JP2017205938A - Heat-sensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-sensitive recording material excellent in plasticizer resistance and oil resistance of a printed part.SOLUTION: The heat-sensitive recording material uses, as developing compounds, a compound represented by the general formula (1) in the figure, where Rrepresents an alkyl group, and a phenolic developing compound.SELECTED DRAWING: None

Description

  The present invention relates to a heat-sensitive recording material excellent in plasticizer resistance and oil 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 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 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 color developing ability. Among them, a bisphenol developer is a 2,2-bis (4-hydroxyphenylpropane) described in Patent Document 1, for example, due to its high color density. Many reports have been reported, including (bisphenol A) and 4,4′-dihydroxydiphenylsulfone (bisphenol S) described in Patent Document 2. However, they are inferior in plasticizer resistance and have disadvantages such as deterioration of the background (background fogging).

  In response to such a request, for example, Patent Document 3 discloses a heat-sensitive recording material using a specific color developing compound, which has excellent plasticizer resistance and the background has high stability against heat. However, it is inferior in image stability (plasticizer resistance) against plasticizers contained in plastic sheets and erasers, and image stability (oil resistance) against oil attached when touched by hand. There is a strong demand for improvement in performance.

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 storage stability for the purpose of solving the drawbacks of storage stability of a color developing portion as described above.

  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］フェノール系顕色性化合物が、２，２−ビス（ｐ−ヒドロキシフェニル）プロパン、４，４’−ジヒドロキシジフェニルスルホン、４−ヒドロキシ−４’−イソプロポキシジフェニルスルホン、４−ヒドロキシ−４’−プロポキシジフェニルスルホン、４−ヒドロキシ−４’−ベンジルオキシジフェニルスルホン、２，４’−ジヒドロキシジフェニルスルホンのいずれかより選ばれ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が無置換又はアリール基で置換されたアルキル基である化合物を使用する事を特徴とする［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が無置換のアルキル基である化合物を使用する事を特徴とする［１］乃至［３］のいずれか一つに記載の感熱記録材料、
［５］一般式（１）において、Ｒ^１がメチル基又はエチル基のいずれかである化合物を使用する事を特徴とする［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、
［７］［１］乃至［６］のいずれか一つに記載の感熱記録材料又は感熱記録層を含む感熱記録紙、
に関する。 That is, the present invention
[1] A heat-sensitive recording material using a compound represented by the following general formula (1) and a phenol-based developer compound,

(In formula (1), R ¹ represents an alkyl group.)
[2] The phenolic color developing compound is 2,2-bis (p-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4 The heat-sensitive recording material according to [1], which is selected from any of '-propoxydiphenylsulfone, 4-hydroxy-4'-benzyloxydiphenylsulfone, and 2,4'-dihydroxydiphenylsulfone,
[3] The heat-sensitive recording material according to [1] or [2], wherein a compound in which R ¹ is an alkyl group unsubstituted or substituted with an aryl group in the general formula (1) is used.
[4] The heat-sensitive recording material according to any one of [1] to [3], wherein a compound in which R ¹ is an unsubstituted alkyl group in the general formula (1) is used.
[5] The heat-sensitive recording material according to any one of [1] to [4], wherein a compound in which R ¹ is either a methyl group or an ethyl group in the general formula (1) is used. ,
[6] A thermal recording layer containing the thermal recording material according to any one of [1] to [5],
[7] A heat-sensitive recording paper comprising the heat-sensitive recording material or heat-sensitive recording layer according to any one of [1] to [6],
About.

  The present invention provides a heat-sensitive recording material in which a coloring portion is excellent in plasticizer resistance and oil resistance by using a compound represented by the general formula (1) and a phenol-based color developing compound as the color developing compound. I was able to.

The present invention will be described in detail.
The present invention usually includes a colorless or light-color developing compound, a compound represented by the above general formula (1) as a developing compound and a phenol developing compound, 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, and the binder and filler described below, and other additives.

  The phenolic color developing compound used in the present invention means a compound having a hydroxy group directly bonded to a benzene ring in the molecule, and a compound known per se can be used. Specific examples include 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'-thio Bisphenol, 4,4′-cyclo-hexylidene diphenol, 2,2′-bis (2,5-dibromo-4-hydroxyphenyl) propane, 4,4′-isopropylidenebis (2-t-butylphenol), 2,2'-methylenebis (4-chlorophenol), 4,4'-dihydroxydiphenylsulfur Hong, 4-hydroxy-4'-methoxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-ethoxydiphenylsulfone, 4-hydroxy-4 '-Propoxydiphenylsulfone, 4-hydroxy-4'-vinyloxydiphenylsulfone, 4-hydroxy-4'-butoxydiphenylsulfone, 4-hydroxy-4'-benzyloxydiphenylsulfone, methyl bis (4-hydroxyphenyl) acetate Butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, 2,4-dihydroxy-2′-methoxybenzanilide and the like.

  Among these phenol-based color developing compounds, 2,2-bis (p-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 2,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′- Isopropoxy diphenyl sulfone, 4-hydroxy-4′-propoxy diphenyl sulfone, and 4-hydroxy-4′-vinyloxydiphenyl sulfone are preferable, and 4,4′-dihydroxydiphenyl sulfone and 2,4′-dihydroxydiphenyl sulfone are particularly preferable. .

Examples of the alkyl group for R ¹ in the general formula (1) include a linear, branched or cyclic alkyl group, but a linear or branched chain is preferable, and a linear 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 further 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 the} general formula (1) may have a substituent, and specific examples thereof are as follows, but are not limited thereto.
That is,
As the aryl group, a C6-C12 aryl group is preferable, and specific examples thereof include phenyl, naphthyl, biphenyl and the like.

  In addition, as 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, the heterocyclic moiety is preferably aromatic, Specific examples include 5-membered alicyclic compounds such as pyrrolidinyl, tetrahydrofuryl, tetrahydrothiophen-2-yl, and tetrahydrothiophen-3-yl; 6-membered materials such as piperidinyl, piperazinyl, dioxane-2-yl, morpholinyl, and thiomorpholinyl. Cycloaliphatics; aromatic 5-membered rings such as pyrrole, pyrazole, imidazole, triazole, furyl, thiophen-2-yl, thiophen-3-yl, oxazole, thiazole; pyridine, pyrazine, pyridazine, triazine, etc. Aromatic 6-membered ring; Of the above, the ring-constituting atoms are preferably selected from either a nitrogen atom or a sulfur atom.

  As the 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, the heterocyclic moiety is preferably aromatic. Examples include 5-membered alicyclics such as pyrrolidinylamino, tetrahydrofurylamino, tetrahydrothiophen-2-ylamino, tetrahydrothiophen-3-ylamino; piperidinylamino, piperazinylamino, dioxane-2- 6-membered alicyclic compounds such as ylamino, morpholinylamino, thiomorpholinylamino; pyrroleamino, pyrazoleamino, imidazolamino, triazoleamino, furylamino, thiophen-2-ylamino, thiophen-3-ylamino, oxazole Aromatic 5-membered rings such as amino and thiazoleamino; pyridyl Mino, Pirajiruamino, pyridazinyl amino, those 6-membered aromatic ring such as triazinylamino; and the like. Of the above, the ring-constituting atoms are preferably selected from either a nitrogen atom or a sulfur atom.

  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 constituent atom The heterocyclic amino group preferably has an aromatic heterocyclic moiety, and specific examples include a 5-membered alicyclic heterocyclic moiety such as phthalanylamino; a heterocyclic moiety such as benzopyranylamino 6 Alicyclic; benzpyrroleamino, benzpyrazoleamino, benzimidazolamino, benzotriazoleamino, benzofuranylamino, benzothiophen-2-ylamino, benzothiophen-3-ylamino, benzoxazoleamino, benzothiazoleamino A heterocyclic moiety such as quinolinylamino, cinnolinylamino, phthalazinylamino, quina Riniruamino, heterocyclic moiety quinoxalinium Li arylsulfonylamino like those aromatic 6-membered ring; and the like are. Of the above, the ring-constituting atoms are preferably selected from either a nitrogen atom or a sulfur atom.

  The linear, branched or cyclic alkoxy group is preferably a C1-C10 alkoxy group, and specific examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n Straight chain such as heptoxy, n-octyloxy, n-nonyloxy, n-decyloxy; isopropoxy, isobutoxy, sec-butoxy, t-butoxy, isoamyloxy, t-amyloxy, isohexyloxy, t-hexyloxy, isoheptoxy, t- Branched chain (preferably C3 to C10) such as heptoxy, isooctyloxy, t-octyloxy, 2-ethylhexyloxy, isononyloxy, isodecyloxy; cyclic (preferably cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexoxy, cycloheptoxy, etc. Properly is C3-C7) ones; and the like, more preferably an alkoxy group having a linear or branched chain.

  The aryloxy group is preferably a C6-C12 aryloxy group, and specific examples thereof include phenoxy, naphthyloxy, biphenyloxy and the like.

  The linear, branched or cyclic alkylcarbonylamino group is preferably a C1 to C10 alkylcarbonylamino group, and specific examples thereof include methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, n-butylcarbonylamino. , N-pentylcarbonylamino, n-hexylcarbonylamino, n-heptylcarbonylamino, n-octylcarbonylamino, n-nonylcarbonylamino, n-decylcarbonylamino and the like; isopropylcarbonylamino, isobutylcarbonylamino , Sec-butylcarbonylamino, t-butylcarbonylamino, isoamylcarbonylamino, t-amylcarbonylamino, isohexylcarbonylamino, t-hexylcarbonylamino, isohept A branched chain (preferably C3 to C10) such as rucarbonylamino, t-heptylcarbonylamino, isooctylcarbonylamino, t-octylcarbonylamino, 2-ethylhexylcarbonylamino, isononylcarbonylamino, isodecylcarbonylamino; Cyclic (preferably C3 to C7) such as cyclopropylcarbonylamino, cyclobutylcarbonylamino, cyclopentylcarbonylamino, cyclohexylcarbonylamino, cycloheptylcarbonylamino; and the like, and a linear or branched alkylcarbonylamino group Are preferred, and a linear alkylcarbonylamino group is more preferred.

  As the arylcarbonylamino group, a C6-C12 arylcarbonylamino group is preferable, and specific examples thereof include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino and the like.

  As the linear, branched or cyclic alkylcarbonyloxy group, a C1-C10 alkylcarbonyloxy group is preferable, and specific examples thereof include methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy group. , N-pentylcarbonyloxy, n-hexylcarbonyloxy, n-heptylcarbonyloxy, n-octylcarbonyloxy, n-nonylcarbonyloxy, n-decylcarbonyloxy and the like; isopropylcarbonyloxy, isobutylcarbonyloxy , Sec-butylcarbonyloxy, t-butylcarbonyloxy, isoamylcarbonyloxy, t-amylcarbonyloxy, isohexylcarbonyloxy, t-hexylcarbonyloxy, isohept A branched chain (preferably C3 to C10) such as rucarbonyloxy, t-heptylcarbonyloxy, isooctylcarbonyloxy, t-octylcarbonyloxy, 2-ethylhexylcarbonyloxy, isononylcarbonyloxy, isodecylcarbonyloxy; Cyclic (preferably C3 to C7) such as cyclopropylcarbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy; and the like. Among them, linear or branched alkylcarbonyloxy Group is preferable, and a linear alkylcarbonyloxy group is more preferable.

  As the arylcarbonyloxy group, a C6-C12 arylcarbonyloxy group is preferable, and specific examples thereof include phenylcarbonyloxy, naphthylcarbonyloxy, biphenylcarbonyloxy and the like.

  As the linear, branched or cyclic alkylcarbonyl group, a C1-C10 alkylcarbonyl group is preferable, and specific examples thereof include methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, n-butylcarbonyl, n-pentylcarbonyl, straight chain such as n-hexylcarbonyl, 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, i A branched chain (preferably C3 to C10) such as nonylcarbonyl, isodecylcarbonyl; and a cyclic (preferably C3 to C7) such as cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl; Among them, a linear or branched alkylcarbonyl group is preferable, and a linear alkylcarbonyl group is more preferable.

  The arylcarbonyl group is preferably a C6-C12 arylcarbonyl group, and specific examples thereof include phenylcarbonyl (benzoyl), naphthylcarbonyl, biphenylcarbonyl and the like.

  Examples of the carbamoyl group include a linear, branched or cyclic monoalkylcarbamoyl group, and a mono C1 to C10 alkylcarbamoyl group is preferable, and specific examples thereof include methylcarbamoyl, ethylcarbamoyl, n-propylcarbamoyl, n Straight chain such as -butylcarbamoyl, n-pentylcarbamoyl, n-hexylcarbamoyl, n-heptylcarbamoyl, n-octylcarbamoyl, n-nonylcarbamoyl, n-decylcarbamoyl; isopropylcarbamoyl, isobutylcarbamoyl, sec-butylcarbamoyl, t-butylcarbamoyl, isoamylcarbamoyl, t-amylcarbamoyl, isohexylcarbamoyl, t-hexylcarbamoyl, isoheptylcarbamoyl, t-heptylcarbamo , Isooctylcarbamoyl, t-octylcarbamoyl, 2-ethylhexylcarbamoyl, isononylcarbamoyl, isodecylcarbamoyl and other branched chains (preferably C3 to C10); cyclopropylcarbamoyl, cyclobutylcarbamoyl, cyclopentylcarbamoyl, cyclohexylcarbamoyl And cyclic (preferably C3 to C7) such as cycloheptylcarbamoyl; and the like, and those having a linear or branched chain are preferred, and those having a straight chain are more preferred.

  As the linear, branched or cyclic dialkylcarbamoyl group, a diC1-C10 alkylcarbamoyl group is preferable, and specific examples thereof include dimethylcarbamoyl, diethylcarbamoyl, di-n-propylcarbamoyl, di-n-butylcarbamoyl, Straight chain such as di-n-pentylcarbamoyl, di-n-hexylcarbamoyl, di-n-heptylcarbamoyl, di-n-octylcarbamoyl, di-n-nonylcarbamoyl, di-n-decylcarbamoyl; Diisobutylcarbamoyl, di-sec-butylcarbamoyl, di-t-butylcarbamoyl, diisoamylcarbamoyl, di-t-amylcarbamoyl, diisohexylcarbamoyl, di-t-hexylcarbamoyl, diisoheptylcarba , Di-t-heptylcarbamoyl, diisooctylcarbamoyl, di-t-octylcarbamoyl, di- (2-ethylhexyl) carbamoyl, diisononylcarbamoyl, diisodecylcarbamoyl, etc. Cyclic groups (preferably having two C3-C7 cyclic groups) such as dicyclopropylcarbamoyl, dicyclobutylcarbamoyl, dicyclopentylcarbamoyl, dicyclohexylcarbamoyl, dicycloheptylcarbamoyl, etc. A straight chain or branched chain is preferable, and a straight chain is more preferable.

  The monoarylcarbamoyl group is preferably a mono C6-C12 arylcarbamoyl group, and specific examples thereof include phenylcarbamoyl, naphthylcarbamoyl, biphenylcarbamoyl and the like.

  The diarylcarbamoyl group is preferably a di-C6-C12 arylcarbamoyl group, and specific examples thereof include diphenylcarbamoyl, dinaphthylcarbamoyl, di (biphenyl) carbamoyl and the like.

  The linear, branched or cyclic alkoxycarbonyl group is preferably a C1-C10 alkoxycarbonyl group, and specific examples thereof include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, and n-pentoxycarbonyl. , N-hexyloxycarbonyl, n-heptoxycarbonyl, n-octyloxycarbonyl, n-nonyloxycarbonyl, n-decyloxycarbonyl; isopropoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, t -Butoxycarbonyl, isoamyloxycarbonyl, t-amyloxycarbonyl, isohexyloxycarbonyl, t-hexyloxycarbonyl, isoheptoxycarbonyl, t-heptoxycarbonyl, isooctyloxy Branched chain (preferably C3 to C10) such as rubonyl, t-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, isononyloxycarbonyl, isodecyloxycarbonyl; cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl , Cyclic (preferably C3 to C7) such as cyclohexyloxycarbonyl, cycloheptoxycarbonyl, and the like; linear or branched ones are preferable, and linear ones are more preferable.

  The aryloxycarbonyl group is preferably a C6-C12 aryloxycarbonyl group, and specific examples thereof include phenoxycarbonyl, naphthyloxycarbonyl, biphenyloxycarbonyl and the like.

  The linear, branched or cyclic alkylsulfonylamino group is preferably a C1 to C10 alkylsulfonylamino group, and specific examples thereof include methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, n-butylsulfonylamino. , N-pentylsulfonylamino, n-hexylsulfonylamino, n-heptylsulfonylamino, n-octylsulfonylamino, n-nonylsulfonylamino, n-decylsulfonylamino, and the like; isopropylsulfonylamino, isobutylsulfonylamino, sec-butylsulfonylamino, t-butylsulfonylamino, isoamylsulfonylamino, t-amylsulfonylamino, isohexylsulfonylamino, t-hexylsulfonylamino, iso A branched chain (preferably C3 to C10) such as ptylsulfonylamino, t-heptylsulfonylamino, isooctylsulfonylamino, t-octylsulfonylamino, 2-ethylhexylsulfonylamino, isononylsulfonylamino, isodecylsulfonylamino; Cyclic (preferably C3 to C7) such as cyclopropylsulfonylamino, cyclobutylsulfonylamino, cyclopentylsulfonylamino, cyclohexylsulfonylamino, cycloheptylsulfonylamino; and the like. A straight chain is more preferable.

  The arylsulfonylamino group is preferably a C6-C12 arylsulfonylamino group, and specific examples thereof include phenylsulfonylamino, toluenesulfonylamino, naphthylsulfonylamino, biphenylsulfonylamino and the like.

  Examples of the sulfamoyl group include a linear, branched or cyclic monoalkylsulfamoyl group, and a mono-C1 to C10 alkylsulfamoyl group is preferable, and specific examples thereof include methylsulfamoyl and ethylsulfamoyl groups. Moyl, n-propylsulfamoyl, n-butylsulfamoyl, n-pentylsulfamoyl, n-hexylsulfamoyl, n-heptylsulfamoyl, n-octylsulfamoyl, n-nonylsulfamoyl , N-decylsulfamoyl, linear; isopropylsulfamoyl, isobutylsulfamoyl, sec-butylsulfamoyl, t-butylsulfamoyl, isoamylsulfamoyl, t-amylsulfamoyl, iso Hexylsulfamoyl, t-hexylsulfamoyl, iso Branched chain such as ptylsulfamoyl, t-heptylsulfamoyl, isooctylsulfamoyl, t-octylsulfamoyl, 2-ethylhexylsulfamoyl, isononylsulfamoyl, isodecylsulfamoyl (preferably C3 To C10); cyclic (preferably C3 to C7) such as cyclopropylsulfamoyl, cyclobutylsulfamoyl, cyclopentylsulfamoyl, cyclohexylsulfamoyl, cycloheptylsulfamoyl, etc. A straight chain or branched chain is preferable, and a straight chain is more preferable.

  The linear, branched or cyclic dialkylsulfamoyl group is preferably a diC1 to C10 alkylsulfamoyl group. Specific examples thereof include dimethylsulfamoyl, diethylsulfamoyl, di-n-propylsulfamoyl. Famoyl, di-n-butylsulfamoyl, di-n-pentylsulfamoyl, di-n-hexylsulfamoyl, di-n-heptylsulfamoyl, di-n-octylsulfamoyl, di- straight chain such as n-nonylsulfamoyl, di-n-decylsulfamoyl; diisopropylsulfamoyl, diisobutylsulfamoyl, di-sec-butylsulfamoyl, di-t-butylsulfamoyl, di Isoamylsulfamoyl, di-t-amylsulfamoyl, diisohexylsulfamoyl, di-t-hex Rusulfamoyl, 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; and the like are mentioned, but linear or branched ones are preferred, and linear ones are more preferred.

  The monoarylsulfamoyl group is preferably a mono C6-C12 arylsulfamoyl group, and specific examples thereof include phenylsulfamoyl, naphthylsulfamoyl, biphenylsulfamoyl and the like.

  As the diarylsulfamoyl group, a di-C6-C12 arylsulfamoyl group is preferable, and specific examples thereof include diphenylsulfamoyl, dinaphthylsulfamoyl, di (biphenyl) sulfamoyl and the like.

  As the linear, branched or cyclic alkylsulfonyl group, a C1-C12 alkylsulfonyl group is preferable, and specific examples thereof include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, n-butylsulfonyl, n-pentylsulfonyl, Straight chain such as n-hexylsulfonyl, n-heptylsulfonyl, n-octylsulfonyl, n-nonylsulfonyl, n-decylsulfonyl, n-undecylsulfonyl, n-dodecylsulfonyl; isopropylsulfonyl, isobutylsulfonyl, sec-butyl Sulfonyl, t-butylsulfonyl, isoamylsulfonyl, t-amylsulfonyl, isohexylsulfonyl, t-hexylsulfonyl, isoheptylsulfonyl, t-heptylsulfonyl, isooctylsulfonyl, t A branched chain (preferably C3 to C12) such as octylsulfonyl, 2-ethylhexylsulfonyl, isononylsulfonyl, isodecylsulfonyl, isoundecylsulfonyl, t-undecylsulfonyl, isododecylsulfonyl, t-dodecylsulfonyl, etc .; cyclo Cyclic (preferably C3 to C7) such as propylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, and cycloheptylsulfonyl; and the like. preferable.

  Examples of the arylsulfonyl group include C6-C12 arylsulfonyl groups, and specific examples thereof include phenylsulfonyl, naphthylsulfonyl, biphenylsulfonyl and the like.

  The linear, branched or cyclic alkylthio group is preferably a C1 to C10 alkylthio group, and specific examples thereof include methylthio, ethylthio, n-propylthio, n-butylthio, n-pentylthio, n-hexylthio, and n-heptylthio. , N-octylthio, n-nonylthio, n-decylthio; isopropylthio, isobutylthio, sec-butylthio, t-butylthio, isoamylthio, t-amylthio, isohexylthio, t-hexylthio, isoheptylthio, t A branched chain (preferably C3 to C10) such as heptylthio, isooctylthio, t-octylthio, 2-ethylhexylthio, isononylthio, isodecylthio; cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio , Of the cyclic (preferably C3-C7) such cycloheptylthio; and the like, preferably a straight chain or branched chain, a straight chain is more preferable.

  As the arylthio group, a C6-C12 arylthio group is preferable, and specific examples thereof include phenylthio, naphthylthio, biphenylthio and the like.

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

  As the linear, branched or cyclic dialkylureido group, a diC1-C10 alkylureido group is preferable, and specific examples thereof include dimethylureido, diethylureido, di-n-propylureido, di-n-butylureido, Straight chain such as di-n-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, di Isooctylureido, di-t-octylureido, -(2-ethylhexyl) ureido, diisononylureido, diisodecylureido and the like (preferably having two C3-C10 branches); dicyclopropylureido, dicyclobutylureido, dicyclopentylureido, dicyclohexylureido And cyclic (preferably having two C3 to C7 cyclic groups) such as dicycloheptylureido; and the like, and those having a straight chain or branched chain are preferred, and those having a straight chain are more preferred.

  The monoarylureido group is preferably a mono C6-C12 arylureido group, and specific examples thereof include phenylureido, naphthylureido, biphenylureido and the like. The diarylureido group is preferably a diC6-C12 arylureido group, and specific examples thereof include diphenylureido, dinaphthylureido, di (biphenyl) ureido and the like.

  Examples of the linear, branched or cyclic alkoxycarbonylamino group include C1-C10 alkoxycarbonylamino groups, and specific examples thereof include methoxycarbonylamino, ethoxycarbonylamino, n-propoxycarbonylamino, n-butoxycarbonyl. Straight chain such as amino, n-pentoxycarbonylamino, n-hexyloxycarbonylamino, n-heptoxycarbonylamino, n-octyloxycarbonylamino, n-nonyloxycarbonylamino, n-decyloxycarbonylamino; iso Propoxycarbonylamino, isobutoxycarbonylamino, sec-butoxycarbonylamino, t-butoxycarbonylamino, isoamyloxycarbonylamino, t-amyloxycarbonylamino, isohexyloxy Rubonylamino, t-hexyloxycarbonylamino, isoheptoxycarbonylamino, t-heptoxycarbonylamino, isooctyloxycarbonylamino, t-octyloxycarbonylamino, 2-ethylhexyloxycarbonylamino, isononyloxycarbonylamino, A branched chain such as isodecyloxycarbonylamino (preferably C3-C10); cyclic such as cyclopropoxycarbonylamino, cyclobutoxycarbonylamino, cyclopentoxycarbonylamino, cyclohexyloxycarbonylamino, cycloheptoxycarbonylamino, etc. Are C3 to C7); linear or branched ones are preferred, and straight ones are more preferred.

  The aryloxycarbonylamino group is preferably a C6-C12 aryloxycarbonylamino group, and specific examples thereof include phenylcarbonylamino, naphthylcarbonylamino, biphenylcarbonylamino and the like.

  As the linear, branched or cyclic monoalkylamino group, a mono-C1 to C10 alkylamino group is preferable, and specific examples thereof include methylamino, ethylamino, n-propylamino, n-butylamino, and n-pentyl. Linear, such as amino, n-hexylamino, n-heptylamino, n-octylamino, n-nonylamino, n-decylamino; isopropylamino, isobutylamino, sec-butylamino, t-butylamino, isoamylamino, t -Branched chain such as amylamino, isohexylamino, t-hexylamino, isoheptylamino, t-heptylamino, isooctylamino, t-octylamino, 2-ethylhexylamino, isononylamino, isodecylamino (preferably C3 To C10); cyclopropyl Cyclic (preferably C3 to C7) such as amino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino; and the like. .

  As the linear, branched or cyclic dialkylamino group, a di-C1 to C10 alkylamino group is preferable, and specific examples thereof include dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino, di- Straight chain such as -n-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, diiso Octylamino, di-t-octylamino, di- (2-ethylhexyl) amino, diisononylamine Branched chain (preferably having two C3 to C10 branched chains) such as dicyclopropylamino, dicyclobutylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, etc. Preferably having two cyclic groups of C3 to C7); linear or branched ones are preferred, and straight ones are more preferred.

  Examples of the arylamino group include a monoarylamino group and a diarylamino group, and a mono C6-C12 arylamino group is preferable. Specific examples thereof include phenylamino (anilino), naphthylamino, biphenylamino and the like. Similarly, examples of the arylamino group include di-C6-C12 arylamino groups, and specific examples thereof include diphenylamino, dinaphthylamino, di (biphenyl) amino and the like.

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

The substituent which R ^{1 in the} general formula (1) may have may have one or two groups selected from the above substituents, and preferably one more.

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.

Examples of the substitution position of the group: -HNCOR ^{1 in} the general formula (1) include an ortho position, a meta position, and a para position, and an ortho position or a meta position is preferable.

Specific examples of the compound represented by the general formula (1) used in the present invention can be listed in Table 1 below, but are not limited thereto.

  Although the compound represented by General formula (1) used for this invention may use a commercially available thing, it can manufacture according to the following manufacturing processes, for example. However, it is not limited to these.

（式中、Ｒ^１は、前記と同義である。） [Manufacturing process 1]

(Wherein R ¹ has the same meaning as described above.)

  The compound of the above formula (1-2) can be produced by reacting phenylenediamine with an acid halide or acid anhydride in the presence or absence of a base.

  Examples of the acid halide used in this reaction include acetyl chloride, propinoyl chloride, isobutyryl chloride, propionyl chloride, pivaloyl chloride, butyryl chloride, 2,2-dimethylylbutyryl chloride, isovaleryl chloride. Etc.

  The usage-amount of an acid halide is 0.1-50 mol normally with respect to 1 mol of phenylenediamine, and 0.1-5 mol is preferable.

（式中、Ｒ^１は前記と同義である。） In general, an acid halide can be produced by reacting a compound represented by the following formula (1-3) with thionyl chloride or oxanyl chloride.

(In the formula, R ¹ has the same meaning as described above.)

  Examples of acid anhydrides used in this reaction include acetic anhydride. The usage-amount of an acid anhydride is 0.1-50 mol with respect to 1 mol of phenylenediamine, and 1-5 mol 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.

（式中、Ｒ^１は、前記と同義である。） [Manufacturing process 2]

(Wherein R ¹ has the same meaning as described above.)

  The compound of general formula (1) can be produced by reacting the compound of general formula (1-2) with phenyl isocyanate in the presence or absence of a base.

  The usage-amount of the phenyl isocyanate used for this reaction is 0.1-50 mol normally with respect to 1 mol of compounds of General formula (1-2), and 0.1-5 mol is preferable.

  In these two production steps, a base may be used as necessary to promote the reaction. For example, an inorganic base such as sodium bicarbonate, sodium carbonate, potassium carbonate, and cesium carbonate; an organic base such as triethylamine and diisopropylethylamine is used. Can be mentioned.

  The usage-amount of these bases is 0.1-50 mol normally with respect to 1 mol of each of the phenylenediamine of the manufacturing process 1, or the compound of the general formula (1-2) of the manufacturing process 2, and 1-5 mol is preferable. .

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

  The solvent used in these two production steps is not particularly limited as long as it does not affect the reaction. Examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. Amide compounds; halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane; aromatic hydrocarbons 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; ester compound such as ethyl acetate and butyl acetate; sulfone compound such as sulfolane; Sulfoxide compounds such as sulfoxide and the like, which may be used alone or in combination.

  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 general formula (1) as a color developing compound and a phenol-based developer. The total amount of the color 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 each (weight%) Is the weight ratio of each component in the thermosensitive coloring layer). As a more preferred embodiment, the weight ratio of the compound represented by the general formula (1) to the phenol-based color developing compound in the above composition is preferably 9: 1 to 1: 9, and 6: 4 to 4: 6. Is particularly preferred. Further, 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 together in the present invention is not particularly limited, and examples thereof include benzotriazole derivatives, saccharin derivatives, sulfonamide derivatives, malonamide derivatives, thiourea derivatives, sulfonylurea derivatives, diphenylsulfone derivatives substituted with amino groups, Examples include aromatic carboxylic acid derivatives.

  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, but 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 and the like can be mentioned.

  The aromatic carboxylic acid derivative is not particularly limited, and specific examples thereof include benzyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, dibenzyl 4-hydroxyphthalate, dimethyl 4-hydroxyphthalate, Examples include ethyl 5-hydroxyisophthalate, 3,5-di-t-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, aromatic carboxylic acid or a polyvalent metal salt thereof.

  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- 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 producing the heat-sensitive recording material of the present invention will be described. A color-forming compound, a compound represented by the general formula (1), and a phenol-based color developing compound used in the present invention, each separately, together with a binder or other additives as necessary, a ball mill, an attritor, After pulverizing and dispersing with a disperser such as a sand mill to form 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 layer coating liquid, It is applied by a bar coater, a blade coater, etc. on a support such as paper (plain paper, fine paper, coated paper, etc.), plastic sheet, synthetic paper, etc., so that the dry weight is usually 1 to 20 g / m ² . It is dried to produce the heat-sensitive recording material of the present invention.

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 thermal recording layer coating solution, for example, together with the above-mentioned 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.

クロロホルム９６４部中に式（１−１０）の２’−アミノアセトアニリド（東京化成工業）２２．２部を加え攪拌し、次いでイソシアン酸フェニル（東京化成工業）１９．３部を室温で滴下し、同温度で２時間攪拌した。反応終了後、析出物をろ別し、ろ物を酢酸エチル、水で順次洗浄し、真空乾燥することで、上記表１に記載の化合物１を白色固体として得た（３３．５部）。
ＭＳ（ＥＳＩ）：［Ｍ−Ｈ］⁻：ｃａｌ．：２６８．１， ｆｏｕｎｄ：２６８．１ [Synthesis Example 1] Synthesis of Compound No. 1 described in Table 1

In 964 parts of chloroform, 22.2 parts of 2′-aminoacetanilide of formula (1-10) (Tokyo Kasei Kogyo) was added and stirred, and then 19.3 parts of phenyl isocyanate (Tokyo Kasei Kogyo) was added dropwise at room temperature, The mixture was stirred at the same temperature for 2 hours. After completion of the reaction, the precipitate was filtered off, and the filtrate was washed successively with ethyl acetate and water, and dried under vacuum to obtain Compound 1 listed in Table 1 as a white solid (33.5 parts).
MS (ESI): [M−H] ⁻ : cal. : 268.1, found: 268.1

[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: 25.0 parts of Compound No. 1 described in Table 1
25% PVA aqueous solution 20.0 parts
55.0 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: 35.0 parts of 3-dibutylamino-6-methyl-7-anilinofluorane
40.0 parts of 15% PVA aqueous solution
25.0 parts of water

A dispersion [C] was prepared by pulverizing and dispersing 4,4′-dihydroxydiphenylsulfone used in combination in the present invention with a sand grinder having the following composition so that the median particle diameter was 1 μm or less.
[C] Solution: 4,4′-dihydroxydiphenylsulfone (Tokyo Chemical Industry) 25.0 parts
25% PVA aqueous solution 20.0 parts
55.0 parts of water

Then, an agent that each liquid and below that obtained above were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is a 5 g / m ² The heat-sensitive recording material of the present invention was prepared by coating and drying.
[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

(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 material with a protective layer.
40% styrene / acrylic ester copolymer emulsion 115.0 parts 5% bentonite aqueous dispersion 17.0 parts 45% styrene / acrylic copolymer aqueous emulsion 44.0 parts 39% aqueous zinc stearate dispersion 103.0 Part 67% calcium carbonate aqueous dispersion 15.0 parts

[Example 2]
A heat-sensitive recording material of the present invention was obtained in the same manner as in Example 1 except that 2,2-bis (p-hydroxyphenyl) propane was used in place of 4,4′-dihydroxydiphenylsulfone.

[Example 3]
A heat-sensitive recording material of the present invention was obtained in the same manner as in Example 1 except that 4-hydroxy-4'-isopropoxydiphenylsulfone was used instead of 4,4'-dihydroxydiphenylsulfone.

[Example 4]
A thermosensitive recording material of the present invention was obtained in the same manner as in Example 1 except that 4-hydroxy-4'-propoxydiphenylsulfone was used instead of 4,4'-dihydroxydiphenylsulfone.

[Example 5]
A heat-sensitive recording material of the present invention was obtained in the same manner as in Example 1 except that 4-hydroxy-4'-benzyloxydiphenylsulfone was used instead of 4,4'-dihydroxydiphenylsulfone.

[Example 6]
Then, [A] solution described above, [B] solution [C] solution were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 21.6 parts [B] Liquid 8.6 parts [C] Liquid 2.4 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Example 7]
Then, [A] solution described above, [B] solution [C] solution were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[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

[Example 8]
Next, the above-mentioned [A] liquid, [B] liquid, and [C] liquid are mixed with the following composition to prepare a thermal recording layer coating liquid, and the weight upon drying is on a fine paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[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 9]
Next, the above-mentioned [A] liquid, [B] liquid, and [C] liquid are mixed with the following composition to prepare a thermal recording layer coating liquid, and the weight upon drying is on a fine paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[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 10]
Then, [A] solution described above, [B] solution [C] solution were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[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 11]
Next, the above-mentioned [A] liquid, [B] liquid, and [C] liquid are mixed with the following composition to prepare a thermal recording layer coating liquid, and the weight upon drying is on a fine paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[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 12]
Next, the above-mentioned [A] liquid, [B] liquid, and [C] liquid are mixed with the following composition to prepare a thermal recording layer coating liquid, and the weight upon drying is on a fine paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[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 13]
Next, the above-mentioned [A] liquid, [B] liquid, and [C] liquid are mixed with the following composition to prepare a thermal recording layer coating liquid, and the weight upon drying is on a fine paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[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

[Example 14]
Next, the above-mentioned [A] liquid, [B] liquid, and [C] liquid are mixed with the following composition to prepare a thermal recording layer coating liquid, and the weight upon drying is on a fine paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 2.4 parts [B] Liquid 8.6 parts [C] Liquid 21.6 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Example 15]
2,4′-Dihydroxydiphenylsulfone used in combination in the present invention was pulverized and dispersed using a sand grinder with the following composition so that the median particle diameter was 1 μm or less to prepare dispersion [D].
[D] Liquid: 25.0 parts of 2,4′-dihydroxydiphenylsulfone
25% PVA aqueous solution 20.0 parts
55.0 parts of water

Then, an agent that each liquid and below that obtained above were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is a 5 g / m ² The heat-sensitive recording material of the present invention was prepared by coating and drying.
[A] Liquid 21.6 parts [B] Liquid 8.6 parts [D] Liquid 2.4 parts 67% calcium carbonate aqueous dispersion 9.0 parts 48% modified styrene / butadiene copolymer latex 6.3 parts Water 52.1 copies

[Example 16]
Then, [A] solution described above, [B] solution [D] solution were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 19.2 parts [B] Liquid 8.6 parts [D] 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

[Example 17]
Next, the above-mentioned [A] liquid, [B] liquid, and [D] liquid are mixed in the following composition to prepare a heat-sensitive recording layer coating liquid, and the weight when dried on a high-quality paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 16.8 parts [B] Liquid 8.6 parts [D] 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 18]
Next, the above [A] liquid, [B] liquid, and [D] liquid are mixed in the following composition to prepare a thermal recording material coating liquid, and the weight upon drying is on a fine paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 14.4 parts [B] Liquid 8.6 parts [D] 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 19]
Next, the above-mentioned [A] liquid, [B] liquid, and [D] liquid are mixed in the following composition to prepare a heat-sensitive recording layer coating liquid, and the weight when dried on a high-quality paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 12.0 parts [B] Liquid 8.6 parts [D] 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 20]
Next, the above-mentioned [A] liquid, [B] liquid, and [D] liquid are mixed in the following composition to prepare a heat-sensitive recording layer coating liquid, and the weight when dried on a high-quality paper having a basis weight of 50 g / m ^2. The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 9.6 parts [B] Liquid 8.6 parts [D] 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 21]
Then, [A] solution described above, [B] solution [D] solution were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is The heat-sensitive recording material of the present invention was prepared by applying and drying so as to be 5 g / m ² .
[A] Liquid 7.2 parts [B] Liquid 8.6 parts [D] 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 22]
Then, [A] solution described above, [B] solution [D] solution were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 4.8 parts [B] Liquid 8.6 parts [D] 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

[Example 23]
Then, [A] solution described above, [B] solution [D] solution were mixed in the following composition to prepare a thermosensitive recording layer coating liquid, the weight at the time of drying fine paper having a basis weight of 50 g / m ² is The heat-sensitive recording material of the present invention was produced by applying and drying so as to be 5 g / m ² .
[A] Liquid 2.4 parts [B] Liquid 8.6 parts [D] Liquid 21.6 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 comparative heat-sensitive recording material was obtained by applying and drying in the same manner as in Example 1 except that the above [A] liquid and [B] liquid were mixed in the following composition ratio.
[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 comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 1 except that 4,4′-dihydroxydiphenylsulfone was used instead of Compound No. 1 shown in Table 1.

[Comparative Example 3]
A comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 1 except that 2,2-bis (p-hydroxyphenyl) propane was used in place of Compound No. 1 shown in Table 1.

[Comparative Example 4]
A comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 1 except that 4-hydroxy-4′-isopropoxydiphenyl sulfone was used instead of Compound No. 1 shown in Table 1.

[Comparative Example 5]
A comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 1 except that 4-hydroxy-4′-propoxydiphenylsulfone was used instead of Compound No. 1 shown in Table 1.

[Comparative Example 6]
A comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 1 except that 4-hydroxy-4′-benzyloxydiphenylsulfone was used instead of Compound No. 1 shown in Table 1.

[Comparative Example 7]
A comparative heat-sensitive recording material was obtained by applying and drying the above [A] liquid and [B] liquid in the same manner as in Example 6 except that they were mixed in the following composition ratio.
[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 8]
A comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 7 except that 4,4′-dihydroxydiphenylsulfone was used instead of Compound No. 1 shown in Table 1.

[Comparative Example 9]
A comparative heat-sensitive recording material was obtained in the same manner as in Comparative Example 7, except that 2,4′-dihydroxydiphenylsulfone was used instead of Compound No. 1 shown in Table 1.

[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 a pulse width of 1.4 msec is applied on it using a thermal printer (TH-M2 / PP) manufactured by Okura Engineering Co., Ltd. The heat-sensitive recording materials obtained in Examples 1 to 5, 7 to 14, 17 to 23 and Comparative Examples 1 to 9 were printed (colored). 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”. Colorimetry was 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 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 clear from Table 2, the heat-sensitive recording material of the present invention using the compound represented by the general formula (1) and the phenolic color developing compound as the color developing compound is a comparative example in which each compound is used alone. Compared with 1 to 9, the residual ratio after the test is high, and the printed portion is excellent in plasticizer resistance.

[Storage stability test (oil resistance test)]
The heat-sensitive recording materials obtained in Examples 1, 6 to 18 and Comparative Examples 1, 2, 7 to 9 were used with a pulse width of 1.4 msec using a thermal printer (TH-M2 / PP) manufactured by Okura Engineering Co., Ltd. Printing was performed (coloring), 4 drops of salad oil were added, and the mixture was allowed to stand 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”. Colorimetry was 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 general formula (1) and the phenolic color developing compound as the color developing compound is a comparative example in which each compound is used alone. Compared with 1, 2, 7 to 9, the residual rate after the test is high, and the printed portion is excellent in oil resistance.

Claims (7)

A heat-sensitive recording material comprising a compound represented by the following general formula (1) and a phenol-based color developing compound.

(In formula (1), R ¹ represents an alkyl group.) The phenolic color developing compound is 2,2-bis (p-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-isopropoxydiphenylsulfone, 4-hydroxy-4′-propoxy. The heat-sensitive recording material according to claim 1, wherein the material is selected from diphenyl sulfone, 4-hydroxy-4'-benzyloxydiphenyl sulfone, and 2,4'-dihydroxydiphenyl sulfone. The heat-sensitive recording material according to claim 1 or 2, wherein a compound in which R ¹ is an alkyl group which is unsubstituted or substituted with an aryl group in the general formula (1) is used. The heat-sensitive recording material according to any one of claims 1 to 3, wherein a compound in which R ¹ is an unsubstituted alkyl group in the general formula (1) is used. The heat-sensitive recording material according to any one of claims 1 to 4, wherein a compound in which R ¹ is either a methyl group or an ethyl group in the general formula (1) is used. A thermosensitive recording layer comprising the thermosensitive recording material according to any one of claims 1 to 5. A heat-sensitive recording paper comprising the heat-sensitive recording material or the heat-sensitive recording layer according to claim 1.