JP2006056168A - Heat-sensitive recording body and aromatic polycyclic compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-sensitive recording body, especially, showing resistance against a plasticizer for plastics and capable of preserving records for a long period of time, and a novel compound useful as a developer or the like. <P>SOLUTION: The heat-sensitive recording body has a heat-sensitive color developing layer including a colorless or light-colored dye precursor and the developer, which develops color under heating through a chemical reaction with the dye precursor. The developer is an aromatic polycyclic compound represented by general formula (I) [wherein R<SP>1</SP>and R<SP>2</SP>represent a 1-4C alkyl group, a 1-4C haloalkyl group or a halogen atom, X represents an oxygen atom, a sulfur atom, -CH<SB>2</SB>-, -SO<SB>2</SB>- or a single bond, m and n respectively represent an integer of 0-3, and A is formula (II) (p is an integer of 0-2 and k is an integer of 0-3)]. The aromatic polycyclic compound has such a structure. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a heat-sensitive recording material and a novel aromatic polycyclic compound.
More specifically, the present invention is a thermal sensor having a thermosensitive coloring layer using a novel developer that exhibits excellent resistance to various environmental conditions, particularly plastic plasticizers, and enables long-term recording storage. The present invention relates to a novel aromatic polycyclic compound useful as a recording material and the developer.

Colorless or light-coloring colorless dyes, for example, heat-sensitive recording materials utilizing the heat-coloring phenomenon of leuco dyes and phenols and organic acids are widely described in, for example, Patent Document 1, Patent Document 2, Patent Document 3 and the like. It has been put into practical use.
Such a heat-sensitive recording material is generally formed on a paper or plastic film as a support on a color developing material represented by a leuco dye and an ISP called ISP which is an organic acidic material represented by a phenolic compound.

The developer represented by the formula (1) is finely dispersed and applied uniformly and thinly to provide a heat-sensitive color developing layer.
When the thermosensitive coloring layer is locally heated, the color developing substance and the developer, which is an organic acidic substance, melt and mix with each other, and color is generated by exchange of protons.
The production technique of the thermal recording material, that is, the coating technique itself is not difficult, and the recording apparatus is compact and inexpensive, and maintenance and inspection are easy.

Therefore, this thermal recording medium is used not only for conventional facsimiles but also for various applications such as prepaid cards, point cards, tickets, ski lift tickets, bar code labels for products, and medical films. Yes.
In recent years, the thermal recording system is used not only in conventional facsimiles but also in fields that require record storability, such as prepaid cards, point cards, tickets, ski lift tickets, product barcode labels, and medical films. It became so.
Accordingly, there is a demand for records not to be lost even when exposed to various environmental conditions.
In particular, when used as a card or film, it is often compounded with plastic, and there is a problem that the recording is lost due to the plasticizer of the plastic, and the developer with excellent plasticizer resistance. Is required.
Examples of the plasticizer-resistant developer include the following formula:

Is disclosed (for example, see Patent Document 4), but this does not always satisfy all of the requirements sufficiently.
Japanese Patent Publication No.43-4160 Japanese Examined Patent Publication No. 45-14039 JP-A-48-27736 JP-A-5-148220

  Under such circumstances, the present invention provides a thermosensitive coloring layer using a novel developer that exhibits excellent resistance to various environmental conditions, particularly plastic plasticizers, and enables long-term recording and storage. It is an object of the present invention to provide a heat-sensitive recording material having a novel compound useful as a developer and the like.

〔式中、Ｒ¹及びＲ²は、それぞれ独立して、Ｃ₁〜Ｃ₄アルキル基、Ｃ₁〜Ｃ₄ハロアルキル基又はハロゲン原子を示し、Ｘは、酸素原子、硫黄原子、−ＣＨ₂−、−ＳＯ₂−又は単結合を示し、ｍ及びｎ、それぞれは０、１、２又は３の整数を示し、Ａは式（II）

（ｐは０、１又は２の整数を示し、ｋは１、２又は３の整数を示す。）
を示す。〕
で表わされる芳香族系多環化合物であることを特徴とする感熱記録体、
（２）一般式（Ｉ）

〔式中、Ｒ¹及びＲ²は、それぞれ独立に、Ｃ₁〜Ｃ₄アルキル基、Ｃ₁〜Ｃ₄ハロアルキル基又はハロゲン原子を示し、Ｘは、酸素原子、硫黄原子、−ＣＨ₂−、−ＳＯ₂−又は単結合を示し、ｍ及びｎ、それぞれ０、１、２又は３の整数を示し、Ａは式（II）

（ｐは０、１又は２の整数を示し、ｋは１、２又は３の整数を示す。）
を示す。〕
で表わされる構造を有する芳香族系多環化合物
を提供するものである。 As a result of intensive research to achieve the above object, the present inventor has developed an aromatic polycyclic compound having a specific structure as a developer that reacts with a dye precursor under heating to develop color. It has been found that by using it, a heat-sensitive recording material suitable for the purpose can be obtained, and that the aromatic polycyclic compound is a novel compound and is extremely useful as the developer.
The present invention has been completed based on such findings.
That is, the present invention
(1) It has a heat-sensitive color developing layer containing a colorless or light-colored dye precursor and a color developer that reacts with the dye precursor under heating to develop the color, and the color developer has the general formula (I )

[Wherein, R ¹ and R ² each independently represent a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ haloalkyl group or a halogen atom, and X represents an oxygen atom, a sulfur atom, —CH ₂ — , —SO ₂ — or a single bond, m and n, each representing an integer of 0, 1, 2 or 3, and A represents the formula (II)

(P represents an integer of 0, 1 or 2, and k represents an integer of 1, 2 or 3.)
Indicates. ]
A heat-sensitive recording material, characterized by being an aromatic polycyclic compound represented by:
(2) General formula (I)

[Wherein, R ¹ and R ² each independently represent a C _{1 to} C ₄ alkyl group, a C _{1 to} C ₄ haloalkyl group or a halogen atom, and X represents an oxygen atom, a sulfur atom, —CH ₂ —, —SO ₂ — or a single bond, m and n, each representing an integer of 0, 1, 2, or 3, and A represents the formula (II)

(P represents an integer of 0, 1 or 2, and k represents an integer of 1, 2 or 3.)
Indicates. ]
An aromatic polycyclic compound having a structure represented by the formula:

According to the present invention, since it exhibits excellent resistance to various environmental conditions, particularly plastic plasticizers, it can be stored for a long period of time. It is possible to provide a thermosensitive recording medium having a thermosensitive coloring layer using a colorant, and a novel aromatic polycyclic compound useful as the developer.
In particular, it is possible to provide an excellent thermal recording material that does not require complicated processing such as providing a protective layer.

The heat-sensitive recording material of the present invention has a heat-sensitive color-developing layer containing a colorless or light-colored dye precursor and a color developer that reacts with the dye precursor under heating to develop color.
The colorless or light-colored dye precursor used in the heat-sensitive color developing layer is not particularly limited, and any one of known dye precursors conventionally used in heat-sensitive color developing layers in heat-sensitive recording media is appropriately selected. Can be used.
Examples of such dye precursors include triphenylmethane, diphenylmethane, fluoran, phenothiazine, auramine, and spiropyran compounds. Specifically, 3- (4-diethylamino-2-ethoxy Phenyl) -3- (1-ethyl-2-methylindol-3-yl) -4-azaphthalide; 3,3-bis (p-dimethylaminophenyl) -phthalide; 3,3-bis (p-dimethylaminophenyl) ) -6-dimethylaminophthalide (common name: crystal violet lactone); 3,3-bis (p-dimethylaminophenyl) -6-diethylaminophthalide; 3,3-bis (p-dimethylaminophenyl) -6 -Chlorophthalide; 3,3-bis (p-dibutylaminophenyl) -phthalide; 3-cyclohexyl Mino-6-chlorofluorane; 3-dimethylamino-5,7-dimethylfluorane; 3-diethylamino-7-methylfluorane; 3-diethylamino-6-methyl-7-anilinofluorane; 3-diethylamino- 7-chlorofluorane; 3-diethylamino-7,8-benzofluorane; 3-diethylamino-6-methyl-7-chlorofluorane; 3- (Np-tolyl-N-ethylamino) -6-methyl -7-anilinofluorane; 3-piperidino-6-methyl-7-anilinofluorane; 2- {N- (3'-trifluoromethylphenyl) amino} -6-diethylaminomethylfluorane; 3,6-bis (diethylamino) -9- (o-chloranilino) xanthine lactam benzoate; 3-diethylamino-6-methyl-7 (M-trichloromethylanilino) fluorane; 3-diethylamino-7- (o-chloroanilino) fluorane; 3-dibutylamino-7- (o-chloroanilino) fluorane; 3-N-methyl-N-amylamino-6-methyl -7-anilinofluorane; 3-N-ethyl-N-isopentylamino-6-methyl-7-anilinofluorane; 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilino Fluorane; 3-diethyl-6-methyl-7-anilinofluorane; 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane; benzoylleucomethylene blue; 6 '-Chloro-8'-methoxy-benzoindolinose pyropyran; 6'-bromo-3'-methoxy-benzoindolinose Pyropyran; 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenyl) phthalide; 3- (2'-hydroxy-4'-dimethylaminophenyl) -3 -(2'-methoxy-5'-nitrophenyl) phthalide; 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide; 3- ( 2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-5'-chlorophenyl) phthalide; 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluorane; 3-pyrrolidino -7-trifluoromethylanilinofluorane; 3-diethylamino-5-chloro-7- (N-benzyl-trifluoromethylanilino) Luolan; 3-piperidino-7- (di-p-chlorophenyl) methylaminofluorane; 3- (N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluorane; 3-diethylamino-7- ( o-methoxycarbonylphenylamino) fluorane; 3-diethylamino-5-methyl-7- (α-phenylethylamino) fluorane; 3-diethylamino-7-piperidinofluorane; 2-chloro-3- (N— Methyltoluidino) -7- (pn-butylanilino) fluorane; 3- (N-benzyl-N-cyclohexylamino) -5,6-benzo-7-α-naphthylamino-4'-bromofluorane; 3-diethylamino -6-methyl-7-mesitidino-4 ', 5'-benzofluorane, 3-N, N-di-n-butylamino- -Methyl-7-anilinofluorane, 3-N, N-di-n-pentylamino-6-methyl-7-anilinofluorane, 2,2-bis (4- (6 '-(N-cyclohexyl) -N-methylamino) -3'-methylspiro (phthalide-3,9'-xanthene) -2'-ylamino) phenyl) propane.

〔式中、Ｒ¹及びＲ²は、それぞれ独立して、Ｃ₁〜Ｃ₄アルキル基、Ｃ₁〜Ｃ₄ハロアルキル基又はハロゲン原子を示し、Ｘは、酸素原子、硫黄原子、−ＣＨ₂−、−ＳＯ₂−又は単結合を示し、ｍ及びｎ、それぞれ０、１、２又は３の整数を示し、Ａは式（II）

（ｐは０、１又は２の整数を示し、ｋは１、２又は３の整数を示す。）
を示す。〕
で表わされる芳香族系多環化合物が用いられる。
前記一般式（Ｉ）において、Ｒ¹及びＲ²のＣ₁〜Ｃ₄アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられ、Ｃ₁〜Ｃ₄ハロアルキル基としては、上記Ｃ₁〜Ｃ₄アルキル基の水素原子が、下記例示のハロゲン原子で適当に置換されたアルキル基が挙げられ、ハロゲン原子としては、フッ素、塩素、臭素及びヨウ素原子が挙げられる。
本発明の一般式（Ｉ）で表わされる芳香族系多環化合物の具体例としては、例えば、９,９−ビス−(４−ヒドロキシフェニルチオ)メチル−９Ｈ−フルオレン、９,９−ビス−（４−ヒドロキシフェニルチオ）エチル−９Ｈ−フルオレン、９,９−ビス−（４−ヒドロキシフェニルチオ）プロピル−９Ｈ−フルオレン、９,９−ビス−（４−ヒドロキシフェニルチオ）メチル−９,１０−ジヒドロアントラセン、９,９−ビス−（４−ヒドロキシフェニルチオ）エチル−９,１０−ジヒドロアントラセン、９,９−ビス−（４−ヒドロキシフェニルチオ）メチル−９,１０−キサンテン、９,９−ビス−（４−ヒドロキシフェニルチオ）エチル−９,１０−キサンテン、９,９−ビス−（４−ヒドロキシフェニルチオ）メチル−９,１０−チオキサンテン、９,９−ビス−（４−ヒドロキシフェニルチオ）エチル−９,１０−チオキサンテン、９,９−ビス−（４−ヒドロキシフェニルスルホニル）メチル−９,１０−ジヒドロアントラセン、９,９−ビス−（４−ヒドロキシフェニルスルホニル）エチル−９,１０−ジヒドロアントラセン、９,９−ビス−（４−ヒドロキシフェニルスルホニル）メチル−９,１０−キサンテン、９,９−ビス−（４−ヒドロキシフェニルスルホニル）エチル−９,１０−キサンテン、９,９−ビス−（４−ヒドロキシフェニルスルホニル）メチル−９,１０−チオキサンテン、９,９−ビス−（４−ヒドロキシフェニルスルホニル）エチル−９,１０−チオキサンテン、９，９−ビス−（４−ヒドロキシフェニルスルホニル）メチル−９Ｈ−フルオレン、９，９−ビス−（４−ヒドロキシフェニルスルホニル）エチル−９Ｈ−フルオレン、９，９−ビス−（４−ヒドロキシフェニルスルホニル）プロピル−９Ｈ−フルオレン等が挙げられる。
これらの化合物は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。 These dye precursors may be used alone or in combination of two or more.
The developer of the present invention, which reacts with the dye precursor under heating to develop the color, has the general formula (I)

[Wherein, R ¹ and R ² each independently represent a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ haloalkyl group or a halogen atom, and X represents an oxygen atom, a sulfur atom, —CH ₂ — , —SO ₂ — or a single bond, m and n each represent an integer of 0, 1, 2 or 3, and A represents the formula (II)

(P represents an integer of 0, 1 or 2, and k represents an integer of 1, 2 or 3.)
Indicates. ]
An aromatic polycyclic compound represented by the formula:
In the general formula (I), the C ₁ -C ₄ alkyl group of R ¹ and R ² includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. , A tert-butyl group, and examples of the C ₁ -C ₄ haloalkyl group include alkyl groups in which the hydrogen atoms of the above C ₁ -C ₄ alkyl groups are appropriately substituted with the halogen atoms exemplified below. Atoms include fluorine, chlorine, bromine and iodine atoms.
Specific examples of the aromatic polycyclic compound represented by the general formula (I) of the present invention include, for example, 9,9-bis- (4-hydroxyphenylthio) methyl-9H-fluorene, 9,9-bis- (4-hydroxyphenylthio) ethyl-9H-fluorene, 9,9-bis- (4-hydroxyphenylthio) propyl-9H-fluorene, 9,9-bis- (4-hydroxyphenylthio) methyl-9,10 -Dihydroanthracene, 9,9-bis- (4-hydroxyphenylthio) ethyl-9,10-dihydroanthracene, 9,9-bis- (4-hydroxyphenylthio) methyl-9,10-xanthene, 9,9 -Bis- (4-hydroxyphenylthio) ethyl-9,10-xanthene, 9,9-bis- (4-hydroxyphenylthio) methyl-9,10-thioxanthene, 9,9 -Bis- (4-hydroxyphenylthio) ethyl-9,10-thioxanthene, 9,9-bis- (4-hydroxyphenylsulfonyl) methyl-9,10-dihydroanthracene, 9,9-bis- (4- Hydroxyphenylsulfonyl) ethyl-9,10-dihydroanthracene, 9,9-bis- (4-hydroxyphenylsulfonyl) methyl-9,10-xanthene, 9,9-bis- (4-hydroxyphenylsulfonyl) ethyl-9 , 10-xanthene, 9,9-bis- (4-hydroxyphenylsulfonyl) methyl-9,10-thioxanthene, 9,9-bis- (4-hydroxyphenylsulfonyl) ethyl-9,10-thioxanthene, 9 , 9-bis- (4-hydroxyphenylsulfonyl) methyl-9H-fluorene, 9,9-bis- (4-hydroxy Ciphenylsulfonyl) ethyl-9H-fluorene, 9,9-bis- (4-hydroxyphenylsulfonyl) propyl-9H-fluorene, and the like.
These compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

In the heat-sensitive recording material of the present invention, in addition to the aromatic polycyclic compound represented by the general formula (I), another color developer can be used in combination as an auxiliary color developer.
Specific examples of the auxiliary developer include the following compounds.

These auxiliary color developers may be used alone or in combination of two or more.
The amount of the aromatic polycyclic compound represented by the general formula (I) of the present invention used as a developer is generally 0.5 to 10 mass relative to 1 part by mass of the colorless or light dye precursor. Parts, preferably 1 to 5 parts by mass.
Moreover, the usage-amount of an auxiliary color developer is generally selected in the range of 0.1 to 10 parts by mass, preferably 0.3 to 3 parts by mass with respect to 1 part by mass of the colorless or light-colored dye precursor. .

  In the heat-sensitive color developing layer of the heat-sensitive recording material of the present invention, in addition to the dye precursor, developer and auxiliary developer, generally a sensitizer and a binder for binding various components on the support, etc. Can be contained.

Examples of the sensitizer include stearic acid amide, 1-hydroxy-2-naphthoic acid phenyl ester (Japanese Patent Laid-Open No. 57-191089), p-benzylbiphenyl (Japanese Patent Laid-Open No. 60-82382), p. -Acetoluidide (JP 59-9092 A), 2-benzyloxynaphthalene (JP 58-87094 A), oxalic acid diesters (JP 64-1583 JP), p-benzyloxybenzoic acid Benzyl (JP 57-148688, 201691), 1,2-bis (m-tolyloxy) ethane (JP 60-56588), dibenzyl terephthalate (JP 58-98285) ), Diphenyl carbonate, ditolyl carbonate (Japanese Patent Laid-Open No. 58-136489), m-Tafel (Japanese Patent Laid-Open No. 57-8). 994), 1,5-bis (p-methoxyphenoxy) -3-oxapentane (Japanese Patent Laid-Open No. 62-181183), 1,4-bis (p-tolyloxy) benzene (Japanese Patent Laid-Open No. 2-153783). Gazette), diphenylsulfone (JP-B-59-25673), p-toluenesulfonic acid phenyl ester (JP-A-59-73990), mesitylenesulfonic acid-p-tolyl ester (JP-A-2-80285) 4,4'-diallyloxydiphenylsulfone, 4,4'-diisopentyloxydiphenylsulfone, 4,4'-dimethoxydiphenylsulfone (Japanese Patent Publication No. 2-9951), 4,4'-di-n- Pentyloxydiphenyl sulfone (JP-A-60-47070), p-toluenesulfonamide (JP-A-11) It can be exemplified 245524 JP) or the like.
These may be used individually by 1 type, and may be used in combination of 2 or more types.

On the other hand, examples of binders include casein, gelatin, starch and derivatives thereof, celluloses such as methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohols and derivatives thereof having various molecular weights, sodium polyacrylate, polyvinylpyrrolidone, Water-soluble polymer materials such as acrylic acid amide / acrylic acid ester copolymer, acrylic acid amide / acrylic acid ester / methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, etc. , Polyvinyl acetate, polyurethane, styrene / butadiene copolymer, polyacrylic acid, polyacrylate ester, vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene · Vinyl acetate copolymer, latexes or solvent-溶高 molecular material such as styrene-butadiene-acrylic copolymer.
These may be used individually by 1 type, and may be used in combination of 2 or more types.

The heat-sensitive color developing layer in the heat-sensitive recording material of the present invention can further contain various additives and auxiliaries as necessary.
Specifically, calcium carbonate and surface-treated calcium carbonate, white carbon (silica), zinc oxide, titanium oxide, aluminum hydroxide, alumina, zinc hydroxide, barium sulfate, clay, calcined clay, talc as fillers Inorganic fine powders or pigments such as urea, and further, organic fine powders such as urea / formalin resin, styrene / methacrylic acid copolymer, and polystyrene resin can be used.
Further, in order to prevent thermal head wear and sticking, etc., higher fatty acid metal salts such as zinc stearate and calcium stearate are further used as antioxidants or ultraviolet absorbers to further improve image storage stability. For example, a phenol compound and a benzotriazole compound having the following structure can be added.

  1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane

  4,4'-butylidene-bis (6-tert-butyl-3-methylphenol)

  2,2'-methylenebis (4-methyl-6-tert-butylphenol)

  2- (2'-Hydroxy-5'-methylphenyl) benzotriazole

  2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]

The method for forming the heat-sensitive color forming layer in the heat-sensitive recording material of the present invention is not particularly limited, and is a conventionally known method, for example, the above-mentioned components constituting the heat-sensitive color forming layer are finely divided and mixed at an appropriate ratio. A method of preparing a coating solution for forming a heat-sensitive color developing layer by dispersing in water or a solvent, coating on a support, and drying treatment can be used.
The thickness of the thermosensitive coloring layer thus formed is usually selected in the range of 0.1 to 100 μm, preferably 0.5 to 50 μm.

As the support, paper is mainly used. In addition to paper, various woven fabrics, non-woven fabrics, synthetic resin films, synthetic resin laminated papers, synthetic papers, metal foils, vapor-deposited sheets, or composites obtained by combining them together A sheet can be arbitrarily used according to the purpose.
Further, if necessary, coating layers such as a protective layer and a printing layer can be formed on the heat-sensitive color forming layer thus formed.

The heat-sensitive recording material of the present invention thus produced exhibits excellent resistance particularly to plastic plasticizers by using the aromatic polycyclic compound represented by the general formula (I) as a developer. Enables long-term record keeping.
Applications include facsimile paper, word processor paper, CRT image printer paper, medical instrument recording paper and recording film, thermal recording type ticket for automatic ticket vending machines, coupons and commuter passes that require storability, or It is useful as a prepaid card, a point card, a ticket, a ski lift ticket, a bar code label of a product, a label of a bar code system for POS, a label, a receipt or the like.
It is also useful as a monomer for producing a polymer having a low birefringence.

The present invention also provides an aromatic polycyclic compound represented by the general formula (I).
These aromatic polycyclic compounds are novel compounds not described in any literature, and as described above, are useful as color developers used in the heat-sensitive color forming layer of the heat-sensitive recording material.
The aromatic polycyclic compound represented by the general formula (I) can be produced according to the following scheme.
[Production of Compound Represented by General Formula (Ia)]
Scheme 1

〔式中、Ｈａｌは、塩素、臭素などのハロゲン原子を示し、Ａ₁は式（IIａ）

（ｋは、前記に同じ。）を示し、Ｒ¹及びＲ²、Ｘ並びにｍ及びｎは前記に同じ。〕

[In the formula, Hal represents a halogen atom such as chlorine or bromine, and A ₁ represents formula (IIa).

(K is the same as above), and R ¹ and R ² , X, and m and n are the same as above. ]

Scheme 1 represents a compound represented by general formula (III) to a compound represented by general formula (Ia) (A ₁ corresponds to the case where p is 0 in the above formula (II). This is a step of obtaining a compound in which p is 0 in the general formula (I).
The compound represented by the general formula (Ia) can be obtained by reacting the compound represented by the general formula (III) with 2 equivalents of 4-hydroxythiophenol.
The above reaction proceeds smoothly by allowing two equivalents or more of a base such as potassium carbonate, sodium carbonate or triethylamine to coexist, and as the solvent, a solvent inert to the reaction can be appropriately used. For example, dimethylformamide ( DMF) and N-methylpyrrolidone (NMP) are preferred.
The reaction temperature is not particularly limited, but is usually in the range of room temperature to 120 ° C.
The compound represented by the general formula (III) as a starting material can be easily produced by reacting a corresponding dihydric alcohol with a halogenating agent such as thionyl chloride (see Production Example 1). ).
[Production of Compound Represented by General Formula (Ib)]
Scheme 2

〔式中、Ａ₂は式（IIｂ）

（ｑは１又は２の整数を示し、ｋは前記に同じ。）を示し、Ｒ¹及びＲ²、Ｘ並びにｍ及びｎは前記に同じ。〕
スキーム２は、前記一般式（Ｉａ）で表わされる化合物に、酸化剤を作用させて、一般式（Ｉｂ）で表わされる化合物（Ａ₂は、前記一般式（II）において、ｐが１又は２の場合に相当し、従って、本化合物は、前記一般式（Ｉ）においてｐが１又は２の化合物である。）を得る工程である。
一般式（Ｉａ）で表される化合物に、酸化剤を２当量反応させることにより、一般式（Ｉｂ）で表わされる化合物において、ｐが１である化合物が得られ、４当量以上の酸化剤を反応させることにより、ｎが２である化合物を得ることができる。
酸化剤としては、過酸化水素、ベンゾイルペルオキシド（ＢＰＯ）、ｍ−クロロ過安息香酸（ＭＣＰＢＡ）、過酢酸、次亜塩素酸ナトリウム、過マンガン酸カリウム、酸素等を使用することができるが、取り扱いや、反応後の廃棄物の処理の容易さ等から、過酸化水素、次亜塩素酸ナトリウム、酸素、特に、過酸化水素が望ましい。
溶媒としては、使用する酸化剤に対して不活性な溶媒、例えば、酢酸、ぎ酸等の有機酸、トルエン、キシレン、クロロベンゼン、ジクロロベンゼン等の芳香族炭化水素系溶媒、塩化メチレン、クロロホルム、１，２−ジクロロエタン、四塩化炭素、１，１，２，２−テトラクロロエタン等の塩素系溶媒を用いることができる。
反応温度は、特に制限はないが、通常、室温〜１２０℃の範囲である。
尚、一般式（Ｉａ）で表わされる化合物において、Ｘが硫黄原子の場合、使用する酸化剤の当量数を増加することにより、Ｘが−ＳＯ₂−である一般式（Ｉｂ）で表わされる化合物を得ることができる。

[Wherein A ₂ represents formula (IIb)

(Q represents an integer of 1 or 2, k is the same as above), and R ¹ and R ² , X, and m and n are the same as above. ]
In Scheme 2, an oxidant is allowed to act on the compound represented by the general formula (Ia), whereby the compound represented by the general formula (Ib) (A ₂ represents p in the general formula (II) is 1 or 2 Therefore, the present compound is a step of obtaining a compound in which p is 1 or 2 in the general formula (I).
By reacting the compound represented by the general formula (Ia) with 2 equivalents of an oxidant, a compound represented by the general formula (Ib) having a p of 1 is obtained. By reacting, a compound in which n is 2 can be obtained.
As the oxidizing agent, hydrogen peroxide, benzoyl peroxide (BPO), m-chloroperbenzoic acid (MCPBA), peracetic acid, sodium hypochlorite, potassium permanganate, oxygen, etc. can be used. Also, hydrogen peroxide, sodium hypochlorite, oxygen, and particularly hydrogen peroxide are desirable from the standpoint of easy disposal of the waste after the reaction.
Solvents are inert to the oxidant used, for example, organic acids such as acetic acid and formic acid, aromatic hydrocarbon solvents such as toluene, xylene, chlorobenzene and dichlorobenzene, methylene chloride, chloroform, 1 , 2-dichloroethane, carbon tetrachloride, 1,1,2,2-tetrachloroethane and other chlorinated solvents can be used.
The reaction temperature is not particularly limited, but is usually in the range of room temperature to 120 ° C.
In the compound represented by the general formula (Ia), when X is a sulfur atom, the compound represented by the general formula (Ib) in which X is —SO ₂ — is obtained by increasing the number of equivalents of the oxidizing agent used. Can be obtained.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Compound production example 1
Production of 9,9-bis- (4-hydroxyphenylthio) methyl-9H-fluorene (Compound No. 1)

Charge 9 g of 9H-fluorene-9,9-dimethanol (0.088 mol), 100 ml of 1,2-dichloroethane and 20 ml of pyridine into a three-necked flask, and add 20 ml (0.28 mol) of thionyl chloride under a nitrogen atmosphere. The reaction was carried out for 3 hours under heating and reflux.
After completion of the reaction, the reaction mixture was diluted by adding 300 ml of water, and the 1,2-dichloroethane layer was separated.
The 1,2-dichloroethane layer was dried over anhydrous sodium sulfate, 1,2-dichloroethane was distilled off under reduced pressure, and the resulting oil was purified with a silica gel column (effluent: n-hexane). 15.6 g (0.066 mol, yield 75%) of -bis (chloromethyl) -9H-fluorene was obtained.
¹ H-NMR (acetone-d ₆ ): 4.10 (4H, s), 7.33-7.46 (4H, m), 7.72-7.81 (4H, m)

Next, 15 g (0.057 mol) of 9,9-bis (chloromethyl) -9H-fluorene obtained above, 50 ml of dimethylformamide, 16 g of 4-hydroxythiophenol (0.13 mol) were added to a three-necked flask. ), 16 g (0.12 mol) of potassium carbonate, and heated at 80 ° C. for 3 hours in a nitrogen atmosphere.
After completion of the reaction, the reaction solution was diluted with 300 ml of water, and extracted with ethyl acetate.
The ethyl acetate solution was dried over anhydrous sodium sulfate, ethyl acetate was removed under reduced pressure, and the resulting oil was purified by a silica gel column (eluent: n-hexane: ethyl acetate = 1: 1) to obtain a solid target. 11.5 g (0.027 mol, yield 47%) of compound was obtained.
Melting point: 105 ° C
¹ H-NMR (CDCl ₃ ): 3.48 (4H, s), 6.57 (4H, d), 6.98 (4H, d), 7.16-7.47 (6H, m), 7 69-7.79 (2H, m)
IR (cm ⁻¹ ): 3208, 1591, 1493, 1443, 1237, 825, 735

Compound production example 2
Production of 9,9-bis- (4-hydroxyphenylsulfonyl) methyl-9H-fluorene (Compound No. 2)

In a 100 ml eggplant flask, the compound No. obtained in Example 1 was obtained. 1,6 g (0.014 mol), 25 ml of acetic acid, and 8 g of 30% by mass hydrogen peroxide were charged, heated to 60 ° C., and reacted for 3 hours.
After completion of the reaction, the reaction solution was diluted by adding 100 ml of water, and the resulting solid was filtered, washed with water, and dried under reduced pressure to obtain 5.6 g (0.011 mol, yield 81%) of the target compound. .
Melting point: 167 ° C
¹ H-NMR (CDCl ₃ ): 4.78 (4H, s), 7.11 to 7.95 (16H, m)

Example 1 for making thermal recording paper
(1) Preparation of heat-sensitive coating solution A dye precursor, 3-diethylamino-6-methyl-7-anilinofluorane (trade name ODB, manufactured by Yamamoto Kasei Co., Ltd.) 5.0 g is added to a 1.25% by mass aqueous polyvinyl alcohol solution. Dispersed in 20 g, and further pulverized using a sand grinder, to obtain a dispersion A liquid.
Subsequently, the compound No. obtained in the above compound production example 1 was obtained. 1 and 5.0 g were similarly pulverized using 20 g of a 1.25 mass% polyvinyl alcohol aqueous solution and a sand grinder to obtain a dispersion liquid B.

Further, 5.0 g of benzyl naphthyl ether was pulverized using 20 g of a 1.25 mass% polyvinyl alcohol aqueous solution and a sand grinder in the same manner as above to obtain a dispersion C liquid.
Further, 30 g of calcium carbonate was pulverized using 70 g of water and a sand grinder to obtain a dispersion D.
35 parts by weight of dispersion A, 70 parts by weight of dispersion B, 70 parts by weight of dispersion C, 100 parts by weight of dispersion D, 57 parts by weight of polyvinyl alcohol, 57 parts by weight of 40% by weight stearin 4 parts by mass of the zinc acid dispersion was mixed to prepare a heat-sensitive coating solution.

(2) Preparation of thermal recording paper The thermal coating solution obtained in (1) above was applied to high-quality paper using a bar coder so that the dry thickness was 50 μm and dried for 24 hours to obtain a thermal recording paper. It was.

Thermal recording paper production example 2
Compound No. 1 used in Example 1 In place of compound 1, compound no. A thermal recording paper was obtained in the same manner as in Example 1 except that No. 2 was used.

Comparative Example 1 for producing thermal recording paper
Compound No. 1 used in Example 1 A heat-sensitive recording paper was obtained in the same manner as in Example 1 except that 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was used instead of 1.

<Evaluation of coloring and plasticizer resistance>
The heat-sensitive recording paper obtained in Examples 1 and 2 and Comparative Example 1 was cut to a width of 1 cm and heated on a hot plate heated to about 200 ° C. to cause color development.
The color density was measured using a Macbeth densitometer (RD917).
Further, the color developed in this manner is immersed in a plasticizer [di (2-ethylhexyl) phthalate], left at room temperature for 2 hours, then pulled up to wipe off excess plasticizer, and the color density is again measured with a Macbeth densitometer. It was measured.
The results thus obtained are shown in Table 1.

In Comparative Example 1, when immersed in a plasticizer, the color faded to such an extent that it was difficult to identify with the naked eye, whereas in Examples 1 and 2, a color development of practically no problem remained.
As is apparent from this result, it has been found that the novel developer of the present invention exhibits much better plasticizer resistance than conventional developers.

The thermosensitive recording material of the present invention exhibits excellent resistance to various environmental conditions, particularly plastic plasticizers, can be stored for a long period of time, and the white background portion does not develop color even when exposed to high temperatures.
Facsimile paper, word processor paper, CRT image printer paper, medical measuring instrument recording paper and recording film, thermal ticketing ticket for automatic ticket vending machines, coupon tickets, commuter passes or prepaid cards that require preservation It can be used for applications such as cards, tickets, ski lift tickets, bar code labels for products, labels for bar code systems for POS, labels, receipts, and the like.
In addition, the aromatic polycyclic compound represented by the general formula (I) of the present invention can be used as a developer, for example, as a monomer for producing a polymer having a low birefringence. Useful.

Claims (2)

It has a heat-sensitive color developing layer containing a colorless or light-colored dye precursor and a developer that reacts with the dye precursor under heating to develop color, and the developer has the general formula (I)

[Wherein, R ¹ and R ² each independently represent a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ haloalkyl group or a halogen atom, and X represents an oxygen atom, a sulfur atom, —CH ₂ — , —SO ₂ — or a single bond, m and n each represent an integer of 0, 1, 2 or 3, and A represents the formula (II)

(P represents an integer of 0, 1 or 2, and k represents an integer of 1, 2 or 3.)
Indicates. ]
A heat-sensitive recording material, which is an aromatic polycyclic compound represented by the formula: Formula (I)

[Wherein, R ¹ and R ² each independently represent a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ haloalkyl group or a halogen atom, and X represents an oxygen atom, a sulfur atom, —CH ₂ — , —SO ₂ — or a single bond, m and n each represent an integer of 0, 1, 2 or 3, and A represents the formula (II)

(P represents an integer of 0, 1 or 2, and k represents an integer of 1, 2 or 3.)
Indicates. ]
An aromatic polycyclic compound having a structure represented by: