JP2017052175A - Heat-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-sensitive recording material excellent in color developability and plasticizer resistance of a recording part.SOLUTION: There is provided a heat-sensitive recording material using a combination of a compound represented by the following general formula (1) as a color developing compound and a non-phenolic color developing compound. [wherein, Rrepresents an alkyl group.]SELECTED DRAWING: None

Description

  The present invention relates to a heat-sensitive recording material having excellent color developability and plasticizer resistance of a printed portion.

  In general, heat-sensitive recording materials are obtained by dispersing a leuco dye and a developer such as a phenolic compound separately into fine particles, and then mixing both of them together, such as a binder, a sensitizer, a filler, and a lubricant. A coating solution obtained by adding additives is applied to paper, film, synthetic paper, etc., and develops color by chemical reaction that occurs when one or both of leuco dye and developer are melted and contacted by heating. Recording (printing) is performed. 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 thermal recording materials has been expanded, and the demand for high-speed recording has been further increased in order to further improve productivity, and development of a thermal recording material that can sufficiently cope with high-speed recording is strongly desired. In this case, a developer having a low melting point and a low heat of fusion is required, but this property is liable to cause deterioration of the unrecorded part (background fogging) of the heat-sensitive recording material during production, use or storage. In addition to high whiteness, improvement in stability is also strongly desired.

  In general, a developer having a phenolic hydroxyl group has a high developing ability. Among them, a bisphenol developer has a high color density, and therefore, for example, 2,2-bis (4-hydroxyphenylpropane) disclosed in Patent Document 1 is used. Many reports have been reported, including (bisphenol A) and 4,4′-dihydroxydiphenylsulfone (bisphenol S) disclosed in Patent Document 2. However, they are inferior in plasticizer resistance and have disadvantages such as deterioration of the background (background fogging). Moreover, the use of phenolic compounds such as bisphenol A is considered to be a problem due to the endocrine problem, and a non-phenolic developer that does not contain a phenol structure is desired.

  In response to such a request, for example, Patent Document 3 discloses that a heat-sensitive recording material using a compound represented by the following general formula (1) as a developer has excellent plasticizer resistance and the background is heated. Although it is disclosed that it exhibits high stability, this heat-sensitive recording material is expected to improve the color development sensitivity and improve the image stability (plasticizer resistance) against plasticizers contained in plastic sheets and erasers. It was rare.

（式（１）中、Ｒ^１はアルキル基を表す。）

(In formula (1), R ¹ represents an alkyl group.)

US Pat. No. 3,539,375 Japanese Patent Laid-Open No. 57-11088 Japanese Patent Application No. 2014-240944

  An object of the present invention is to provide a heat-sensitive recording material excellent in color developability for the purpose of solving the above-mentioned drawbacks of color developability.

  The inventor of the present invention has completed the present invention as a result of intensive studies to achieve the above object.

（式（１）中、Ｒ^１はアルキル基を表す。）
［２］非フェノール系顕色性化合物が、ベンゾトリアゾール誘導体、サッカリン誘導体、スルホンアミド誘導体、マロンアミド誘導体、チオ尿素誘導体、安息香酸誘導体、スルホニルウレア誘導体、及びアミノ基で置換されたジフェニルスルホン誘導体のいずれかより選ばれる一種であることを特徴とする［１］に記載の感熱記録材料、
［３］式（１）において、Ｒ^１が無置換またはアリール基で置換されているアルキル基である事を特徴とする［１］または［２］に記載の感熱記録材料、
［４］式（１）において、Ｒ^１が無置換のアルキル基である事を特徴とする［１］乃至［３］のいずれか一つに記載の感熱記録材料、
［５］式（１）において、Ｒ^１がメチル基またはエチル基である事を特徴とする［１］乃至［４］のいずれか一つに記載の感熱記録材料、
［６］［１］乃至［５］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、
に関する。 That is, the present invention
[1] A heat-sensitive recording material comprising a compound represented by the following general formula (1) and a non-phenolic color developing compound in combination:

(In formula (1), R ¹ represents an alkyl group.)
[2] Any of a non-phenolic color developing compound, a benzotriazole derivative, a saccharin derivative, a sulfonamide derivative, a malonamide derivative, a thiourea derivative, a benzoic acid derivative, a sulfonylurea derivative, and a diphenylsulfone derivative substituted with an amino group The heat-sensitive recording material according to [1], which is a kind selected from the group consisting of:
[3] The thermosensitive recording material according to [1] or [2], wherein in formula (1), R ¹ is an alkyl group which is unsubstituted or substituted with an aryl group,
[4] The thermosensitive recording material according to any one of [1] to [3], wherein in formula (1), R ¹ is an unsubstituted alkyl group,
[5] The heat-sensitive recording material according to any one of [1] to [4], wherein in formula (1), R ¹ is a methyl group or an ethyl group,
[6] A thermal recording layer containing the thermal recording material according to any one of [1] to [5],
About.

  The present invention provides a heat-sensitive recording material excellent in color developability and printed portion plasticizer resistance by using a compound represented by formula (1) as a color developing compound and a non-phenolic color developing compound. We were able to.

The present invention will be described in detail.
In the present invention, usually a colorless or light-color developing compound, a compound represented by the above formula (1) as a developing compound and a non-phenolic developing compound are included, and if necessary, other developing properties. The present invention relates to a heat-sensitive recording material containing a compound, a sensitizer, a storage stability improver, a binder shown below, and, if necessary, a filler and other additives.

  In the present invention, the non-phenolic color developing compound means a compound having no phenol structure in the molecule, and a compound known per se can be used. Specific examples include benzotriazole derivatives, saccharin derivatives, sulfonamide derivatives, malonamide derivatives, thiourea derivatives, sulfonylurea derivatives, diphenylsulfone derivatives substituted with amino groups, and the like.

  The benzotriazole derivative is not particularly limited, and specific examples thereof include benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, phenyl-6benzotriazole, and phenyl-5. Examples include benzotriazole, chloro-5 benzotriazole, chloro-5 methylbenzotriazole, chloro-5 isopropyl-7 methyl-4 benzotriazole, bromo-5 benzotriazole, and the like.

  The saccharin derivative is not particularly limited, and specific examples thereof include saccharin, 1-bromosaccharin, 1-nitrosaccharin, 1-aminosaccharin and the like.

  The sulfonamide derivative is not particularly limited, and specific examples thereof include methanylanilide, N-phenyl-4-aminobenzenesulfonamide, neourilone, N-phenyl-3-nitrobenzenesulfonamide, N- (4- Methyl-2-nitrophenyl) benzenesulfonamide, N- (2-methoxyphenyl) -p-ruenesulfonamide, N- (4-toxylphenyl) -p-toluenesulfonamide, N- (2-chlorophenyl) -p -Toluenesulfonamide, N- (4-methylphenyl) -4-methylbenzenesulfonamide, N- (2-methylphenyl) -p-toluenesulfonamide, N-phenylbenzenesulfonamide, 4-bromo-4'- Methylbenzenesulfonanilide, N- (4-bromophenyl) ben Sulfonamide, N- (3-nitrophenyl) benzenesulfonamide, N- (4-nitrophenyl) -4-methylbenzenesulfonamide, N- (4-methylphenyl) benzenesulfonamide, N-phenyl-p- Toluenesulfonamide, N-phenylbenzenesulfonamide and the like can be mentioned.

  The malonamide derivative is not particularly limited, and specific examples thereof include N, N′-bis (2-hydroxy-5-phenyl) phenyl-malonamide, N, N′-diphenylmalonamide, N, N '-Bis (2,4,6-tribromophenyl) malonamide, N, N'-bis (2-aminophenyl) malonamide, N, N'-bis (m-trifluoromethylphenyl) malonamide, N, N' -Bis (m-trifluoromethylphenyl) α, α-dichloromalonamide, diethylmalondianilide and the like.

  The thiourea derivative is not particularly limited, and specific examples thereof include 1,3-bis (4-methylphenyl) thiourea, 1,3-bisphenylthiourea, 1,3-bis (4 -Chlorophenyl) thiourea, 1,3-bis (4-methoxyphenyl) thiourea, N, N'-bis (3-chlorophenyl) thiourea, 1,3-bis (3-methoxyphenyl) thiourea, 3-bis (3-methylphenyl) thiourea, 1,3-bis (4-benzylphenyl) thiourea, 1,3-bis (4-bromophenyl) thiourea, 1-phenyl-3-butylthiourea, 1 -Phenyl-3-ethylthiourea and the like.

  The sulfonylurea derivative is not particularly limited, and specific examples thereof include N- (p-toluenesulfonyl) -N ′-(3-n-butylaminosulfonylphenyl) urea, N- (p-toluenesulfonyl). ) -N '-(4-trimethylacetophenyl) urea, N- (benzenesulfonyl) -N'-(3-p-toluenesulfonyloxyphenyl) urea, N- (p-toluenesulfonyl) -N '-(3 -P-toluenesulfonylphenyl) urea, N- (p-toluenesulfonyl) -N '-(3-phenylsulfonyloxyphenyl) urea, tolbutamide, chloropropamide and the like.

  The diphenylsulfone derivative substituted with an amino group is not particularly limited, and specific examples thereof include 2-aminodiphenylsulfone, 2,2′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, 4,4'-diaminodiphenyl sulfone, etc. are mentioned.

  Of these non-phenolic color developing compounds, saccharin derivatives, sulfonamide derivatives, sulfonylurea derivatives, and diphenylsulfone derivatives substituted with amino groups are preferred, and sulfonylurea derivatives and diphenylsulfone derivatives substituted with amino groups are particularly preferred. .

Examples of the alkyl group in R ¹ of the formula (1) include a linear, branched or cyclic alkyl group. Among these, a straight chain or a branched chain is preferable, and a straight chain is more preferable. The range of the carbon number is usually C1 to C12, preferably C1 to C8, more preferably C1 to C6, and still more preferably C1 to C4. Specific examples thereof include linear chains such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl. Alkyl groups; branched chain alkyl groups such as isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, isohexyl, and isooctyl; cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl;

R ^{1 in} formula (1) may have a substituent, and specific examples thereof are as follows, but are not limited thereto.
That is,
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 or a sulfur atom as a ring-constituting atom (preferably the heterocyclic moiety is aromatic. 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 atoms include nitrogen atoms, and Preferably selected from a sulfur atom;

  A 5- or 6-membered heterocyclic amino group containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom as a ring-constituting atom (preferably the heterocyclic moiety is aromatic, As pyrrolidinylamino, tetrahydrofurylamino, tetrahydrothiophen-2-ylamino, tetrahydrothiophen-3-ylamino and the like; piperidinylamino, piperazinylamino, dioxan-2-ylamino , Morpholinylamino, thiomorpholinylamino, and the like; pyrroleamino, pyrazoleamino, imidazolamino, triazoleamino, furylamino, thiophen-2-ylamino, thiophen-3-ylamino, oxazoleamino Aromatic 5-membered rings such as thiazoleamino; pyridylami , Pyrazylamino, pyridazinylamino, triazinylamino, and the like; and the like. Among them, the ring-constituting atom is selected from a nitrogen atom and a sulfur atom. Is preferred;

  A condensed 5- or 6-membered ring in which one benzene ring is condensed to a 5- or 6-membered ring containing 1 to 3 atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom as a ring-constituting atom Heterocyclic amino group (preferably the heterocyclic moiety is aromatic, and 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, quinazolin A heterocyclic moiety such as ruamino, 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;

  A linear, branched or cyclic alkoxy group, preferably a 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 A branched chain (preferably C3 to C10) such as octyloxy, 2-ethylhexyloxy, isononyloxy, isodecyloxy; cyclic such as cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptoxy (preferably C3 to C ) Ones; preferably an alkoxy group having a linear or branched chain).;

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

  Linear, branched or cyclic alkylcarbonylamino group, preferably 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- Butylcarbonylamino, t-butylcarbonylamino, isoamylcarbonylamino, t-amylcarbonylamino, isohexylcarbonylamino, t-hexylcarbonylamino, isoheptylcarbo A branched chain (preferably C3 to C10) such as ruamino, t-heptylcarbonylamino, isooctylcarbonylamino, t-octylcarbonylamino, 2-ethylhexylcarbonylamino, isononylcarbonylamino, isodecylcarbonylamino; cyclopropyl Cyclic (preferably C3-C7) such as carbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino; preferably linear or branched alkylcarbonylamino group, more preferably straight Chain alkylcarbonylamino groups));

  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 compounds such as pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, n-decylcarbonyloxy; isopropylcarbonyloxy, isobutylcarbonyloxy, sec- Butylcarbonyloxy, t-butylcarbonyloxy, isoamylcarbonyloxy, t-amylcarbonyloxy, isohexylcarbonyloxy, t-hexylcarbonyloxy, isoheptylcarbo A branched chain (preferably C3 to C10) such as ruoxy, t-heptylcarbonyloxy, isooctylcarbonyloxy, t-octylcarbonyloxy, 2-ethylhexylcarbonyloxy, isononylcarbonyloxy, isodecylcarbonyloxy, etc .; cyclopropyl Cyclic (preferably C3 to C7) such as carbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy; among them, a linear or branched alkylcarbonyloxy group is preferable, An alkylcarbonyloxy group is more preferred.); An arylcarbonyloxy group, preferably a C6-C12 arylcarbonyloxy group (specific examples include phenylcarbonyloxy, Chill carbonyloxy, biphenyl carbonyloxy, etc.).;

  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-amyl Carbonyl, isohexylcarbonyl, t-hexylcarbonyl, isoheptylcarbonyl, t-heptylcarbonyl, isooctylcarbonyl, t-octylcarbonyl, 2-ethylhexylcarbonyl, isononylcarbonyl A branched chain (preferably C3 to C10) such as bonyl, isodecylcarbonyl; cyclic (preferably C3 to C7) such as cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl; A linear or branched alkylcarbonyl group is preferred, and a linear alkylcarbonyl group is more preferred);

  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 Straight chain such as -hexylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, n-nonylcarbamoyl, n-decylcarbamoyl; 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 to 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-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, isoheptyl sulfamoyl, t-heptyl sulf A branched chain (preferably C3 to C10) such as moyl, 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.);

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 linear 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.

  Monoarylureido groups, preferably monoC6-C12 arylureido groups (specific examples include phenylureido, naphthylureido, biphenylureido, etc.); diarylureido groups, preferably diC6-C12 arylureido groups (specifically Examples include diphenylureido, dinaphthylureido, di (biphenyl) ureido, etc.);

  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-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 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, as the arylamino group, a di-C6-C12 arylamino group (specific examples include diphenylamino, dinaphthylamino, di (biphenyl) amino, etc.);

  Mercapto group (in this specification, meaning a group represented by “—SH”); halogen atom (specific examples include fluorine atom, chlorine atom, bromine atom; preferably fluorine atom, chlorine atom, bromine atom) An atom)); a hydroxy group, a cyano group, a nitro group, an amino group, a carboxy group, and the like.

The above substituents for R ¹ may have one or two groups, preferably one further, selected from these substituents.

In R ¹ , the alkyl group which may have a substituent is preferably unsubstituted or substituted with an aryl group, more preferably unsubstituted, and particularly preferably a methyl group or an ethyl group.

In the above formula (1), examples of the substitution position of the substituent: -HNCOR ¹ include an ortho position, a meta position, and a para position, and an ortho position and a meta position are preferable.

Specific examples of the compound represented by the formula (1) of the present invention include the following Table 1-1 to Table 1-9, but are not limited thereto.

  In forming the heat-sensitive recording material in the present invention, the color developing compound is usually 1 to 50% by weight, preferably 5 to 30% by weight, and the compound represented by the above formula (1) as a color developing compound and a non-phenol based color developing. The total amount of the organic compound is usually 1 to 50% by weight, preferably 5 to 30% by weight, the sensitizer is 1 to 80% by weight, the preservability improver is usually 0 to 30% by weight, and the binder is usually 1 to 90%. % By weight, filler is usually 0 to 80% by weight, and other lubricants, surfactants, antifoaming agents, and UV absorbers are each used in an arbitrary ratio, for example, usually 0 to 30% by weight (weight% is The weight ratio of each component in the thermosensitive coloring layer). In a more preferred embodiment, the weight ratio of the compound represented by the formula (1) to the non-phenolic color developing compound in the above composition is preferably 9: 1 to 1: 9, and 6: 4 to 2: 8. Particularly preferred. In addition, in the heat-sensitive recording material of the present invention, a known color developing compound, a sensitizer, 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, 3- (N-methyl-N- Cyclohexylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isopentylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutyl) Amino) -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-me Ru-7-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 -Fluoroanilino) fluorane, 3-dibutylamino-7- (o-fluoroanilino) fluorane, 3-diethylamino-7- 3,4-dichloroanilino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-ethoxyethylaminofluorane, 3-diethylamino-6-chloro-7 -Anilinofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-octylfluorane, 3- [N-ethyl-N- (p-tolyl) Amino] -6-methyl-7-phenethylfluorane and the like, and 3-dibutylamino-6-methyl-7-anilinofluorane is preferred.

  Specific examples of triarylmethane compounds include, for example, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone or CVL), 3,3-bis (p-dimethyl). Aminophenyl) 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 Dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis 9-ethylcarbazol-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 the spiro compound include, for example, 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3′-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-propylspirobenzo. Pyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 1,3,3-trimethyl-6-nitro-8′-methoxyspiro (indoline-2,2′-benzopyran), etc .; specific examples of diphenylmethane compounds Are, for example, N-halophenyl-leucooramine, 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-2,4,5-trichlorophenylleucooramine, and the like. Specific examples of thiazine compounds include For example, benzoylleucomethylene blue, p-nitrobenzoylleucome Specific examples of lactam compounds include, for example, rhodamine B anilinolactam, rhodamine Bp-chloroanilinolactam, etc .; specific examples of fluorene compounds include, for example, 3,6-bis (dimethylamino) fluorene Spiro (9,3 ′)-6′-dimethylaminophthalide, 3,6-bis (dimethylamino) fluorene spiro (9,3 ′)-6′-pyrrolidinophthalide, 3-dimethylamino-6-diethylamino Fluorene spiro (9,3 ′)-6′-pyrrolidinophthalide and the like. These color forming compounds are used alone or in combination.

  The color developing compound that can be used in combination in the present invention is not particularly limited, and may be any compound that is generally used for pressure-sensitive recording paper and heat-sensitive recording paper. For example, α-naphthol, β-naphthol, p-octylphenol. 4-tert-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'-isopropylidene Bis (2-t-butylphenol), 2,2′-methylenebis (4-chlorophenol), 4,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-methoxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-ethoxydiphenylsulfone, 4-hydroxy-4′-butoxydiphenylsulfone, 4-hydroxy-4′-benzyloxydiphenylsulfone, bis (4 Phenolic compounds such as -hydroxyphenyl) methyl acetate, bis (4-hydroxyphenyl) butyl acetate, bis (4-hydroxyphenyl) acetate benzyl, 2,4-dihydroxy-2'-methoxybenzanilide, p-hydroxybenzoic acid Benzyl, p- Such as ethyl droxybenzoate, dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate, ethyl 5-hydroxyisophthalate, 3,5-di-t-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, etc. An aromatic carboxylic acid derivative, an aromatic carboxylic acid or a polyvalent metal salt thereof can be used.

  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. used.

  Specific examples of waxes include, for example, wood wax, carnauba wax, shellac, paraffin, montan wax, oxidized paraffin, polyethylene wax, polyethylene oxide, etc .; higher fatty acids such as stearic acid, behenic acid, etc .; higher fatty acid amides 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 .; Linoleic acid anilide, etc .; As naphthalene derivatives, for example, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, etc .; As aromatic ethers, for example, 1,2- Phenoxyethane, 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, phenylmesitylene sulfonate, 4-methylphenyl Mesitylene sulfonate, etc .; carbonic acid or dioxalic acid Examples of the steal derivatives include diphenyl carbonate, oxalic acid dibenzyl ester, oxalic acid di (4-chlorobenzyl) ester, and oxalic acid di (4-methylbenzyl) ester; examples of the biphenyl derivative include p-benzyl biphenyl, p -Allyloxybiphenyl and the like; 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, 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- Tilphenyl) 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-methylglyci (Zyloxy) diphenylsulfone, diglycidyl terephthalate, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type 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, and the like.

  Specific examples of the binder used in the present invention include, for example, 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 / anhydrous Water-soluble maleic acid copolymer such as alkali salt, (meth) acrylic acid ester copolymer, styrene / (meth) acrylic acid ester copolymer , Polyurethane, polyester polyurethane, polyether polyurethane, polyvinyl acetate, ethylene / vinyl acetate copolymer, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, polyvinylidene chloride, polystyrene, styrene / butadiene (SB) Polymer, carboxylated styrene / butadiene (SB) copolymer, styrene / butadiene / acrylic acid copolymer, acrylonitrile / butadiene (NB) copolymer, carboxylated acrylonitrile / butadiene (NB) copolymer, colloidal silica And hydrophobic polymer emulsions such as composite particles of (meth) acrylic resin.

  Specific examples of the filler used in the present invention include, for example, calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, talc, clay, alumina, magnesium hydroxide, aluminum hydroxide, aluminum oxide, barium sulfate, polystyrene resin. And 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 chromogenic compound, the compound represented by the general formula (1), and the non-phenolic compound used in the present invention, such as a ball mill, an attritor, and a sand mill, together with a binder or other additives as required After pulverizing and dispersing with a disperser to prepare a dispersion (usually, water is used as a medium when pulverization or dispersion is performed in a wet manner), the dispersion is mixed to prepare a thermal recording material coating liquid, and paper (ordinary Paper, fine paper, coated paper, etc. can be used), coated on a support such as plastic sheet, synthetic paper, etc. with a bar coater, blade coater, etc. so that the dry weight is usually 1-20 g / m ^2. A sample having the thermosensitive recording layer of the present invention is prepared.

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” are parts by weight, and “%” in the description of the solution is% by weight.

[Example 1] Production of heat-sensitive recording material Dispersion liquid [A] obtained by pulverizing and dispersing Compound No. 1 shown in Table 1 using a sand grinder with the following composition to a median particle diameter of 1 µm or less. Prepared.

[A] Solution: 25 parts of Compound No. 1 described in Table 1
20 parts of 25% PVA aqueous solution
55 parts of water

A mixture of the following composition was pulverized and dispersed using a sand grinder so that the median particle diameter was 1 μm or less to prepare a color developing compound dispersion [B].
[B] Liquid: 35 parts of 3-dibutylamino-6-methyl-7-anilinofluorane
40 parts of 15% PVA aqueous solution
25 parts of water

A dispersion [C] was prepared by pulverizing and dispersing 4,4′-diaminodiphenyl sulfone used in the present invention with a sand grinder with the following composition so that the median particle diameter was 1 μm or less.
[C] Liquid: 25 parts of 4,4′-diaminodiphenyl sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.)
20 parts of 25% PVA aqueous solution
55 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 heat-sensitive recording layer of the present invention was prepared by coating and drying as described above.
[A] Liquid 19.2 parts [B] Liquid 8.6 parts [C] Liquid 4.8 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% Modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

(Formation of protective layer)
Next, a protective layer coating solution having the following composition was applied onto the thermosensitive recording layer so that the weight upon drying was 2 g / m ² and dried to prepare a thermosensitive recording layer with a protective layer.
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 2]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[A] Liquid 16.8 parts [B] Liquid 8.6 parts [C] Liquid 7.2 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Example 3]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[A] Liquid 14.4 parts [B] Liquid 8.6 parts [C] Liquid 9.6 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% Modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Example 4]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[A] Liquid 12.0 parts [B] Liquid 8.6 parts [C] Liquid 12.0 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Example 5]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[A] Liquid 9.6 parts [B] Liquid 8.6 parts [C] Liquid 14.4 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% Modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Example 6]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[A] liquid 7.2 parts [B] liquid 8.6 parts [C] liquid 16.8 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene / butadiene copolymer latex 6.3 parts water 52.1 copies

[Example 7]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[A] Liquid 4.8 parts [B] Liquid 8.6 parts [C] Liquid 19.2 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% Modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Comparative Example 1]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[A] Liquid 24.0 parts [B] Liquid 8.6 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene-butadiene copolymer latex 6.3 parts Water 52.1 parts

[Comparative Example 2]
A sample having the heat-sensitive recording material of the present invention was obtained by applying and drying the above [A], [B], and [C] liquids in the same manner as in Example 1 except that they were mixed at the following composition ratios.
[B] Liquid 8.6 parts [C] Liquid 24.0 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene-butadiene copolymer latex 6.3 parts Water 52.1 parts

[Color development test (static color development sensitivity)]
Each sample having the heat-sensitive recording layer obtained in Examples 1 to 7 and Comparative Examples 1 and 2 was printed with a thermal inclination tester (model: HG-100-2) manufactured by Toyo Seiki Seisakusho. . The applied temperature was heated at 150 ° C., 160 ° C. and 170 ° C. for 1 second. The Macbeth reflection density of the printed portion 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 2 below. It can be seen that the higher the Macbeth reflection density, the better the color developability.

  As is clear from Table 2, the heat-sensitive recording material of the present invention in which the compound represented by the formula (1) and the non-phenolic color developing compound are used in combination as the color developing compound is a comparison using each compound alone. Compared to Example 1 and Comparative Example 2, the color density (Macbeth reflection density) is high, and the color developability is excellent.

[Storage stability test (plasticizer resistance test)]
A vinyl chloride wrap film (containing a plasticizer) is wrapped around a glass plate in a single layer, and the heat-sensitive recording obtained in Examples 1 to 7 and Comparative Examples 1 and 2 above. Each sample having a layer was printed and pasted with a pulse width of 1.4 msec using a thermal printer (TH-M2 / PP) manufactured by Okura Engineering Co., Ltd. Further, the vinyl chloride wrap film was wound on it in a single layer and allowed to stand at 45 ° 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 3 below. It can be seen that the higher the residual ratio, the better the plasticizer resistance. The residual rate was calculated by the following formula.
Residual rate (%) = (Macbeth reflection density of the colored portion of the sample after the test) / (Macbeth reflection density of the colored portion of the sample before the test) × 100

As is apparent from Table 3, the heat-sensitive recording material of the present invention using the compound represented by the formula (1) and the non-phenolic color developing compound as the color developing compound is a comparative example in which each compound is used alone. Compared to 1 and Comparative Example 2, the residual ratio after the test is high, and the printed portion has excellent plasticizer resistance.

Claims (6)

A heat-sensitive recording material comprising a compound represented by the following general formula (1) and a non-phenolic color developing compound in combination.

[In the formula (1), R ¹ represents an alkyl group. ] The non-phenolic color developing compound is selected from any of benzotriazole derivatives, saccharin derivatives, sulfonamide derivatives, malonamide derivatives, thiourea derivatives, benzoic acid derivatives, sulfonylurea derivatives, and diphenylsulfone derivatives substituted with amino groups. The heat-sensitive recording material according to claim 1, which is a kind. The heat-sensitive recording material according to claim 1 or 2, wherein in the formula (1), R ¹ is an alkyl group which is unsubstituted or substituted with an aryl group. The thermosensitive recording material according to any one of claims 1 to 3, wherein in the formula (1), R ¹ is an unsubstituted alkyl group. The thermosensitive recording material according to any one of claims 1 to 4, wherein in the formula (1), R ¹ is a methyl group or an ethyl group. A thermosensitive recording layer comprising the thermosensitive recording material according to any one of claims 1 to 5.