2-ylamino, thiophen-3-ylamino, oxazoleamino, thiazole Aromatic 5-membered ring such as amino; pyridylamino, pyra Aromatic 6-membered ring such as ruamino, pyridazinylamino, triazinylamino, etc.), etc., and among the above, the ring-constituting atoms are selected from nitrogen atoms and sulfur atoms Is preferred;

  A condensed 5- or 6-membered ring in which one benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom as ring constituent atoms A heterocyclic amino group of the ring (preferably the heterocyclic moiety is aromatic. Specific examples include a 5-membered alicyclic heterocyclic moiety such as phthalanylamino; a 6-membered heterocyclic moiety such as benzopyranylamino; Alicyclic ones: benzpyrrololamino, benzpyrazoleamino, benzimidazolamino, benzotriazoleamino, benzofuranylamino, benzothiophen-2-ylamino, benzothiophen-3-ylamino, benzoxazoleamino, benzothiazoleamino, etc. In which the heterocyclic moiety is an aromatic 5-membered ring; quinolinylamino, cinnolinylamino, phthalazinylamino, quinazolinyl A heterocyclic moiety such as mino, quinoxalinylamino and the like having an aromatic 6-membered ring; and the like.) Of these, the ring-constituting atoms are selected from a nitrogen atom and a sulfur atom. preferable;

  Linear, branched or cyclic alkoxy group, preferably C1-C10 alkoxy group (specific examples include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptoxy, n- Straight chain such as octyloxy, n-nonyloxy, n-decyloxy; isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isoamyloxy, t-amyloxy, isohexyloxy, t-hexyloxy, isoheptoxy, t-heptoxy, isooctyloxy, t- Branched chain (preferably C3 to C10) such as octyloxy, 2-ethylhexyloxy, isononyloxy, isodecyloxy; cyclic such as cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptoxy (preferably C3 7) ones; preferably include a straight-chain or branched-chain).;

  An aryloxy group, preferably a C6-C12 aryloxy group (specific examples include phenoxy, naphthyloxy, biphenyloxy and the like);

  A linear, branched or cyclic alkylcarbonylamino group, preferably a C1-C10 alkylcarbonylamino group (specific examples include methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino, n- Straight chain such as pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, n-octylcarbonylamino, n-nonylcarbonylamino, n-decylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec-butyl Carbonylamino, t-butylcarbonylamino, isoamylcarbonylamino, t-amylcarbonylamino, isohexylcarbonylamino, t-hexylcarbonylamino, isoheptylcal A branched chain (preferably C3 to C10) such as nylamino, t-heptylcarbonylamino, isooctylcarbonylamino, t-octylcarbonylamino, 2-ethylhexylcarbonylamino, isononylcarbonylamino, isodecylcarbonylamino; cyclopropyl Cyclic (preferably C3 to C7) such as carbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino; preferably linear or branched, more preferably linear );

  An arylcarbonylamino group, preferably a C6-C12 arylcarbonylamino group (specific examples include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino, etc.);

  A linear, branched or cyclic alkylcarbonyloxy group, preferably a C1-C10 alkylcarbonyloxy group (specific examples include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy, n- Linear chain such as pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, n-decylcarbonyloxy; isopropylcarbonyloxy, isobutylcarbonyloxy, sec-butyl Carbonyloxy, t-butylcarbonyloxy, isoamylcarbonyloxy, t-amylcarbonyloxy, isohexylcarbonyloxy, t-hexylcarbonyloxy, isoheptylcal A branched chain (preferably C3 to C10) such as nyloxy, t-heptylcarbonyloxy, isooctylcarbonyloxy, t-octylcarbonyloxy, 2-ethylhexylcarbonyloxy, isononylcarbonyloxy, isodecylcarbonyloxy; cyclopropyl Cyclic (preferably C3 to C7) such as carbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy; preferably linear or branched, more preferably linear );

  An arylcarbonyloxy group, preferably a C6-C12 arylcarbonyloxy group (specific examples include phenylcarbonyloxy, naphthylcarbonyloxy, biphenylcarbonyloxy and the like);

  Linear, branched or cyclic alkylcarbonyl group, preferably C1-C10 alkylcarbonyl group (specific examples include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, n-hexyl) Straight chain such as carbonyl, n-heptylcarbonyl, n-octylcarbonyl, n-nonylcarbonyl, n-decylcarbonyl; isopropylcarbonyl, isobutylcarbonyl, sec-butylcarbonyl, t-butylcarbonyl, isoamylcarbonyl, t-amylcarbonyl , Isohexylcarbonyl, t-hexylcarbonyl, isoheptylcarbonyl, t-heptylcarbonyl, isooctylcarbonyl, t-octylcarbonyl, 2-ethylhexylcarbonyl, isononyl A branched chain (preferably C3 to C10) such as rubonyl and isodecylcarbonyl; a cyclic group (preferably C3 to C7) such as cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl; Is linear or branched, more preferably linear));

  An arylcarbonyl group, preferably a C6-C12 arylcarbonyl group (specific examples include phenylcarbonyl (benzoyl), naphthylcarbonyl, biphenylcarbonyl, etc.);

A carbamoyl group;
A linear, branched or cyclic monoalkylcarbamoyl group, preferably a mono-C1 to C10 alkylcarbamoyl group (specific examples include methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, n-butylcarbamoyl, n-pentylcarbamoyl, n -Hexylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, n-nonylcarbamoyl, n-decylcarbamoyl and the like; isopropylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, t-butylcarbamoyl, isoamylcarbamoyl, t- Amylcarbamoyl, isohexylcarbamoyl, t-hexylcarbamoyl, isoheptylcarbamoyl, t-heptylcarbamoyl, isooctylcarbamoyl, t-octy A branched chain (preferably C3 to C10) such as carbamoyl, 2-ethylhexylcarbamoyl, isononylcarbamoyl, isodecylcarbamoyl; cyclic such as cyclopropylcarbamoyl, cyclobutylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl, cycloheptylcarbamoyl C3 to C7); preferably linear or branched, more preferably linear));

  A linear, branched or cyclic dialkylcarbamoyl group, preferably a diC1-C10 alkylcarbamoyl group (specific examples include dimethylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl, di-n-butylcarbamoyl, di-n -Straight chain such as pentylcarbamoyl, di-n-hexylcarbamoyl, di-n-heptylcarbamoyl, di-n-octylcarbamoyl, di-n-nonylcarbamoyl, di-n-decylcarbamoyl; diisopropylcarbamoyl, diisobutylcarbamoyl, Di-sec-butylcarbamoyl, di-t-butylcarbamoyl, diisoamylcarbamoyl, di-t-amylcarbamoyl, diisohexylcarbamoyl, di-t-hexylcarbamoyl, diisoheptylcarbamoyl, di- -Branched chains such as heptylcarbamoyl, diisooctylcarbamoyl, di-t-octylcarbamoyl, di- (2-ethylhexyl) carbamoyl, diisononylcarbamoyl, diisodecylcarbamoyl (preferably having two C3-C10 branched chains) Cyclic (preferably having two C3-C7 cyclic groups) such as dicyclopropylcarbamoyl, dicyclobutylcarbamoyl, dicyclopentylcarbamoyl, dicyclohexylcarbamoyl, dicycloheptylcarbamoyl; preferably linear or branched , More preferably a linear one).

A monoarylcarbamoyl group, preferably a mono C6-C12 arylcarbamoyl group (specific examples include phenylcarbamoyl, naphthylcarbamoyl, biphenylcarbamoyl, etc.);
A diarylcarbamoyl group, preferably a diC6-C12 arylcarbamoyl group (specific examples include diphenylcarbamoyl, dinaphthylcarbamoyl, di (biphenyl) carbamoyl);

  A linear, branched or cyclic alkoxycarbonyl group, preferably a C1-C10 alkoxycarbonyl group (specific examples include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, n-pentoxycarbonyl, n- Straight chain such as hexyloxycarbonyl, n-heptoxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n-decyloxycarbonyl; isopropoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t-butoxycarbonyl , Isoamyloxycarbonyl, t-amyloxycarbonyl, isohexyloxycarbonyl, t-hexyloxycarbonyl, isoheptoxycarbonyl, t-heptoxycarbonyl, isooctyloxycarbonyl, A branched chain (preferably C3-C10) such as octyloxycarbonyl, 2-ethylhexyloxycarbonyl, isononyloxycarbonyl, isodecyloxycarbonyl; cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl, cyclohexyloxy Cyclic (preferably C3 to C7) such as carbonyl and cycloheptoxycarbonyl; preferably linear or branched, more preferably linear.);

  An aryloxycarbonyl group, preferably a C6-C12 aryloxycarbonyl group (specific examples include phenoxycarbonyl, naphthyloxycarbonyl, biphenyloxycarbonyl and the like);

  Linear, branched or cyclic alkylsulfonylamino group, preferably C1-C10 alkylsulfonylamino group (specific examples include methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino, n- Straight chain such as pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, n-nonylsulfonylamino, n-decylsulfonylamino; isopropylsulfonylamino, isobutylsulfonylamino, sec-butyl Sulfonylamino, t-butylsulfonylamino, isoamylsulfonylamino, t-amylsulfonylamino, isohexylsulfonylamino, t-hexylsulfonylamino, isoheptylsulfur A branched chain (preferably C3 to C10) such as nylamino, t-heptylsulfonylamino, isooctylsulfonylamino, t-octylsulfonylamino, 2-ethylhexylsulfonylamino, isononylsulfonylamino, isodecylsulfonylamino; cyclopropyl Cyclic (preferably C3-C7) such as sulfonylamino, cyclobutylsulfonylamino, cyclopentylsulfonylamino, cyclohexylsulfonylamino, cycloheptylsulfonylamino; preferably linear or branched, more preferably linear );

  An arylsulfonylamino group, preferably a C6-C12 arylsulfonylamino group (specific examples include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, biphenylsulfonylamino, etc.);

A sulfamoyl group;
A linear, branched or cyclic monoalkylsulfamoyl group, preferably a mono-C1 to C10 alkylsulfamoyl group (specific examples include methylsulfamoyl, ethylsulfamoyl, n-propylsulfamoyl, n Linear chain such as -butylsulfamoyl, n-pentylsulfamoyl, n-hexylsulfamoyl, n-heptylsulfamoyl, n-octylsulfamoyl, n-nonylsulfamoyl, n-decylsulfamoyl Isopropylsulfamoyl, isobutylsulfamoyl, sec-butylsulfamoyl, t-butylsulfamoyl, isoamylsulfamoyl, t-amylsulfamoyl, isohexylsulfamoyl, t-hexylsulfa Moyl, isoheptylsulfamoyl, t-heptylsulfa A branched chain (preferably C3 to C10) such as yl, isooctylsulfamoyl, t-octylsulfamoyl, 2-ethylhexylsulfamoyl, isononylsulfamoyl, isodecylsulfamoyl; cyclopropylsulfa Cyclic (preferably C3 to C7) such as moyl, cyclobutylsulfamoyl, cyclopentylsulfamoyl, cyclohexylsulfamoyl, cycloheptylsulfamoyl; preferably linear or branched, more preferably straight Chain));

  A linear, branched or cyclic dialkylsulfamoyl group, preferably a diC1-C10 alkylsulfamoyl group (specific examples include dimethylsulfamoyl, diethylsulfamoyl, di-n-propylsulfamoyl, Di-n-butylsulfamoyl, di-n-pentylsulfamoyl, di-n-hexylsulfamoyl, di-n-heptylsulfamoyl, di-n-octylsulfamoyl, di-n-no Straight chain such as nylsulfamoyl, di-n-decylsulfamoyl; diisopropylsulfamoyl, diisobutylsulfamoyl, di-sec-butylsulfamoyl, di-t-butylsulfamoyl, diisoamylsulfa Moyl, di-t-amylsulfamoyl, diisohexylsulfamoyl, di-t-hexylsulfa Yl, diisoheptylsulfamoyl, di-t-heptylsulfamoyl, diisooctylsulfamoyl, di-t-octylsulfamoyl, di- (2-ethylhexyl) sulfamoyl, diisononylsulfamoyl, diisodecylsulfur Branched chain such as famoyl (preferably having two C3 to C10 branched chains); dicyclopropylsulfamoyl, dicyclobutylsulfamoyl, dicyclopentylsulfamoyl, dicyclohexylsulfamoyl, dicyclo Cyclic (preferably having two C3-C7 cyclic groups) such as heptylsulfamoyl; preferably linear or branched, more preferably linear).

  A monoarylsulfamoyl group, preferably a mono C6-C12 arylsulfamoyl group (specific examples include phenylsulfamoyl, naphthylsulfamoyl, biphenylsulfamoyl and the like);

  A diarylsulfamoyl group, preferably a di-C6-C12 arylsulfamoyl group (specific examples include diphenylsulfamoyl, dinaphthylsulfamoyl, di (biphenyl) sulfamoyl, etc.);

A hydroxy group;
Linear, branched or cyclic alkylsulfonyl group, preferably C1-C12 alkylsulfonyl group (specific examples include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, n-pentylsulfonyl, n-hexyl) Straight chain such as sulfonyl, n-heptylsulfonyl, n-octylsulfonyl, n-nonylsulfonyl, n-decylsulfonyl, n-undecylsulfonyl, n-dodecylsulfonyl; isopropylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, t -Butylsulfonyl, isoamylsulfonyl, t-amylsulfonyl, isohexylsulfonyl, t-hexylsulfonyl, isoheptylsulfonyl, t-heptylsulfonyl, isooctylsulfonyl, t-octyls A branched chain (preferably C3 to C12) such as phonyl, 2-ethylhexylsulfonyl, isononylsulfonyl, isodecylsulfonyl, isoundecylsulfonyl, t-undecylsulfonyl, isododecylsulfonyl, t-dodecylsulfonyl, etc .; cyclopropyl Cyclic (preferably C3-C7) such as sulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, cycloheptylsulfonyl; preferably linear or branched, more preferably linear. ;

An arylsulfonyl group, a C6-C12 arylsulfonyl group (specific examples include phenylsulfonyl, naphthylsulfonyl, biphenylsulfonyl, etc.);
Linear, branched or cyclic alkylthio group, preferably C1-C10 alkylthio group (specific examples include methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n- Straight chain such as octylthio, n-nonylthio, n-decylthio; isopropylthio, isobutylthio, sec-butylthio, t-butylthio, isoamylthio, t-amylthio, isohexylthio, t-hexylthio, isoheptylthio, t-heptylthio, A branched chain (preferably C3 to C10) such as isooctylthio, t-octylthio, 2-ethylhexylthio, isononylthio, isodecylthio; cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclohexane Cyclic such Chiruchio (preferably C3-C7) ones; those preferably a straight chain or branched chain, or more preferably a straight chain).;
An arylthio group, preferably a C6-C12 arylthio group (specific examples include phenylthio, naphthylthio, biphenylthio and the like);

Ureido group;
A linear, branched or cyclic monoalkylureido group, preferably a mono C1-C10 alkylureido group (specific examples include methylureido, ethylureido, n-propylureido, n-butylureido, n-pentylureido, n A straight chain such as hexylureido, n-heptylureido, n-octylureido, n-nonylureido, n-decylureido; isopropylureido, isobutylureido, sec-butylureido, t-butylureido, isoamylureido, t-amylureido, Branched chains such as isohexylureido, t-hexylureido, isoheptylureido, t-heptylureido, isooctylureido, t-octylureido, 2-ethylhexylureido, isononylureido, isodecylureido, etc. C3-C10); cyclic (preferably C3-C7) such as cyclopropylureido, cyclobutylureido, cyclopentylureido, cyclohexylureido, cycloheptylureido; preferably linear or branched Preferably a straight chain is mentioned.);

  Linear, branched or cyclic dialkylureido groups, preferably diC1-C10 alkylureido groups (specific examples include dimethylureido, diethylureido, di-n-propylureido, di-n-butylureido, di-n -Straight chain such as pentylureido, di-n-hexylureido, di-n-heptylureido, di-n-octylureido, di-n-nonylureido, di-n-decylureido; diisopropylureido, diisobutylureido, di- sec-butylureido, di-t-butylureido, diisoamylureido, di-t-amylureido, diisohexylureido, di-t-hexylureido, diisoheptylureido, di-t-heptylureido, diisooctylureido , Di-t-octylureido, di- (2-e Ruhexyl) having a branched chain such as ureido, diisononylureido, diisodecylureido (preferably having two C3 to C10 branched chains); dicyclopropylureido, dicyclobutylureido, dicyclopentylureido, dicyclohexylureido, dicycloheptyl Cyclic (preferably having two C3-C7 cyclic groups) such as ureido; preferably linear or branched, and more preferably linear.

A monoarylureido group, preferably a mono C6-C12 arylureido group (specific examples include phenylureido, naphthylureido, biphenylureido, etc.);
A diarylureido group, preferably a di-C6-C12 arylureido group (specific examples include diphenylureido, dinaphthylureido, di (biphenyl) ureido);

  Linear, branched or cyclic alkoxycarbonylamino group, preferably C1-C10 alkoxycarbonylamino group (specific examples include methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, n-butoxycarbonylamino, n- Straight chain such as pentoxycarbonylamino, n-hexyloxycarbonylamino, n-heptoxycarbonylamino, n-octyloxycarbonylamino, n-nonyloxycarbonylamino, n-decyloxycarbonylamino; isopropoxycarbonylamino, Isobutoxycarbonylamino, sec-butoxycarbonylamino, t-butoxycarbonylamino, isoamyloxycarbonylamino, t-amyloxycarbonylamino, isohexyloxycarbonyla , T-hexyloxycarbonylamino, isoheptoxycarbonylamino, t-heptoxycarbonylamino, isooctyloxycarbonylamino, t-octyloxycarbonylamino, 2-ethylhexyloxycarbonylamino, isononyloxycarbonylamino, iso Branched chain such as decyloxycarbonylamino (preferably C3 to C10); cyclic such as cyclopropoxycarbonylamino, cyclobutoxycarbonylamino, cyclopentoxycarbonylamino, cyclohexyloxycarbonylamino, cycloheptoxycarbonylamino (preferably C3-C7); preferably linear or branched, more preferably linear));

An aryloxycarbonylamino group, preferably a C6-C12 aryloxycarbonylamino group (specific examples include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino, etc.);
A cyano group;
A nitro group;

An amino group;
A linear, branched or cyclic monoalkylamino group, preferably a mono-C1-C10 alkylamino group (specific examples include methylamino, ethylamino, n-propylamino, n-butylamino, n-pentylamino, n Straight chain such as -hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino; isopropylamino, isobutylamino, sec-butylamino, t-butylamino, isoamylamino, t-amylamino, Branched chain such as isohexylamino, t-hexylamino, isoheptylamino, t-heptylamino, isooctylamino, t-octylamino, 2-ethylhexylamino, isononylamino, isodecylamino (preferably C3 to C10) Cyclopropylamino, Robuchiruamino, cyclopentylamino, those cyclohexylamino, annular, etc. cycloheptylamino (preferably C3-C7); those preferably a straight chain or branched chain, or more preferably a straight chain).;

  Linear, branched or cyclic dialkylamino group, preferably diC1-C10 alkylamino group (specific examples include dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di-n- Straight chain such as pentylamino, di-n-hexylamino, di-n-heptylamino, di-n-octylamino, di-n-nonylamino, di-n-decylamino; diisopropylamino, diisobutylamino, di-sec -Butylamino, di-t-butylamino, diisoamylamino, di-t-amylamino, diisohexylamino, di-t-hexylamino, diisoheptylamino, di-t-heptylamino, diisooctylamino, Di-t-octylamino, di- (2-ethylhexyl) amino, diisononylamino, diiso A branched chain such as silamino (preferably having two C3 to C10 branched chains); cyclic such as dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, etc. (preferably C3 ˜C7 cyclic groups); preferably linear or branched, more preferably linear).

An arylamino group (monoarylamino group or diarylamino group, preferably a mono C6-C12 arylamino group) is a mono C6-C12 arylamino group (specific examples include phenylamino (anilino), naphthylamino, biphenylamino, etc.) );
Similarly, an arylamino group may be a di-C6-C12 arylamino group (specific examples include diphenylamino, dinaphthylamino, di (biphenyl) amino);
A mercapto group (in the present specification, a group represented by "-SH");
A carboxy group;
A sulfone group;

  A halogen atom (specific examples include a fluorine atom, a chlorine atom and a bromine atom; preferably a fluorine atom, a chlorine atom and a bromine atom);

R ^{1 to} R ¹⁰ of the general formula (1) may further have one or two, preferably one, selected from the above substituents.

The substituents R ^{1 to} R ^{10 in the} general formula (1) include a hydrogen atom, an alkyl group, an arylalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylcarbonylamino group, an arylcarbonylamino group, and an alkylsulfonyl group. A group selected from the group consisting of: an arylsulfonyl group, an arylthio group, a cyano group, a nitro group, an amino group, an arylamino group (monoarylamino group or diarylamino group), a halogen atom; a hydrogen atom or an alkyl group Is particularly preferred.

  The respective substituents represented by the following general formula (1-2) and general formula (1-3), which are partial structures of the above general formula (1), are respectively present at both ends of the following general formula (1-1). The position bonded to the benzene ring is not particularly limited.

（式中、Ｒ^１〜Ｒ^１０は前記と同義である。）

(In the formula, R ^{1 to} R ¹⁰ are as defined above.)

  Although the specific example of the compound in this invention can be given to the following Table 1-Table 3, it is not limited to these.

Next, the manufacturing method of this invention compound is demonstrated.
The compound of the present invention is produced, for example, by combining the following two known production methods.

（式中、Ｒ^１〜Ｒ^５は前記と同義である。） [Manufacturing process 1]
First, a compound of the following general formula (10-2) can be produced by reacting a compound of the following general formula (10-1) with a phenyl isocyanate derivative in the presence or absence of a base.

(In the formula, R ^{1 to} R ⁵ are as defined above.)

  The solvent used in this reaction is not particularly limited as long as it does not affect the reaction. For example, amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone Halogenated hydrocarbon compounds such as methylene chloride, chloroform, and dichloroethane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; ethers such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether Compound; Nitrile compound such as acetonitrile; ketone compound such as acetone and 2-butanone; carboxylic acid ester such as ethyl acetate and butyl acetate; sulfone compound such as sulfolane; Sulfoxide compound and the like, such as sulfoxide, it may be used which are mixed.

  The usage-amount of the phenyl isocyanate derivative used for this reaction is 0.1-50 times mole normally with respect to the compound of general formula (10-1), and 0.1-5 times mole is preferable.

  Examples of the base that is optionally used in this reaction include inorganic bases such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; and organic bases such as triethylamine and diisopropylethylamine. The usage-amount of these bases is 0.1-50 times mole with respect to the compound of general formula (10-1), and 1-5 times mole is preferable.

  The reaction temperature of this reaction is usually −78 to 100 ° C., preferably 0 to 80 ° C. The reaction may be performed for 10 minutes to 24 hours.

  Moreover, the compound of the following general formula (10-3) can also be manufactured similarly to the said general formula (10-2).

（式中、Ｒ^６〜Ｒ^１０は前記と同義である。）

(Wherein R ^{6 to} R ¹⁰ are as defined above.)

[Manufacturing process 2]
The compound of the following general formula (10-4) can be produced by reacting the compound of the general formula (10-2) with an acid halide in the presence or absence of a base.

（式中、Ｒ^１〜Ｒ^５は前記と同義である。）

(In the formula, R ^{1 to} R ⁵ are as defined above.)

  The solvent used in this reaction is not particularly limited as long as it does not affect the reaction. For example, amide compounds such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone Halogenated hydrocarbon compounds such as methylene chloride, chloroform, and dichloroethane; aromatic hydrocarbon compounds such as benzene, toluene, and xylene; ethers such as dioxane, tetrahydrofuran, anisole, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether Compound; Nitrile compound such as acetonitrile; ketone compound such as acetone and 2-butanone; carboxylic acid ester such as ethyl acetate and butyl acetate; sulfone compound such as sulfolane; Sulfoxide compound and the like, such as sulfoxide, it may be used which are mixed.

  Examples of the acid halide used in this reaction include phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, 4,4′-biphenyldicarbonyl chloride, 1,4-naphthalenedicarbonyl chloride, and 2,6-naphthalene. Dicarbonyl chloride, malonyl chloride, dimethyl malonyl chloride, succinyl chloride, glutaryl chloride, adipoyl chloride, heptane dioil chloride, suberoyl chloride, azela oil chloride, sebacoyl chloride, undecanedioyl chloride, dodecanedioyl chloride Etc. The usage-amount of an acid halide is 0.1-50 times mole with respect to the compound of said Formula (10-2) or Formula (10-3), and 0.5-5 times mole is preferable.

  In general, an acid halide can be produced by reacting a compound represented by the following general formula (10-5) with thionyl chloride or oxanyl chloride.

（式中、Ｘは前記と同義である。）

(Wherein X is as defined above.)

  Examples of the base that is optionally used in this reaction include inorganic bases such as sodium bicarbonate, sodium carbonate, potassium carbonate, and cesium carbonate; and organic bases such as triethylamine, pyridine, and diisopropylethylamine. The amount of the base used may be 0.1 to 50 times mol, preferably 1 to 5 times mol, of the compound of the general formula (10-2) or general formula (10-3).

  The reaction temperature of this reaction is usually −78 to 100 ° C., preferably 0 to 80 ° C. The reaction may be performed for 10 minutes to 24 hours.

  The compound of the following general formula (10-6) is produced in the same manner as the above general formula (10-4) except that the above general formula (10-3) is used instead of the above general formula (10-2). Can do.

  The compound of the following general formula (1) can be produced in the same manner as the general formula (10-4) except that the compound of the general formula (10-2) and the compound of the general formula (10-3) are used in combination. it can.

  In forming the heat-sensitive recording material in the present invention, the color-forming compound is usually 1 to 50% by weight, preferably 5 to 30% by weight, and the compound represented by the general formula (1) is usually 1 to 70% by weight, Preferably 10 to 50 wt%, sensitizer is usually 1 to 80 wt%, preservability improver is usually 0 to 30 wt%, binder is usually 1 to 90 wt%, filler is usually 0 to 80 wt% , Other lubricants, surfactants, antifoaming agents, and ultraviolet absorbers are used in arbitrary ratios, for example, 0 to 30% by weight, usually (% by weight is the weight ratio of each component in the heat-sensitive recording material). . In the heat-sensitive recording material of the present invention, known color developing compounds, sensitizers or other additives other than the above components may be used in combination.

  The color-forming compound used in the present invention is not particularly limited as long as it is generally used for pressure-sensitive recording paper and heat-sensitive recording paper. Examples of the chromogenic compound used include fluoran compounds, triarylmethane compounds, spiro compounds, diphenylmethane compounds, thiazine compounds, lactam compounds, and fluorene compounds, with fluorane compounds being preferred.

  Specific examples of the fluorane compound include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, and 3- (N-methyl-N-cyclohexyl). Amino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutylamino) ) -6-Methyl-7-anilinofluorane, 3- [N-ethyl-N- (3-ethoxypropyl) amino] -6-methyl-7-anilinofluorane, 3- (N-ethyl-N) -Hexylamino) -6-methyl-7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-propylamino) -6-methyl- -Anilinofluorane, 3- (N-ethyl-N-tetrahydrofurylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (p-chloroanilino) fluorane, 3- Diethylamino-6-methyl-7- (p-fluoroanilino) fluorane, 3- [N-ethyl-N- (p-tolyl) amino] -6-methyl-7-anilinofluorane, 3-diethylamino-6 -Methyl-7- (p-toluidino) fluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloroanilino) fluorane, 3-diethylamino-7- (o-fluoroani Lino) fluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3-diethylamino-7- (3 -Dichloroanilino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-ethoxyethylaminofluorane, 3-diethylamino-6-chloro-7-anilino Fluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-octylfluorane, 3- [N-ethyl-N- (p-tolyl) amino]- Examples include 6-methyl-7-phenethylfluorane, and 3-dibutylamino-6-methyl-7-anilinofluorane is preferable.

  Specific examples of triarylmethane compounds include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone or CVL), 3,3-bis (p-dimethylamino). Phenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylaminoindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole-3) -Yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethyl Aminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9- Tilcarbazol-3-yl) -5-dimethylaminophthalide, 3,3- (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1- Methylpyrrol-2-yl) -6-dimethylaminophthalide and the like.

  Specific examples of spiro compounds include 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3′-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, and 3-propylspirobenzopyran. , 3-methylnaphtho- (3-methoxybenzo) spiropyran, 1,3,3-trimethyl-6-nitro-8′-methoxyspiro (indoline-2,2′-benzopyran), etc .; specific examples of diphenylmethane compounds N-halophenyl-leucooramine, 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-2,4,5-trichlorophenylleucooramine, and the like; specific examples of thiazine compounds include benzoylleuco Methylene blue, p-nitrobenzoyl leucomethylene blue, etc .; Specific examples of the tam compound include rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, etc .; specific examples of the fluorene compound include 3,6-bis (dimethylamino) fluorene spiro (9,3 ') -6'-dimethylaminophthalide, 3,6-bis (dimethylamino) fluorene spiro (9,3')-6'-pyrrolidinophthalide, 3-dimethylamino-6-diethylaminofluorene spiro (9, 3 ′)-6′-pyrrolidinophthalide and the like. These color forming compounds are used alone or in combination.

  In the present invention, the developer is not particularly limited, and may be any developer generally used for pressure-sensitive recording paper or thermal recording paper. For example, α-naphthol, β-naphthol, p-octylphenol, 4-t -Octylphenol, pt-butylphenol, p-phenylphenol, 1,1-bis (p-hydroxyphenyl) propane, 2,2-bis (p-hydroxyphenyl) propane (also known as bisphenol A or BPA), 2, 2-bis (p-hydroxyphenyl) butane, 1,1-bis (p-hydroxyphenyl) cyclohexane, 4,4′-thiobisphenol, 4,4′-cyclo-hexylidene diphenol, 2,2′-bis (2,5-Dibromo-4-hydroxyphenyl) propane, 4,4′-isopropylidenebis (2-tert-butyl) Tilphenol), 2,2′-methylenebis (4-chlorophenol), 4,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-methoxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy- 4′-isopropoxydiphenyl sulfone, 4-hydroxy-4′-ethoxydiphenyl sulfone, 4-hydroxy-4′-butoxydiphenyl sulfone, 4-hydroxy-4′-benzyloxydiphenyl sulfone, bis (4-hydroxyphenyl) acetic acid Phenolic compounds such as methyl, bis (4-hydroxyphenyl) acetic acid butyl, bis (4-hydroxyphenyl) acetic acid benzyl, 2,4-dihydroxy-2′-methoxybenzanilide, benzyl p-hydroxybenzoate, p-hydroxy Benzo Aromatic carboxyl such as ethyl, dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate, ethyl 5-hydroxyisophthalate, 3,5-di-t-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid Acid derivatives, aromatic carboxylic acids or polyvalent metal salts thereof, benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, phenyl-6benzotriazole, phenyl-5benzotriazole, chloro-5 Benzotriazole derivatives such as benzotriazole, chloro-5methylbenzotriazole, chloro-5isopropyl-7methyl-4benzotriazole, bromo-5benzotriazole, saccharin, 1-bromosaccharin, 1-nitrosaccharin, 1-aminosaccharin, etc. of Saccharin derivatives, methanilanilide, N-phenyl-4-aminobenzenesulfonamide, neourilone, N-phenyl-3-nitrobenzenesulfonamide, N- (4-methyl-2-nitrophenyl) benzenesulfonamide, N- (2-methoxy Sulfonamide derivatives such as phenyl) -p-toluenesulfonamide, N- (2- (3-phenylureido) phenyl) benzenesulfonamide, N- (p-toluenesulfonyl) -N ′-(3-n-butylamino) Sulfonylphenyl) urea, N- (p-toluenesulfonyl) -N '-(4-trimethylacetophenyl) urea, N- (benzenesulfonyl) -N'-(3-p-toluenesulfonyloxyphenyl) urea, N- (P-Toluenesulfonyl) -N '-(3-p-toluenesulfo Butylphenyl) urea, N-(p-toluenesulfonyl) -N '- (3- phenylsulfonyloxy phenyl) urea, tolbutamide, etc. sulfonylurea derivatives such as chlorpropamide and the like.

  Specific examples of the sensitizer (thermofusible compound) used in the present invention include waxes such as animal and vegetable waxes and synthetic waxes, higher fatty acids, higher fatty acid amides, higher fatty acid anilides, naphthalene derivatives, aromatic ethers, Aromatic carboxylic acid derivatives, aromatic sulfonic acid ester derivatives, carbonic acid or oxalic acid diester derivatives, biphenyl derivatives, terphenyl derivatives, sulfone derivatives, etc. are mentioned. Among them, those which are solid at room temperature and have a melting point of 60 ° C. or more are preferably used. Is done.

  Specific examples of waxes include wood wax, carnauba wax, shellac, paraffin, montan wax, oxidized paraffin, polyethylene wax, oxidized polyethylene, etc .; higher fatty acids such as stearic acid, behenic acid, etc .; For example, stearic acid amide, oleic acid amide, N-methyl stearic acid amide, erucic acid amide, methylol behenic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, etc .; examples of higher fatty acid anilide include stearic acid anilide, linole Acid anilide and the like; naphthalene derivatives such as 1-benzyloxynaphthalene, 2-benzyloxynaphthalene and 1-hydroxynaphthoic acid phenyl ester; and aromatic ethers such as 1,2-diphenyl Xyethane, 1,4-diphenoxybutane, 1,2-bis (3-methylphenoxy) ethane, 1,2-bis (4-methoxyphenoxy) ethane, 1,2-bis (3,4-dimethylphenyl) ethane 1-phenoxy-2- (4-chlorophenoxy) ethane, 1-phenoxy-2- (4-methoxyphenoxy) ethane, 1,2-diphenoxymethylbenzene, etc .; examples of aromatic carboxylic acid derivatives include p- Hydroxybenzoic acid benzyl ester, p-benzyloxybenzoic acid benzyl ester, terephthalic acid dibenzyl ester, etc .; examples of aromatic sulfonic acid ester derivatives include p-toluenesulfonic acid phenyl ester, phenyl mesitylene sulfonate, 4-methylphenyl mesitylene Sulfonate, etc .; Carbonic acid or oxalic acid dieste Derivatives include, for example, diphenyl carbonate, oxalic acid dibenzyl ester, oxalic acid di (4-chlorobenzyl) ester, oxalic acid di (4-methylbenzyl) ester, etc .; biphenyl derivatives include, for example, p-benzylbiphenyl, p- Examples of the terphenyl derivative include m-terphenyl and the like. Examples of the sulfone derivative include diphenylsulfone and the like.

  Specific examples of the storage stability improver used in the present invention include 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and 2,2′-methylenebis (4-ethyl-6-tert-butylphenol). 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 4,4′-thiobis (2-methyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl) -M-cresol), 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4′-hydroxyphenyl) ethyl] benzene, 1,1, 3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl Enyl) butane, tris (2,6-dimethyl-4-tertiarybutyl-3-hydroxybenzyl) isocyanurate, 4,4′-thiobis (3-methylphenol), 4,4′-dihydroxy-3,3 ′ , 5,5′-tetrabromodiphenylsulfone, 4,4′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenylsulfone, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Hindered phenol compounds such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,4-di Glycidyloxybenzene, 4,4′-diglycidyloxydiphenylsulfone, 4-benzyloxy-4 ′-(2-methylglycidylo Xi) diphenyl sulfone, diglycidyl terephthalate, cresol novolac epoxy resin, phenol novolac epoxy resin, epoxy compound such as bisphenol A epoxy resin, N, N′-di-2-naphthyl-p-phenylenediamine, 2,2 Examples include sodium or polyvalent metal salts of '-methylenebis (4,6-di-tert-butylphenyl) phosphate, bis (4-ethyleneiminocarbonylaminophenyl) methane, and the like. For example, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-) -Tert-butylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-m-cresol), 1- [α-methyl-α -(4'-hydroxyphenyl) ethyl] -4- [α ', α'-bis (4'-hydroxyphenyl) ethyl] benzene, 1,1,3-tris (2-methyl-4-hydroxy-5- Cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tris (2,6-dimethyl) 4-tertiarybutyl-3-hydroxybenzyl) isocyanurate, 4,4′-thiobis (3-methylphenol), 4,4′-dihydroxy-3,3 ′, 5,5′-tetrabromodiphenylsulfone, 4 , 4′-dihydroxy-3,3 ′, 5,5′-tetramethyldiphenylsulfone, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-) Hindered phenol compounds such as 3,5-dichlorophenyl) propane and 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,4-diglycidyloxybenzene, 4,4′-diglycidyloxy Diphenyl sulfone, 4-benzyloxy-4 ′-(2-methylglycidyloxy) diphenyl sulfone, terephthalic acid digg Epoxy compounds such as lysidyl, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, N, N′-di-2-naphthyl-p-phenylenediamine, 2,2′-methylenebis (4,6 -Di-tert-butylphenyl) phosphate sodium or polyvalent metal salt, bis (4-ethyleneiminocarbonylaminophenyl) methane, urea urethane compound (such as developer UU manufactured by Chemipro Kasei Co., Ltd.), and the following formula (11 ) Diphenylsulfone crosslinkable compounds represented by (2) or a mixture thereof.

（式中、ａは０〜６の整数である。）

(In the formula, a is an integer of 0 to 6.)

  Specific examples of the binder used in the present invention include methyl cellulose, methoxy cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose, polyvinyl alcohol (PVA), carboxyl group-modified polyvinyl alcohol, sulfonic acid group-modified polyvinyl alcohol, silyl Group-modified polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polyacrylic acid, starch and derivatives thereof, casein, gelatin, water-soluble isoprene rubber, alkali salt of styrene / maleic anhydride copolymer, iso (or diiso) butylene / maleic anhydride Water-soluble ones such as alkali salts of acid copolymers, (meth) acrylic acid ester copolymers, styrene / (meth) acrylic acid ester copolymers, polymers Urethane, polyester polyurethane, polyether polyurethane, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, polyvinylidene chloride, polystyrene, styrene / butadiene (SB) copolymer Coalesced, carboxylated styrene / butadiene (SB) copolymer, styrene / butadiene / acrylic acid copolymer, acrylonitrile / butadiene (NB) copolymer, carboxylated acrylonitrile / butadiene (NB) copolymer, colloidal silica and Examples include hydrophobic polymer emulsions such as (meth) acrylic resin composite particles.

  Specific examples of the filler used in the present invention include calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, polystyrene resin, Examples include urea-formalin resin.

  Furthermore, various additives other than those described above can be used in the present invention. For example, higher fatty acid metal salts such as zinc stearate and calcium stearate for the purpose of preventing thermal head wear and sticking, and preventing oxidation or aging. Examples thereof include ultraviolet absorbers such as phenol derivatives, benzophenone compounds, and benzotriazole compounds for imparting effects, various surfactants, and antifoaming agents.

Next, a method for preparing the heat-sensitive recording material of the present invention will be described. The developer and sensitizer used in the present invention are separately pulverized and dispersed in a dispersing machine such as a ball mill, an attritor or a sand mill together with a binder or other additives as necessary. (Normally, water is used as a medium when pulverization and dispersion are carried out in a wet manner), and then the dispersion is mixed to prepare a thermal recording material coating solution. Paper (plain paper, fine paper, coated paper, etc.) is used. A sample having the heat-sensitive recording material of the present invention is applied on a support such as a plastic sheet or synthetic paper by a bar coater, a blade coater or the like so as to have a dry weight of 1 to 20 g / m ^2. Make it.

If necessary, an intermediate layer may be provided between the heat-sensitive recording layer and the support, or an overcoat layer (protective layer) may be provided on the heat-sensitive recording layer. The intermediate layer and the overcoat layer (protective layer) are crushed and dispersed as necessary in the same manner as in the preparation of the heat-sensitive recording material coating solution, for example, together with the binder or other additives as necessary. After the layer coating liquid or overcoat layer (protective layer) coating liquid is applied, the coating weight is usually about 0.1 to 10 g / m ^{2 in} terms of the weight during drying, followed by drying.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following examples. In the examples, “parts” is parts by weight and “%” is% by weight.

[Example 1] Synthesis of Compound No. 2 in Table 1 [Step 1-1]
In 130 parts of methylene chloride, 3.2 parts of 1,2-diaminobenzene (Tokyo Kasei) of the following compound (2-1) was added and stirred, and then 3.6 parts of phenyl isocyanate (Tokyo Chemical Industry) was added dropwise at room temperature. After stirring at the same temperature for 2 hours, the precipitate was collected by filtration, the filtrate was washed successively with hexane and water, and dried under vacuum to give the following compound (2-2) as a pale yellow solid, 2.8. I got a part.
MS (ESI): [M−H] ⁻ : cal. : 226.1, found: 226.1

[Step 1-2]
In 200 parts of methylene chloride, 3.0 parts of the above compound (2-2), 1.3 parts of dicycloid isophthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.3 parts of triethylamine were added and stirred at room temperature for 5 hours. The precipitate was collected by filtration, washed successively with ethyl acetate and water, and dried under vacuum to obtain 3.0 parts of compound number 2 in Table 1 as a white solid.
MS (ESI): [M−H] ⁻ : cal. : 583.2, found: 583.2

[Example 2] Synthesis of Compound No. 3 in Table 1 [Step 2-1]
In 200 parts of methylene chloride, 3.0 parts of compound (2-2), 1.3 parts of dicycloid terephthalate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.3 parts of triethylamine were added and stirred at room temperature for 5 hours. The precipitate was collected by filtration, washed successively with ethyl acetate and water, and dried under vacuum to obtain 3.2 parts of the compound of Compound No. 3 in Table 1 as a white solid.
MS (ESI): [M−H] ⁻ : cal. : 583.2, found: 583.2

[Example 3] Production of heat-sensitive recording material Compound No. 2 described in Table 1 obtained in Example 1 was used as a multi-bead shocker manufactured by Yasui Kikai Co., Ltd. (model: PV1001 (S)) with the following composition. [A] liquid was prepared by pulverizing and dispersing for 1 hour.

[A] Solution: 15 parts of Compound No. 2 listed in Table 1
20 parts of 25% PVA aqueous solution
65 parts of water

Dispersion of chromophoric compound by pulverizing and dispersing a mixture having the following composition with a sand grinder using a laser diffraction / scattering particle size distribution measuring apparatus LA-950 (manufactured by Horiba, Ltd.) so that the median particle size becomes 1 μm. Liquid [B] was prepared.
[B] Liquid: 35 parts of 3-dibutylamino-6-methyl-7-anilinofluorane
40 parts of 15% PVA aqueous solution
25 parts of water

Next, each liquid obtained above and the following chemicals were mixed in the following composition to prepare a thermal recording material coating liquid, and the weight when dried on a fine paper having a basis weight of 50 g / m ² was 5 g / m ² . The sample having the heat-sensitive recording layer of the present invention was prepared by coating and drying as described above.
[A] Liquid 40.0 parts [B] Liquid 8.6 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene-butadiene copolymer latex 6.3 parts Water 36.1 parts

(Formation of protective layer)
Next, a protective layer coating solution having the following composition was applied onto the heat-sensitive recording layer so that the weight upon drying was 2 g / m ² and dried to prepare a sample having a heat-sensitive recording layer with a protective layer. did.
40% styrene / acrylic ester copolymer emulsion 115 parts 5% bentonite aqueous dispersion 17 parts 45% styrene / acrylic copolymer aqueous emulsion 44 parts 39% zinc stearate aqueous dispersion 103 parts 67% calcium carbonate aqueous dispersion 15 copies

[Example 4]
A heat-sensitive recording material of the present invention was obtained in the same manner as in Example 3 except that compound number 3 in table 1 was used instead of compound number 2 in table 1.

[Comparative Example 1]
The mixture of the following composition was pulverized and dispersed with a sand grinder using a laser diffraction / scattering particle size distribution measuring apparatus LA-950 (manufactured by Horiba, Ltd.) so that the median particle diameter was 1 μm, and the solution [C] was obtained. A sample having a heat-sensitive recording material for comparison in the same manner as in Example 3 except that the composition [A] in the composition of the heat-sensitive recording layer coating liquid described in Example 1 above was changed to [C] liquid. Got.
[C] Liquid: 25 parts of bisphenol S
20 parts of 25% PVA aqueous solution
55 parts of water

[Water resistance test]
The sample having the heat-sensitive recording material obtained in Examples 3 and 4 and Comparative Example 1 was printed with a pulse width of 1.4 msec using a thermal printer (TH-M2 / PP) manufactured by Okura Engineering Co., Ltd. It was immersed in water at 25 ° C. for 24 hours. The Macbeth reflection density of the colored portion of the sample before and after the test was measured using a colorimeter manufactured by GRETAG-MACBETH, trade name “SpectroEye”. When measuring colors, all were performed under the conditions of Illuminant C as the light source, ANSI A as the density standard, and a viewing angle of 2 degrees. The results are shown in Table 4 below. In addition, it turns out that it is excellent in water resistance, so that a residual rate is high. The residual rate was determined by the following calculation formula (I).
Residual rate (%) = (Macbeth reflection density of the coloring portion of the sample after the test) / (Macbeth reflection density of the coloring portion of the sample before the test) × 100 (I)

上記の表４より明らかなように、本発明化合物を顕色性化合物に用いた実施例３、４は、特許文献２に記載の顕色性化合物であるビスフェノールＳを用いた比較例１に比べて残存率が高く、本発明は従来技術よりも記録画像の耐水性が優れていると言える。

As is apparent from Table 4 above, Examples 3 and 4 using the compounds of the present invention as the color developing compounds were compared with Comparative Example 1 using bisphenol S which is the color developing compound described in Patent Document 2. Therefore, it can be said that the present invention is superior in water resistance of recorded images to the prior art.

[Heat resistance of the skin]
The samples obtained in Examples 3 and 4 and Comparative Example 1 were held at 90 ° C. for 1 hour using a blast incubator manufactured by Yamato Scientific Co., Ltd., trade name DKN402. The ISO whiteness of the background before and after the test was measured using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye. When measuring colors, all were performed under the conditions of Illuminant C as the light source, ANSI A as the density standard, and a viewing angle of 2 degrees. The results are shown in Table 5 below. In addition, it turns out that the background is excellent in heat resistance, so that the variation | change_quantity of ISO whiteness before and behind a test is small.

As is apparent from Table 5 above, Examples 3 and 4 using the compound of the present invention as the color developing compound described in Patent Document 2 because the amount of change in ISO whiteness before and after the heat resistance test was small. Compared to Comparative Example 1 using bisphenol S, which is a color developing compound, the background has extremely high stability to heat.

Claims (8)

A heat-sensitive recording material comprising at least one compound represented by the following general formula (1).

[In the formula (1), X represents a divalent bridging group, and R ^{1 to} R ¹⁰ each independently represent a hydrogen atom, an alkyl group, an arylalkyl group, an aryl group, or a ring atom as a nitrogen atom, oxygen atom, sulfur. 5 or 6-membered heterocyclic group containing 1 to 3 atoms selected from atoms, 1 to 3 atoms selected from nitrogen atom, oxygen atom, sulfur atom as ring constituting atoms, 5 or 6 One benzene ring is condensed to a 5- or 6-membered heterocyclic group containing 1 to 3 atoms selected from a heterocyclic amino group as a ring member, a nitrogen atom, an oxygen atom, and a sulfur atom as ring constituent atoms Condensed 5- or 6-membered heterocyclic amino group, alkoxy group, aryloxy group, alkylcarbonylamino group, arylcarbonylamino group, alkylcarbonyloxy group, arylcarbonyloxy group, alkylcarbo Group, arylcarbonyl group, carbamoyl group, monoalkylcarbamoyl group, dialkylcarbamoyl group, monoarylcarbamoyl group, diarylcarbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, Monoalkylsulfamoyl group, dialkylsulfamoyl group, monoarylsulfamoyl group, diarylsulfamoyl group, hydroxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group, arylthio group, ureido group, dialkylureido group, Monoarylureido group, diarylureido group, alkoxycarbonylamino group, cyano group, nitro group, amino group, monoalkylamino group, dialkylamino group Arylamino group (mono-arylamino group or diarylamino group), a mercapto group, a carboxyl group, a sulfonic group, a halogen atom. ] In the general formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, alkyl group, arylalkyl group, aryl group, alkoxy group, aryloxy group, alkylcarbonylamino group, arylcarbonylamino group, alkylsulfonyl group. An arylsulfonyl group, an arylthio group, a cyano group, a nitro group, an amino group, an arylamino group (monoarylamino group or diarylamino group), a halogen atom; a group selected from the group consisting of: Item 2. The heat-sensitive recording material according to Item 1. 3. The heat-sensitive recording material according to claim 1, wherein in the general formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom or an alkyl group. 4. The heat-sensitive recording material according to claim ¹ , wherein, in the general formula (1), R ^{1 to} R ¹⁰ are all hydrogen atoms. The heat-sensitive recording material according to any one of claims 1 to 4, wherein in the general formula (1), X is an aliphatic hydrocarbon residue or an aromatic residue. 6. The heat-sensitive recording material according to claim 1, wherein X in the general formula (1) is a benzene ring. A heat-sensitive recording layer comprising the heat-sensitive recording material according to any one of claims 1 to 6. A compound in which general formula (1) is represented by the following formula (2) or formula (3).