JP2010105917A - New phenol compound, and heat sensitive recording material comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat sensitive recording material having excellent storage stability. <P>SOLUTION: A phenol compound represented by formula (I) is included in a heat sensitive recording layer of the heat sensitive recording material constituted of the heat sensitive recording layer and a support. In the formula, X, Y, and Z each independently represents a 1-10C alkyl group that may be substituted with a halogen atom, a 6-20C aryl group that may be substituted with a halogen atom, a 7-20C arylalkyl group that may be substituted with a halogen atom, a 2-20C heterocyclic group that may be substituted with a halogen atom, or a halogen atom; k represents a number of 0 to 4; and p and r each represents a number of 0 to 4, provided that k+p+r is an integer of 1 or greater. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel phenol compound and a heat-sensitive recording material containing the compound.

  A heat-sensitive recording material usually comprises a colorless or light-colored color developing substance and a developer that develops the color developing substance when heated, together with a sensitizer, a binder, and other additives, paper, and synthetic paper. It is manufactured by coating on the surface of a support such as a plastic film or sheet. In the recording apparatus, when a heating element such as a thermal head or a thermal pen comes into contact, the color former and the developer react to develop a color such as black and record. Such heat-sensitive recording materials do not require complicated processing such as development and fixing compared to other recording materials, and can be recorded in a relatively simple device in a short time, and noise generation is low. In addition to copying books, documents, etc., various measurement recording paper, computers, facsimiles, vending machines such as tickets, prepaid cards, labels, etc. Is widely used as a recording material.

  In a conventional heat-sensitive recording material, by using an appropriate combination of a color-forming substance (leuco dye), a color developer that thermally develops this and a sensitizer that is used as necessary, the initial color sensitivity and From the viewpoint of dirt on the background (background fogging), a practically satisfactory one is obtained.

  However, when these heat-sensitive recording materials are exposed to sunlight, illumination, etc. for a long time, the color-development part may fade or disappear, or the background part may turn yellow. When a printed out product such as a personal computer is left on the desktop, the recorded image becomes unclear, which causes a problem in terms of document storage.

  Furthermore, the conventional heat-sensitive recording material not only has inferior light resistance, but also when it is stored under high temperature and / or high humidity conditions, the color-development part may be decolored or background fogging may occur. There has been a demand for further improvement with respect to the storage stability of the heat-sensitive recording material.

  As a developer, a phenol compound is generally used in many cases, but the phenol compound is also used for improving storage stability. Patent Document 1 below describes an example in which a phenol compound is used as a preservability improver. Further, as disclosed in Patent Document 2 and Patent Document 3 below, thermosensitive recording materials having improved storage stability using various phenolic compounds as a developer have been disclosed, but thermosensitive recordings containing these compounds are disclosed. The material was also unsatisfactory in terms of storage stability such as moisture and heat resistance and chemical resistance of the print coloring area.

JP 58-57990 A Japanese Patent Laid-Open No. 7-164749 Japanese Patent Laid-Open No. 11-11022

  Accordingly, an object of the present invention is to provide a heat-sensitive recording material having excellent storage stability.

  As a result of repeated studies to solve the above problems, the present inventors have found that a thermosensitive recording material having excellent storage stability can be obtained by using a phenol compound having a specific molecular structure.

  This invention is made | formed based on the said knowledge, and provides the phenolic compound represented by the following general formula (I).

（式中、Ｘ、Ｙ及びＺは、それぞれ独立して、ハロゲン原子で置換されていてもよい炭素原子数１〜１０のアルキル基、ハロゲン原子で置換されていてもよい炭素原子数６〜２０のアリール基、ハロゲン原子で置換されていてもよい炭素原子数７〜２０のアリールアルキル基、ハロゲン原子で置換されていてもよい炭素原子数２〜２０の複素環基又はハロゲン原子を表し、該アルキル基、アリール基、アリールアルキル基中のメチレン基は、不飽和結合、−Ｏ−又は−Ｓ−で中断されていてもよく、ｋは０〜４の数を表し、ｋが２以上の数であるとき、複数のＸは、それぞれ異なる置換基であってもよく、複数のＸは、Ｘ同士で環を形成していてもよく、それらの環は芳香環でもよく、ｐ及びｒは０〜４の数を表し、ｋ＋ｐ＋ｒは１以上の整数である。）

(In the formula, X, Y and Z are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. An aryl group of the above, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom, The methylene group in the alkyl group, aryl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, k represents a number of 0 to 4, and k is a number of 2 or more. The plurality of X may be different from each other, the plurality of X may form a ring with each other, the ring may be an aromatic ring, and p and r are 0. Represents a number of ~ 4, k + p + r is an integer of 1 or more In is.)

  The present invention also provides a heat-sensitive recording material containing the phenol compound represented by the general formula (I).

  According to the present invention, it is possible to provide a heat-sensitive recording material that has less color fading and has excellent storage stability even after being stored under severe conditions.

Hereinafter, the present invention will be described in detail based on preferred embodiments thereof.
First, the phenol compound of the present invention represented by the general formula (1) will be described.

  In the general formula (I), an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom represented by X, Y and Z, or 6 to 20 carbon atoms which may be substituted with a halogen atom. And the methylene group in the arylalkyl having 7 to 20 carbon atoms which may be substituted with a halogen atom may be interrupted by an unsaturated bond, —O— or —S—. The substitution position and the interruption position of -O- or -S- are optional, and include those in which -O- or -S- is directly bonded to each ring. Examples of the alkyl group having 1 to 10 carbon atoms that may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, isobutyl, amyl, isoamyl, and t-amyl. , Hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl, 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoro Ethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl, tetrafluoropropyl, trifluoropropyl, perfluorobutyl, methoxy, methoxyethoxy, methoxyethoxyethoxy, meso Ruthio, ethoxy, vinyloxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, t-butoxycarbonylmethoxy, pentyloxy, isopentyloxy, t-pentyloxy, neopentyloxy, hexyloxy, cyclohexyloxy, isohexyloxy Linear, branched and cyclic alkyl groups such as heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc., halogen Examples of the aryl group having 6 to 20 carbon atoms which may be substituted with atoms include phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl and 1-phenane. Lyl, o-tolyl, m-tolyl, p-tolyl, 3-fluorenyl, 9-fluorenyl, 1-tetrahydronaphthyl, 2-tetrahydronaphthyl, 1-acenaphthenyl, 1-indanyl, 2-indanyl, 4-vinylphenyl, 3 -Isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2-ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-t- Butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t- Butylphenyl, 2,4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-trichloromethyl Phenyl, 4-trifluoromethylphenyl, perfluorophenyl, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2 , 4,5-trimethylphenoxy, 2,4,6-trimethylpheno 3,4,5-trimethylphenoxy, 2,3,4,5-tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy, pentamethyl Phenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec-butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n-tetradecylphenoxy, cyclohexyl Phenoxy, 1-naphthoxy, 2-naphthoxy, 1-anthryloxy, 1-phenanthryloxy, o-tolyloxy, m-tolyloxy, p-tolyloxy, 9-fluorenyloxy, 1-tetrahydronaphthoxy, 2- Tetrahydronaphthoxy, -Acenaphthenyloxy, 1-indanyloxy, 2-indanyloxy and the like. Examples of the arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom include benzyl and phenethyl. , 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl, benzyloxy group, 1-naphthylmethoxy group, 2-naphthylmethoxy group, 1-anthrylmethoxy, etc., halogen atom Examples of the heterocyclic group which may be substituted with pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl , Benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, yurolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone -1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl and the like, and halogen atoms include fluorine, chlorine, bromine and iodine, Examples of the ring structure that may be formed by X include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone ring, lactam ring, and the like, naphthalene ring, anthracene Ring, fluorene ring, Senafuten ring, indan ring, and a condensed ring of a tetralin ring.

  Among the phenolic compounds of the present invention, a phenolic compound represented by the following general formula (II) is preferable because it is advantageous in terms of production.

（式中、Ｘ、Ｙ、Ｚ、ｋ及びｒは、上記一般式（Ｉ）と同じである。）

(In the formula, X, Y, Z, k and r are the same as those in the general formula (I).)

  Moreover, in the said general formula (I) or the said general formula (II), when Y is a phenyl group, k is 0 or 1, when k is 1, X is C1-C10. A phenol compound which is an alkyl group or an aryl group having 6 to 20 carbon atoms is more preferable in that the resistance to chemicals is good.

  More specifically, examples of the phenol compound represented by the general formula (I) include compounds represented by the following [Chemical Formula 3] to [Chemical Formula 5]. However, this invention is not restrict | limited at all by the following illustrations.

  The phenol compound of the present invention represented by the above general formula (I) is not particularly limited by the production method thereof, and can be obtained by a method using a known general reaction. For example, the phenol compound (I) of the present invention can be obtained by reacting a benzo or naphthocycloalkanone derivative (III) with a phenol derivative in the presence of an acidic catalyst at a temperature of 20 to 200 ° C. for 1 to 40 hours. .

  Examples of the acidic catalyst include methanesulfonic acid, benzenesulfonic acid, m-xylenesulfonic acid, p-toluenesulfonic acid, hydroxymethylsulfonic acid, 2-hydroxyethylsulfonic acid, hydroxypropylsulfonic acid, trifluoromethanesulfonic acid, Sulfonic acids such as sulfosalicylic acid and sulfophthalic acid; sulfuric acid, sulfuric anhydride, fuming sulfuric acid, chlorosulfuric acid, fluorosulfuric acid, hydrochloric acid, hydrogen chloride gas, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, silicotungstic acid, phosphorus Examples include heteropolyacids such as tungstic acid, strongly acidic ion exchange resins, activated clay, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The acidic catalyst is preferably used in an amount of 0.1 to 50 parts by mass, and more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the benzo or naphthocycloalkanone derivative (III).

  Further, a mercaptan catalyst can be used to promote the reaction. Examples of the mercaptan catalyst include methyl mercaptan, ethyl mercaptan, propyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 1,6-hexanedithiol, and the like. Alkyl mercaptans such as thiophenol and thiocresol; mercapto organic acids such as mercaptoacetic acid (thioglycolic acid), 3-mercaptopropionic acid, mercaptoundecanoic acid and thiobenzoic acid; 2-mercaptobenzothiazole, etc. And heterocyclic mercaptans.

  Moreover, a conventionally well-known solvent can be used for the said reaction, For example, Terpene, such as aromatic hydrocarbon solvents, such as toluene, xylene, cumene; terpine oil, D-limonene, pinene, etc. Hydrocarbon oils; mineral spirits, paraffinic solvents such as Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); alcoholic solvents such as methanol and ethanol; esters such as ethyl acetate Solvents: Halogen solvents such as dichloroethane, carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, chlorobenzene; cyclic ether solvents such as tetrahydrofuran and dioxane; ethers, cellosolve solvents, ketone solvents, aniline, triethylamine, pyridine, dioxane , Acetic acid, acetonitrile Carbon disulfide, and the like.

The phenol compound of the present invention is used as a developer in a heat-sensitive recording material described below, and also in an antioxidant, a bactericide, a fungicide, and the like.

Next, the heat-sensitive recording material of the present invention will be described.

  The heat-sensitive recording material of the present invention comprises a heat-sensitive recording layer and a support, and the heat-sensitive recording layer contains at least one phenol compound represented by the above general formula (I). The thermosensitive recording layer is formed of a phenol compound represented by the general formula (I) and a color former, and if necessary, other than the sensitizer and the phenol compound represented by the general formula (I). Other developers, storage stabilizers, fillers, binders, light stabilizers, UV absorbers, pigments, metal soaps, hydrotalcites, plasticizers, amides, waxes, antioxidants, water resistance It can be formed by adding agents, dispersants, antifoaming agents, surfactants, fluorescent dyes, antibacterial agents, antifungal agents, preservatives, and the like. The heat-sensitive recording material of the present invention preferably contains 0.1 to 50% by weight, particularly 1.0 to 10% by weight, of the phenol compound represented by the general formula (I) in the heat-sensitive recording layer. And it is preferable to contain 10-1000 mass parts, especially 100-500 mass parts of the phenolic compound represented by the said general formula (I) with respect to 100 mass parts of said color formers.

  Examples of the color former include various known dyes that are usually colorless to light, and are not particularly limited as long as they are used for general recording materials. Specific examples of the color former include (i) 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (2-phenyl). -3-Indolyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethyl-3-indolyl) phthalide, 3,3-bis (9-ethyl-3-carbazolyl) -5-dimethyl Aminophthalide, 3,3-bis (2-phenyl-3-indolyl) -5-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) ) Triaryl, such as phthalide, 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) vinyl] -4,5,6,7-tetrachlorophthalide Emissions-based compounds;

(Ii) Diphenylmethane compounds such as 4,4-bis (dimethylamino) benzhydrin benzyl ether and N-2,4,5-trichlorophenylleucooramine;
(Iii) Rhodamine-β-anilinolactam, 3- (N-methyl-N-cyclohexylamino) -6-methyl-7-anilinofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino- 7- (2-chloroanilino) fluorane, 3-diethylamino-7- (2-fluoroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- ( 2,4-dimethylanilino) fluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-6-chloro-7- (β-ethoxyethylamino) fluorane, 3-diethylamino-6-chloro-7 -(Γ-chloropropylamino) fluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-ethoxyethylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) ) -6-methyl-7-anilinofluorane, 3-dibutylamino-7- (2-chloroanilino) fluorane, 3- (N-ethyl-N-tolylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilino Xanthene compounds such as fluorane, 3- (4-anilino) anilino-6-methyl-7-chlorofluorane;

(Iv) thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue;
(V) Spiro compounds such as 3-methylspirodinaphthopyrans, 3-ethylspirodinaphthopyrans, 3-benzylspirodinaphthopyrans, 3-methylnaphtho- (3-methoxybenzo) spiropyrans, 3-propylspirodinaphthopyrans ;
(Vi) In addition, 3,5 ′, 6-tris (dimethylamino) -spiro [9H-fluorene-9,1 ′-(3′H) -isobenzofuran] -3′-one, 1,1-bis [ 2- (4-Dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7-tetrachloro-3H-isobenzofuran-3-one, 3- (4-diethylamino-2- Ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide, 3- (4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindole- 3-yl) -4-azaphthalide, phenoxazine derivatives, and the like. These color formers may be used in combination of several kinds.

Of these (i) to (vi), 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamylamino) -6 Methyl-7-anilinofluorane and the like are preferably used. In addition, if necessary, a chelate coloring agent such as aliphatic ferric iron may be used in combination with the heat-sensitive recording material of the present invention.
The amount of the color former used is preferably 0.1 to 50% by mass, more preferably 1.0 to 10% by mass in the heat-sensitive recording layer.

Examples of the sensitizer that can be added to the heat-sensitive recording material of the present invention as needed include zinc acetate, zinc octylate, zinc laurate, zinc stearate, zinc oleate, zinc behenate, and benzoic acid. Zinc, salicylic acid dodecyl ester zinc salt, organic acid metal salt such as calcium stearate, magnesium stearate, aluminum stearate; stearic acid amide, behenic acid amide, stearic acid methylolamide, stearoylurea, acetanilide, acetoluidide, acetoacetanilide, Amido compounds such as acetoacetic acid-o-chloroanilide, benzoylacetic acid anilide, benzoic acid stearylamide, ethylenebisstearic acid amide, hexamethylenebisoctylic acid amide; 1,2-bis (3,4-dimethylphenyl) ethane M-terphenyl, 1,2-diphenoxyethane, 1,2-bis (3-methylphenoxy) ethane, p-benzylbiphenyl, p-benzyloxybiphenyl, diphenyl carbonate, bis (4-methylphenyl) carbonate, Dibenzyl oxalate, bis (4-methylbenzyl) oxalate, bis (4-chlorobenzyl) oxalate, phenyl 1-hydroxy-2-naphthalenecarboxylate, benzyl 1-hydroxy-2-naphthalenecarboxylate, 3-hydroxy- 2-naphthalene carboxylate phenyl, methylene benzoate, 1,4-bis (2-vinyloxyethoxy) benzene, 2-benzyloxynaphthalene, 4-benzyloxybenzoate benzyl, dimethyl phthalate, dibenzyl terephthalate, dimethyl terephthalate, tele Diethyl talate, dibutyl terephthalate, di (2-hydroxyethyl) terephthalate, terephthalic acid (2-hydroxypropyl), dibenzoylmethane, diphenylsulfone, p-toluenesulfonic acid anilide, 4-methylphenoxy-p-biphenyl, 4-chlorophenyl phenyl sulfone and the like can be mentioned. Of these, dimethyl terephthalate, diethyl terephthalate, dibutyl terephthalate, di (2-hydroxyethyl) terephthalate, terephthalic acid (2-hydroxypropyl), bis (4-methylbenzyl) oxalate, bis (4-chlorobenzyl) ) Oxalate, acetoacetic acid-o-chloroanilide, diphenylsulfone, stearamide, stearic acid methylolamide and the like are preferably used. These sensitizers may be used alone or in combination of two or more in order to increase the color development sensitivity.
When the sensitizer is added, the addition amount is preferably 0.1 to 50% by mass, and more preferably 1.0 to 10% by mass in the heat-sensitive recording layer.

Examples of the developer other than the above-described phenol compound that can be added to the heat-sensitive recording material of the present invention as necessary include, for example, p-octylphenol, p-tert-butylphenol, p-phenylphenol, and p-hydroxy. Acetophenone, α-naphthol, β-naphthol, p-tert-octylcatechol, 2,2′-dihydroxybiphenyl, bisphenol A, 1,1-bis (p-hydroxyphenyl) butane, 2,2-bis (4-hydroxy) Phenyl) heptane, 2,2-bis-((3-methyl-4-hydroxyphenyl) propane), 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis ( 3,5-dichloro-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (3 Allyl-4-hydroxyphenyl) sulfone, bis (3,4-dihydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) ether Bis [2- (4-hydroxyphenylthio) ethoxy] methane, 4- (4-isopropoxybenzenesulfonyl) phenol, dimethyl 4-hydroxyphthalate, butyl bis (4-hydroxyphenyl) acetate, p-hydroxybenzoic acid Benzyl, 3,5-ditert-butylsalicylic acid, 2,4-dihydroxybenzanilide, 2,4-dihydroxy-2′-methoxybenzanilide, 2,4-dihydroxy-2 ′, 4′-dimethylbenzanilide, 2 , 4-Dihydroxy-2'-methoxy-5'-methylbenzene Phenols such as dansanilide, bis (4- (2,4-dihydroxyphenylcarbonylamino) -3-methoxyphenyl) methane, 4-methylbenzenesulfonic acid-2-hydroxyanilide, phenol resins such as novolak phenol, and resorcinols And organic carboxylic acids such as benzoic acid or metal salts thereof, salicylic acid derivatives or metal salts thereof, N, N-diarylthiourea derivatives, sulfonylurea derivatives, urethane urea compounds, sulfonamide compounds, and the like. These other developers may be used alone or in combination of two or more in order to increase the color development sensitivity.
When the other developer is added, the addition amount thereof is preferably 0.1 to 50% by mass, more preferably 1.0 to 10% by mass in the heat-sensitive recording layer. It is preferable to contain 1 to 10000 parts by mass, particularly 10 to 1000 parts by mass of the other developer, based on 100 parts by mass of the phenol compound represented by the general formula (I).

Examples of the storage stabilizer that can be added to the heat-sensitive recording material of the present invention as needed include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 4,4′-butylidenebis (2-tert-butyl-5-methylphenol), 4,4′-thiobis (2 -Tert-butyl-5-methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-methylphenol), etc. Hindered phenol compound, 4-benzyloxy-4 ′-(2-methylglycidyloxy) diphenylsulfone, sodium-2,2′-methylenebis (4,6-ditert-butylphenyl) phospho Feto, and the like. These storage stabilizers may be used alone or in combination of two or more.
When the above storage stabilizer is added, the addition amount thereof is preferably 0.001 to 10% by mass, more preferably 0.1 to 1.0% by mass in the thermosensitive recording layer.

Examples of the filler that can be added to the heat-sensitive recording material of the present invention as necessary include kaolin, silica, diatomaceous earth, talc, titanium dioxide, calcium carbonate, magnesium carbonate, aluminum hydroxide, melamine, and polystyrene resin. Examples of the binder include polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, polyvinyl pyrrolidone, polyacrylamide, starches, gelatin, casein, sodium polyacrylate, sodium alginate, polycarboxylic acid ammonium salt, polyurethane, styrene-maleic anhydride Examples thereof include binders such as copolymers, vinyl acetate-maleic anhydride copolymers, styrene-butadiene copolymers, and modified products thereof.
When the filler or the binder is added, the amount of the filler added is preferably 0.1 to 50% by mass, more preferably 10 to 30% by mass in the thermosensitive recording layer. The addition amount of the binder is preferably 0.1 to 50% by mass, more preferably 1.0 to 10% by mass in the thermosensitive recording layer.

  Furthermore, when the heat-sensitive recording material of the present invention is required to have particularly high light resistance and storage stability of the background portion, a known hindered amine light stabilizer and / or ultraviolet absorber is added to the heat-sensitive recording layer. One kind or two or more kinds can be added.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidylbenzoate, N- (2,2,6,6-tetramethyl-4-piperidyl) dodecylsuccinimide, 1-[(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] -2,2,6,6-tetramethyl-4-piperidyl- (3,5-ditert-butyl-4- Hydroxyphenyl) propionate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, N, N-bis (2,2,6, -Tetramethyl-4-piperidyl) hexamethylenediamine, tetra (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetra (1,2,2,6,6-pentamethyl-4- Piperidyl) butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) -di (tridecyl) butanetetracarboxylate, 3,9-bis [1,1-dimethyl-2- {tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy } Ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl] Ru-2- {tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane 1,5,8,12-tetrakis [4,6-bis {N- (2,2,6,6-tetramethyl-4-piperidyl) butylamino} -1,3,5-triazin-2-yl ] -1,5,8,12-tetraazadodecane, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / dimethyl succinate condensate, 2-tert-octylamino -4,6-dicyclo-s-triazine / N, N-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine condensate, N, N'-bis (2,2,6 , 6-Tetramethyl- - piperidyl) hexamethylenediamine / dibromoethane condensate and the like.
When the hindered amine light stabilizer is added, the addition amount is preferably 0.001 to 10% by mass and more preferably 0.1 to 1.0% by mass in the heat-sensitive recording layer.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5 -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tertiary Octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzo Triazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) ) Phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyl) Oxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl ] 2- (2-hydroxyphenyl) such as benzotriazole Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl -1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-ditert-butylphenyl-3,5-di Benzoates such as tert-butyl-4-hydroxybenzoate and hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4′-dodecyloxy Substituted oxanilides such as zanylide; ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) Cyanoacrylates nil) acrylate; various metal salts or metal chelates, especially be mentioned salts or chelates of nickel or chromium or the like, particularly, 2- (2-hydroxyphenyl) benzotriazoles are preferred.
When adding the said ultraviolet absorber, it is preferable that the addition amount is 0.001-10 mass% in a thermosensitive recording layer, and it is more preferable that it is 0.1-1.0 mass%.

  In the heat-sensitive recording material of the present invention, the phenol compound represented by the general formula (I), the color former, the sensitizer used as necessary, the other color developer, the storage stabilizer, etc. are usually a ball mill, Finely divided by a grinder such as an attritor or a sand grinder or an appropriate emulsifying device, and further prepared by adding various additives according to the purpose. The coating liquid is made of paper, non-woven fabric, metal foil or various films. The heat-sensitive recording material of the present invention can be obtained by coating on an arbitrary support such as a kind.

  The thermosensitive recording material of the present invention may be provided with an overcoat layer for the purpose of imparting higher storage stability, and may be provided with an undercoat layer in order to improve the color development sensitivity.

  As the overcoat layer, for example, a photocurable resin, an electron beam curable resin, a thermosetting resin, or the like is applied and then cured to form a film, or a latex or water-soluble highly soluble film capable of forming a film. It is formed by coating molecules, and the above various additives may be used in addition to a crosslinking agent or a curing agent such as an epoxy compound. Any known method may be used for the coating, and the thickness of the coating layer is not limited at all, and is appropriately selected so as to obtain a desired performance. Examples of the undercoat layer include a layer mainly composed of an inorganic pigment and / or an organic pigment and an adhesive, a layer mainly composed of a foaming filler and an adhesive, and a granular and / or fibrous form. A layer mainly composed of an inorganic and / or organic hollow material and an adhesive, and a foam layer formed from a coating liquid obtained by mechanical foaming of an aqueous solution containing a water-soluble polymer or a water-dispersible polymer compound By using a material having excellent heat insulation properties such as, it is possible to develop color with less energy. Also in the undercoat layer, the coating method and the thickness of the coat layer are not particularly limited, and are appropriately selected so as to obtain a desired performance.

  The heat-sensitive recording material of the present invention can be used in various applications to which heat-sensitive recording materials such as various measurement recording papers, computers, facsimiles, telex, vending machines such as tickets, prepaid cards, labels, and receipts are applied.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further in detail, this invention is not restrict | limited to these Examples.
In addition, Example 1-1 and 1-2 show the manufacture example of the phenolic compound of this invention, Example 2-1 shows the evaluation example of the thermosensitive recording material of this invention.

[Example 1-1]
Production of 1,1-bis (4-hydroxyphenyl) -3-phenylindane (Compound No. 1)

  In a 1 L four-necked flask equipped with a stirrer, a nitrogen inlet tube, a reflux condenser, and a thermometer, 93.6 g of 3-phenyl-1-indanone, 254 g of phenol, and 2.4 g of 3-mercaptopropionic acid were added under a nitrogen atmosphere. And 17.7 g of sulfuric acid was added dropwise. After 10 hours of reaction at 60 ° C., 300 g of water and 800 g of ethyl acetate were added. A 48% aqueous sodium hydroxide solution was added to the solution until neutral, and then washed with 300 g of 20% brine. Ethyl acetate in the organic layer was distilled off, and the precipitate formed by adding 200 g of toluene was recovered to obtain 135 g of a crude product. The crude product was crystallized with a mixed solvent of ethyl acetate and toluene to obtain 110 g (yield 65%) of white crystals. As a result of various analyses, the white crystals are the target compound No. 1 was confirmed.

(Analysis result) Purity 99%
(1) Melting point: 212 ° C
(2) 1H-NMR chemical shift: (ppm)
9.32 (s: 1H), 9.28 (s: 1H), 7.33 (t: 2H), 7.29 to 7.19 (m: 4H), 7.19 to 7.10 (m: 1H), 7.04 (d: 1H), 6.99 (d: 2H), 6.92 (d: 2H), 6.74 (d: 1H), 6.71 to 6.64 (m: 4H) ), 4.15 to 4.08 (m: 1H), 3.17 to 3.09 (m: 1H), 2.69 to 2.60 (m: 1H)
(3) IR absorption (cm ^-1 )
3276, 3062, 3025, 2960, 2930, 2878, 1612, 1596, 1559, 1506, 1469, 1450, 1375, 1350, 1308, 1231, 1180, 1150, 1113, 1073, 1012, 912, 836, 763, 754, 733

[Example 1-2]
Production of 1,1-bis (4-hydroxyphenyl) -3,5-diphenylindane (Compound No. 2)

  Under a nitrogen atmosphere, 92.8 g of 3,5-diphenyl-1-indanone, 184 g of phenol, 3-mercaptopropionic acid were added to a 1 L four-necked flask equipped with a stirrer, a nitrogen introducing tube, a reflux condenser, and a thermometer. 73 g was charged and 12.8 g of sulfuric acid was added dropwise. After 15 hours of reaction at 60 ° C., 300 g of water and 800 g of ethyl acetate were added. A 48% aqueous sodium hydroxide solution was added to the solution until neutral, and then washed with 300 g of 20% brine. Ethyl acetate in the organic layer was distilled off, and the precipitate produced by adding 200 g of toluene was recovered to obtain 112.4 g of a crude product. The crude product was crystallized from a mixed solvent of ethyl acetate and toluene to obtain 61.7 g (yield 42%) of white crystals. As a result of various analyses, the white crystals are the target compound No. 2 was confirmed.

(Analysis result) Purity 98%
(1) Melting point: 197 ° C
(2) Chemical shift of ¹ H-NMR: (ppm)
9.32 (s: 1H), 9.28 (s: 1H) 7.55 to 7.48 (m: 3H), 7.41 to 7.25 (m: 8H), 7.14 (d: 1H) ), 7.06 (d: 2H), 6.96 to 6.93 (m: 3H), 6.70 (t: 4H), 4.22 to 4.15 (m: 1H), 3.23 to 3.15 (m: 1H), 2.68 (t: 1H)
(3) IR absorption (cm ^-1 )
3592, 3293, 3025, 2955, 2930, 2876, 1608, 1595, 1509, 1474, 1441, 1368, 1350, 1298, 1252, 1236, 1177, 1112, 1012, 901, 864, 831, 765, 703

[Example 2-1 and Comparative Examples 1-1 and 1-2]
A thermal recording paper was prepared and evaluated according to the following procedure. In the following, “%” means “% by weight”.

“Preparation of 10% PVA solution” (for developer, preservative, filler)
In a 2000 ml beaker, 900 g of water was added, the temperature was raised to about 60 ° C., and stirred and maintained, 100 g of PVA (Kuraray Kuraray Poval KL-318) was dissolved little by little, and 10% PVA solution no. It was set to 1.

“Preparation of 10% PVA solution” (for dyes)
In a 2000 ml beaker, 900 g of water was added, the temperature was raised to about 60 ° C., and stirred and maintained, 100 g of PVA (Kuraray Kuraray Poval PVA405) was dissolved in small portions to obtain a 10% PVA solution no. 2.

"Preparation of developer dispersion"
A 10% PVA aqueous solution No. 1, 2 g of 10% PEX SSH aqueous solution made by Kao, 8.3 g of water, 2.0 g of 4- (4-isopropoxyphenylsulfonyl) phenol as a developer, glass beads (average particle size 1.5-2) .5 mm) 20 g was added, set to SPEED 3.5 with Thermo Shaker MODEL Z-1 manufactured by Thermonics Co., Ltd., and vibrated for 12 hours to obtain a developer dispersion.

"Preparation of preservative improver dispersion"
A 10% PVA aqueous solution No. 1, 2 g of 10% Kao Perex SSH aqueous solution 0.2 g, water 8.3 g, compound No. 1 as a preservative improver. 1 or the following comparative compound No. 1 2.0g each and glass beads (average particle size 1.5-2.5mm) 20g were added, set to SPEED3.5 with Thermonics MODEL · Z-1 manufactured by Thermonics Co., Ltd., and vibrated for 12 hours. A storage stability improving agent dispersion was obtained.

  Comparative Compound No. 1: 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane

“Preparation of filler dispersion”
A 10% PVA aqueous solution No. 1 g of 2%, 10% Kao Perex SSH aqueous solution 0.2 g, water 8.3 g, filler (calcium carbonate), glass beads (average particle size 1.5 to 2.5 mm) 20 g were added, Thermonics Co., Ltd. The dispersion was set to SPEED 3.5 with a thermo shaker MODEL • Z-1 and vibrated for 12 hours.

"Preparation of dye dispersion"
A 10% PVA solution no. 2 g, 0.02 g of Epan 420 from Daiichi Kogyo Seiyaku, 8.48 g of water, 2 g of 3-dibutylamino-6-methyl-7-anilinofluorane as a dye (color former), glass beads (average particle size 1.5 to 2.5 mm) was added, and the temperature was set to SPEED 3.5 with a thermo shaker MODEL • Z-1 manufactured by Thermonics Co., Ltd., and the mixture was vibrated for 12 hours to obtain a dispersion.

"Preparation of coating liquid"
2 g of the developer dispersion prepared above, 0.2 g of the storage stability improving agent dispersion, 3 g of the filler dispersion, and 1 g of the dye dispersion were added to the screw tube No. 2 (6 cc) was weighed, stirred for about 1 hour, and then allowed to stand until no foaming occurred to obtain a coating solution.

“Production and evaluation of thermal recording paper”
The coating solution was applied to a base paper with a thickness of 32 μm using a bar coater, and dried to obtain a heat-sensitive recording paper. An evaluation piece was printed on the thermal recording paper at 220 ° C. using a static color tester manufactured by Okura Engineering. The density of the printed portion of this evaluation piece was measured with a Macbeth densitometer (RD-933 type manufactured by Macbeth). This evaluation piece was stored under the following heat-resistant storage test conditions, wet heat-resistant storage test conditions, and plasticizer resistance test conditions, and the density of the printed portion was measured again to calculate the residual ratio of density. The results are shown in [Table 1].

・ Heat-resistant storage test conditions 80 ° C., dry, 30 minutes storage, equipment: “EYRLAWFO-400” manufactured by Tokyo Science Machine Co., Ltd.
-Humidity and heat storage stability test conditions 60 ° C., 90% RH, storage for 30 minutes, apparatus: “Small environmental testing machine JUINOR series SD-01” manufactured by Enomoto Kasei Co., Ltd.
-Plasticizer resistance test conditions An evaluation piece is wrapped with a vinyl chloride wrap film ("High Wrap SAS" manufactured by Mitsui Chemicals Fabro Co., Ltd.), a heat-sensitive recording material is inserted, and the above-described vinyl chloride wrap film is further wound under an environment of 20 ° C. 30 minutes.

From the results of the above [Table 1], the following is clear.
As a preservability improver, compound no. 1 or comparative compound no. In the case of adding 1 the heat resistance was improved to the same extent as compared with the case of adding no preservative.
In addition, those without the storage improver, Comparative Compound No. No. 1, Compound No. With the addition of 1, the heat and moisture resistance and plasticizer resistance improved in this order. In particular, the heat and humidity resistance has improved dramatically.

  From the above, it is clear that the phenolic compound of the present invention has a preservability not found in conventional phenolic compounds.

Claims (5)

A phenol compound represented by the following general formula (I).

(In the formula, X, Y and Z are each independently an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, or 6 to 20 carbon atoms which may be substituted with a halogen atom. An aryl group of the above, an arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom, a heterocyclic group having 2 to 20 carbon atoms which may be substituted with a halogen atom, or a halogen atom, The methylene group in the alkyl group, aryl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, k represents a number of 0 to 4, and k is a number of 2 or more. The plurality of X may be different from each other, the plurality of X may form a ring with each other, the ring may be an aromatic ring, and p and r are 0. Represents a number of ~ 4, k + p + r is an integer of 1 or more In is.) The phenol compound of Claim 1 represented by the following general formula (II).

(In the formula, X, Y, Z, k and r are the same as those in the general formula (I).)   The phenol compound according to claim 1 or 2, wherein Y is a phenyl group in the general formula (I) or the general formula (II).   In the general formula (I) or the general formula (II), when k is 0 or 1 and k is 1, X is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. The phenolic compound according to any one of claims 1 to 3.   A heat-sensitive recording material comprising the phenol compound according to claim 1.