JPH07116087B2 - Novel phenolic compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a novel phenolic compound.

The phenolic compound according to the present invention is a very useful compound as an electron-accepting compound in a recording material such as a heat-sensitive recording material.

<Prior Art> Phenolic compounds or metal salts thereof are compounds used as heat-sensitive and pressure-sensitive recording materials, polymer additives, and polymer monomers. Further, the use as a photographic recording material, an electronic capacitor material, a polymer polymerization catalyst, and a racemic resolving agent is disclosed, and it is one of the most useful compounds in the industry.

Examples of the use of a phenolic compound as a recording material include pressure-sensitive copying paper (US Pat. Nos. 2505470 and 2505489).
No. specification) and thermal recording paper (Japanese Patent Publication No. 45-14039). These are recording materials that are colored by contact, dissolution, or heat melting of an electron-donating, usually colorless or pale-colored dye precursor and an electron-accepting compound, and various phenolic compounds are used as the electron-accepting compound. It is in practical use. However, the basic performance required for recording materials, that is, sufficient color image density, that the coated surface and color image density do not change due to light, water, heat, atmospheric gases, chemicals such as plasticizers, etc. There is no recording material that satisfies all the properties.

<Object of the Invention> An object of the present invention is to provide a novel derivative of a phenolic compound which is one of the most useful compounds in the industry. It is also to provide a recording material using the same.

<Structure of Invention> The present invention has the following formula The present invention relates to a phenolic compound represented by

Phenolic compounds or metal salts thereof are compounds used as heat-sensitive and pressure-sensitive recording materials, polymer additives and polymer monomers. Further, the use as a photographic recording material, an electronic capacitor material, a polymer polymerization catalyst, and a racemic resolving agent is disclosed, and it is one of the most useful compounds in the industry.

Examples of materials using a phenolic compound as a recording material include heat-sensitive recording paper and pressure-sensitive copying paper, which are usually colored by contact, dissolution, or heat melting between a colorless or light-colored dye precursor and an electron-accepting compound. It is a recording material. Recording materials were prepared by using the novel phenolic compound shown in the present invention as the electron accepting compound in these recording materials. As a result, a heat-sensitive recording material having a stable color density was obtained. Further, a pressure-sensitive recording material having a color density that can be practically used was obtained.

Next, a specific method for producing the recording material according to the present invention will be described.

The heat-sensitive recording material according to the present invention is generally provided with a heat-sensitive recording layer mainly composed of an electron-donating, usually colorless or light-colored dye precursor and an electron-accepting compound on a support, and a heat head, a heat pen, and a laser beam. By heating at a temperature such as the above, a dye precursor and an electron-accepting compound react instantaneously to obtain a recorded image, which is disclosed in JP-B-43-4160 and JP-B-45-14039. Further, a pigment, a sensitizer, an antioxidant, an anti-sticking agent, etc. are added to the heat-sensitive recording layer as needed.

Examples of binders used in heat-sensitive recording materials include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid soda, acrylic acid amide / acrylic acid ester copolymer acrylic acid amide. / Acrylic ester / methacrylic acid terpolymer, water-soluble adhesive such as alkali salt of styrene / maleic anhydride copolymer, alkali salt of ethylene / maleic anhydride copolymer, polyvinyl acetate, polyurethane, Examples thereof include latex such as polyacrylic acid ester, styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, methyl acrylate / butadiene copolymer, ethylene / vinyl acetate copolymer and the like.

Further, in order to further improve the sensitivity, N is used as an additive.
-Waxes such as hydroxymethylstearic acid amide, stearic acid amide and palmitic acid amide, naphthol derivatives such as 2-benzyloxynaphthalene, biphenyl derivatives such as p-benzylbiphenyl and 4-allyloxybiphenyl, 1,2-bis ( 3-methylphenoxy)
Polyether compounds such as ethane, 2,2'-bis (4-methoxyphenoxy) diethyl ether, bis (4-methoxyphenyl) ether, diphenyl carbonate, dibenzyl oxalate, di (p-fluorobenzyl) oxalate, etc. Carbonic acid or an oxalic acid diester derivative or the like can be added.

In addition, for the purpose of preventing head wear and sticking, higher fatty acid metal salts such as zinc stearate and calcium stearate, waxes such as paraffin, oxidized paraffin, polyethylene, oxidized polyethylene, stearic acid amide, and castor wax, A dispersant such as sodium dioctylsulfosuccinate, a UV absorber such as a benzophenone-based or benzotriazole-based, a surfactant, a fluorescent dye, and the like are added as necessary.

Pressure-sensitive recording materials are US Patent Nos. 2505470, 2505471 and
No. 2505489, No. 2548366, No. 2712507, No. 2730456,
It can take various forms as described in the prior patents such as 2730457 and 3418250. The pressure-sensitive recording material can be produced by applying the methods disclosed in these to the electron-accepting compound of the present invention.

The color-developing layer of the pressure-sensitive recording material is usually obtained by dissolving a colorless or light-colored dye precursor in a solvent, incorporating it in a microcapsule, and then coating it on a support.
On the other hand, the electron-accepting compound is dissolved or dispersed in a medium such as water together with a binder and coated on a support to obtain a color-developing sheet.

Generally, the dye precursor and the electron-accepting compound are coated on the same side or opposite sides of the support. Then, the dye precursor in the microcapsules is released by the writing pressure or the pressing pressure, comes into contact with the electron accepting compound, and recording according to the pressure is obtained.

As the binder used in the pressure-sensitive recording material, natural rubber latex, synthetic rubber-based nitrile rubber, urethane rubber, styrene-butadiene rubber, methylmethacrylate-butadiene rubber, chloroprene rubber, butyl rubber, synthetic resin-based biryl acetate, vinyl chloride. , Vinylidene chloride,
An emulsion such as an acrylic ester may be used.
Further, polyvinyl alcohol, casein, starch, gelatin, carboxymethyl cellulose and the like may be used in combination.

The dye precursor used in the heat-sensitive and pressure-sensitive recording material of the present invention is not particularly limited as long as it is generally used for pressure-sensitive recording paper or heat-sensitive recording paper. Specific examples are (1) triarylmethane compounds 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylamino) Phenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,
2-dimethylindol-3-yl) phthalide, 3-
(P-Dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-phenylindole-3-
Yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis (1,2-dimethylindol-3-yl) -6-dimethyl Aminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3
-Bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrol-2-yl) -6-dimethylaminophthalide, etc. (2 ) Diphenylmethane compound 4,4'-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-halophenylleuco auramine, N-2,4,5-trichlorophenyl leuco auramine and the like.

(3) Xanthene compound Rhodamine B anilinolactam, Rhodamine B p-chloroanilinolactam, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7 -Phenylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7- (3,4-dichloroanilino) fluorane, 3-diethylamino- 7-
(2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3- (N-
Ethyl-N-tolyl) amino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-tolyl) amino-6-methyl -7-phenethylfluorane, 3-diethylamino-7- (4-nitroanilinofluorane, 3
-Dibutylamino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-propyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N)
-Isoamyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane, 3- (N-
Ethyl-N-tetrahydrofuryl) amino-6-methyl-7-anilinofluorane and the like.

(4) Thiazine-based compounds benzoyl leuco methylene blue, p-nitrobenzoyl leuco methylene blue and the like.

(5) Spiro compound 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3′-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo ) Spiropyran, 3-propyl spiro benzopyran, etc. can be mentioned, and these can be used individually or in mixture of 2 or more.

Paper is mainly used as the support used in the present invention, but a non-woven fabric, a plastic film, a synthetic paper, a metal foil, or a composite sheet in which these are combined can be optionally used.

The novel phenolic compound shown in the present invention is, for example, p-
It can be obtained by the following method using a phenylphenol derivative as a raw material. That is, the formula [I] By the oxidative dimerization of the p-phenylphenol derivative represented by the formula [II] A compound of formula [III] is prepared by the dealkylation reaction of a compound of formula [II] The novel phenol compound of the present invention shown by is obtained.

In addition, the compound of formula [I] or 3-cumyl-
Compounds of the formula [I] such as 4-hydroxybiphenyl and 3-amyl-4-hydroxybiphenyl, or derivatives thereof can be easily synthesized by known methods. In addition, the derivatives of the compounds of the formulas [II] and [III] are presumed to be produced by a method such as halogenation or alkylation of these compounds, or a derivative of the compound represented by the formula [I] or a related compound thereof.

<Examples> Next, the present invention will be described in more detail with reference to Examples.

The parts and% shown below are based on weight.

(Synthesis example) 4 ', 6 "-dihydroxy [1,1': 3 ', 1": 3 ", 1]-
Synthesis of quarterphenyl. This compound was synthesized from p-phenylphenol as a raw material by the following three-step synthetic method.

(1) Synthesis of 3-tert-butyl-4-hydroxybiphenyl After dissolving p-phenylphenol (26 g) in 100 ml of isopropyl ether and 100 ml of tert-butyl alcohol, the system is cooled to 0 ° C. While stirring the solution, 60 ml of concentrated sulfuric acid is added dropwise over about 1 hour. After finishing the dropping, bring the system to 50
Keep stirring at ℃ and continue stirring. After completion of the reaction, the system is cooled to 0 ° C. and 100 ml of pure water is carefully added. The organic layer was separated, washed with water, and the solvent was distilled off to obtain an oily product. Crystallization of this oily product was difficult and was used for the next synthesis without further purification.

(2) Synthesis of 5 ', 5 "-di-tert-butyl-4', 6" -dihydroxy [1,1 ': 3', 1 ": 3", 1] -quarterphenyl Obtained in (1) above. Sodium hydroxide on the crude product
Add 12g and pure water 50ml and heat to 80 ℃. Add 10 ml of hydrogen peroxide solution (30%) for about 1 hour. Stirring is continued for about 1 hour after the completion of dropping. The reaction mixture is added to 300 ml of 10% hydrochloric acid, ethyl acetate is added to dissolve the product, and the product is washed with water. After distilling off the solvent, recrystallize from ethanol to give 28g of product.
Got Yield 81 based on p-phenylphenol
%. Melting point 120-123 ° C. Nuclear magnetic resonance spectrum (t-butyl group-derived signal δ value 2.03 [in deuterated chloroform] Single, showing a symmetrical form. Hydroxy group-derived signal δ value 5.5 (broad signal)).

(3) 4 ', 6 "-dihydroxy- [1,1': 3 ', 1": 3 ",
1] -Synthesis of quarterphenyl 25 g of the product obtained by the method of (2) was dissolved in 150 ml of toluene, and Nafion-H (manufactured by du Pont, fluoropolymer acid,
10 g of ion exchange resin) is added and refluxed for about 4 hours. After filtration, the solvent was distilled off from the filtrate and recrystallized from ethanol-water to obtain 16 g of a product. Yield 85%. Melting point 176-177 [deg.] C.
Mass spectrum Molecular ion peak m / e = 338.

(Example 1) Preparation of thermosensitive recording material (1) Preparation of thermosensitive coating liquid 3-dibutylamino-6-methyl-7 which is a dye precursor
30 parts of anilinofluorane were pulverized with 120 parts of 2.5% aqueous solution of polyvinyl alcohol in a ball mill for 24 hours to obtain a dye dispersion liquid. Then 4 ', 6 "-dihydroxy- [1,
1 ': 3', 1 ": 3", 1] -Quaterphenyl 40 parts 2.5
% Polyvinyl alcohol aqueous solution together with a ball mill for 24 hours to obtain a color developer dispersion.

After mixing the above-mentioned two kinds of dispersions, the following were added under stirring and well mixed to prepare a heat-sensitive coating liquid.

50% dispersion 60 parts zinc stearate 40% dispersion 25 parts of 10% aqueous solution of polyvinyl alcohol 40 parts Water 250 parts of calcium carbonate (2) basis weight The coating liquid comprising a blend of the creation of the following heat-sensitive coating paper 40 g / m ² The heat-sensitive coated paper was prepared by applying a solid coating amount of 6 g / m ² to the base paper and drying.

Calcined kaolin 100 parts Styrene-butadiene latex 50% aqueous dispersion 24 parts 10% Polyvinyl alcohol aqueous solution 40 parts Water 68 parts (3) Preparation of heat-sensitive recording material The heat-sensitive coating solution obtained in (1) was applied to the above heat-sensitive coated paper. The solid dye was smeared on the smeared surface so that the solid dye content was 0.5 g / m ^2, and dried to prepare a heat-sensitive recording material.

Comparative Example 1 4 ′, 6 ″ -dihydroxy- [1,1 ′:
A thermal recording material was prepared in the same manner as in Example 1 except that 3 ′, 1 ″: 3 ″, 1] -quarterphenyl was changed to 2,2-bis (4-hydroxyphenyl) propane.

(Evaluation 1) The heat-sensitive recording materials obtained in Example 1 and Comparative Example 1 were calendered so that the Bekk smoothness of the heat-sensitive coated surface was 400 to 500 seconds, and then the facsimile tester TH-P manufactured by Okura Electric Co., Ltd.
A printing test was performed using MD. Dot density 8 dots / m
Using a thermal head with m and head resistance of 185Ω, energize at a head voltage of 12V for printing, and the color density is Macbeth RD-918.
It was measured by a reflection densitometer. In addition, the printed sample was left for 24 hours under the conditions of 40 ° C and 90% humidity, and the optical density
The image residual ratio after processing was compared for those near 1.0.

The image residual rate was calculated by the following formula.

(Application Example 1) In the same manner as in Example 1, 4 ', 6 "-dihydroxy- [1,
A 1 ′: 3 ′, 1 ″: 3 ″, 1] -quarterphenyl dispersion was prepared. Further, 2 parts of sodium hexametaphosphate, 200 parts of calcium carbonate and 120 parts of kaolin were added to 750 parts of water to prepare a pigment dispersion liquid. Next, mix the above two types of liquid and
A developer coating solution was prepared by adding 20 parts of an acrylamide aqueous solution and 20 parts of 48% carboxy-modified styrene-butadiene latex (trade name, manufactured by Dow 1876-06 Asahi Kasei).

This coating liquid was applied to a high-quality paper of 40 g / m ^{2 so} that the dry coating amount was 4 g / m ² , and dried at 105 ° C. to prepare a color developing sheet.

(Evaluation 2) In order to evaluate the color-developing sheet prepared in Application Example 1, a commercially available Mitsubishi NCR paper blue is applied so that the coated surfaces face each other, and calendar pressure is applied to develop the entire surface of the color-developed sheet. The color density after 1 minute was measured with a Macbeth RD-514 reflection densitometer. As a result, a color density of 0.63 was obtained.

<Effect> As is clear from the examples, the compounds shown in the present invention are novel industrially useful substances. For example, as is clear from the results in Table 1, the thermal recording paper using the novel substance of the present invention as an electron-accepting compound has a stable color density as compared with the conventionally used substances, The usefulness of the substance as a thermal recording material was shown. Further, a pressure-sensitive copying paper using the novel substance of the present invention as an electron-accepting compound also has a sufficient color density and is useful as a pressure-sensitive recording material.

Claims (2)

[Claims] 1. The following formula Is a novel phenolic compound. 2. A phenol according to claim 1, which is a thermosensitive recording material containing a colorless or light-colored dye precursor and an electron-accepting compound which reacts when heated to develop the color of the dye precursor. A heat-sensitive recording material containing a photosensitive compound.