JP2772381B2 - Recording material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material, and more particularly to a recording material having excellent coloring properties.

[Conventional technology]

Between a colorless or pale leuco dye and a developer,
Various recording materials utilizing a coloring reaction by heat, pressure and the like have been proposed.

One of the heat-sensitive recording materials does not require complicated processing such as development and fixing, and can be recorded in a short time with a relatively simple device, has less noise, and has further advantages such as lower cost. Thus, it is useful as various recording materials for electronic computers, facsimile machines, ticket vending machines, labels, recorders and the like.

As the color-forming dye used in the heat-sensitive recording material, for example, a colorless or light-colored leuco dye having a lactone, lactam or spiropyran ring is used, and as a developer, an organic acid, a phenolic substance, or the like is conventionally used. Recording materials using this leuco dye and a developer are widely used because of their high image density and high whiteness of the background.

On the other hand, as the demand for the thermal recording method has increased in recent years,
There has been an increasing demand for faster recording. For this reason, it is strongly desired to develop not only a high-speed recording apparatus but also a recording material that can cope with this.

[Problems to be solved by the invention]

In order to respond to high-speed recording, as a high-speed developer, for example, p-hydroxybenzoic acid ester is disclosed in JP-A-56-144193 and the like, and hydroxynaphthoic acid ester is disclosed in JP-A-59-22793 and the like. Has been proposed. Furthermore, Japanese Patent Application Laid-Open No. 59-165680 discloses that a thioester compound is used as a color developer, but a recording material using the compound has high fastness to oils and fats in an image area, but has high sensitivity and high sensitivity. Is hard to say. There have also been various proposals for increasing the sensitivity by adding various heat-fusible substances.
For example, a naphthol derivative is proposed in JP-A-58-87094 and the like, and benzylbiphenyl and the like are proposed in JP-A-60-82382 and the like.

However, recording materials using these developers or heat-fusible substances are not yet sufficient in terms of color sensitivity, background whiteness, storability (image fading, generation of white powder, etc.). Hard to say.

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material which is excellent in color sensitivity and suitable for high-speed recording, and has high background whiteness and excellent preservability.

[Means for solving the problem]

According to the present invention, in a recording material utilizing a color-forming reaction between a colorless or light-colored leuco dye and a color developer that causes the leuco dye to develop color upon contact, the following general formulas (I) and (I) are used as the color developer. A recording material characterized by using at least one of the phenolic compounds represented by II).

(Wherein, R ₁ represents an aryl group or an aralkyl group which may have a substituent, R ₂ represents a divalent saturated or unsaturated hydrocarbon group which may have a substituent, and X represents Lower alkyl group,
An alkoxy group, an alkenyl group and a halogen atom are respectively shown. M represents an integer of 0 to 4, and n represents an integer of 1 to 3, respectively. In the above general formula (I), R ₁ is an aryl group such as a phenyl group or a naphthyl group or an aralkyl group such as a benzyl group or a phenylethyl group, which may have a substituent. Preferred substituents include an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a nitro group, a hydroxyl group and a halogen atom.

In the general formula (II), R ₂ is a divalent saturated or unsaturated hydrocarbon group which may have a substituent, preferably an alkylene group having 2 to 6 carbon atoms or an unsaturated bond. Which may have an ether, a thioether, an ester, a sulfonyl, or the like.

The recording material of the present invention comprises a compound represented by the general formula (I)
Alternatively, by using the compound represented by (and) (II), the color development sensitivity is excellent and the composition is suitable for high-speed recording, and the background whiteness is high and the storage stability is excellent.

The following formulas (I) and (II) used in the present invention
Specific examples of the phenolic compound represented by are shown below, but the present invention is not limited thereto.

The leuco dyes used in the present invention are applied alone or as a mixture of two or more types. As such leuco dyes, those applied to this type of recording material are arbitrarily applied. Leuco compounds of dyes such as methane, fluoran, phenothiazine, auramine, spiropyran and indolinophthalide are preferably used. Specific examples of such leuco dyes include, for example, those shown below.

3,3-bis (p-dimethylaminophenonyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis (p- Dimethylaminophenyl) -6-diethylaminophthalide, 3,3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6-chloro Fluoran, 3-dimethylamino-5,7-dimethylfluoran, 3- (N-methyl-N-isobutylamino) -6-methyl-7-anilinofluoran, 3- (N-ethyl-N-isoamyl Amino) -6-methyl-7-aninofluoran, 3-diethylamino-7-chlorofluoran, 3-diethylamino-7-methylfluora 3-diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3- (Np-tolyl-N-ethylamino) -6-methyl-7-aniline Linofluoran, 3-pyrrolidino-6-methyl-7-anilinofluoran, 2- {N- (3'-trifluoromethylphenyl) amino} -6-diethylaminofluoran, 2- {3,6-bis (Diethylamino) -9- (o-chloroanilino) xanthyl lactam benzoate, 3-diethylamino-6-methyl-7- (m-trichloromethylanilino) fluoran, 3-diethylamino-7- (o-chloroanilino) fluoran, 3-dibutylamino-7- (o-chloroanilino) fluoran, 3-N-methyl-N-amylamino-6-methyl-7
-Anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl -7- (2 ', 4'-
Dimethylanilino) fluoran, 3- (N, N-diethylamino) -5-methyl-7-
(N, N-dibenzylamino) fluoran, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindolino-
Pyrirospiran, 6'-bromo-3'-methoxy-benzoindolino-
Pyrirospiran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-chlorophenol) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl)- 3- (2'-methoxy-5'-nitrophenol) phthalide, 3- (2'-hydroxy-4'-diethylaminophenyl) -3- (2'-methoxy-5'-methylphenyl) phthalide, 3- ( 2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-
Methylphenyl) phthalide, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7-trifluoromethylanilinofluoran, 3-diethylamino-5-chloro-7- (N -Benzyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluoran, 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoran, 3 -(N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluoran, 3-diethylamino-5-methyl-7- (α -Phenylethylamino) fluoran, 3-diethylamino-7-piperidi Fluoran, 2-chloro-3-(N-Mechirutoruijino) -7-
(Pn-butylanilino) fluoran, 3- (N-methyl-N-isopropylamino) -6
Methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluoran, 3,6-bis (dimethylamino) fluorenespiro (9,
3 ')-6'-dimethylaminophthalide, 3- (N-benzyl-N-cyclohexylamino)-
5,6-benzo-7-α-naphthylamino-4′-bromofluoran, 3-diethylamino-6-chloro-7-anilinofluoran, 3-N-ethyl-N- (2-ethoxypropyl) amino -6-methyl-7-anilinofluoran, 3-N-ethyl-N-tetrahydrofurfurylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-mesitidino-
4 ', 5'-benzofluoran, 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl} phthalide, 3- (p-dimethylaminophenyl) -3- {1,1-
Bis (p-dimethylaminophenyl) ethylene-2-yl} -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (1-p
-Dimethylaminophenyl-1-phenylethylene-2
-Yl) phthalide, 3- (p-dimethylaminophenyl) -3- (1-p
-Dimethylaminophenyl-1-p-chlorophenylethylene-2-yl) -6-dimethylaminophthalide, 3- (4'-dimethylamino-2'-methoxy) -3
-(1 "-p-dimethylaminophenyl-1" -p-chlorophenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3- (4'-dimethylamino-2'-benzyloxy) -3 -(1 "-p-dimethylaminophenyl-1"
-Phenyl-1 ", 3" -butadiene-4 "-yl) benzophthalide, 3-dimethylamino-6-dimethylamino-fluorene-9-spiro-3 '-(6'-dimethylamino) phthalide, 3,3- Bis {2- (p-dimethylaminophenyl)-
2- (p-methoxyphenyl) ethenyl} -4,5,6,7-
Tetrachlorophthalide, 3-bis {1,1-bis (4-pyrrolidinophenyl) ethylene-2-yl} -5,6-dichloro-4,7-dibromophthalide, bis (p-dimethylaminostyryl) -1-naphthalenesulfonylmethane and the like.

In the present invention, a phenolic compound represented by the above general formula (I) or (and) (II) is used as a color developer. If necessary, various compounds having an electron accepting property, for example, a phenolic compound , Thiophenolic compounds, thiourea derivatives, organic acids and metal salts thereof, and the like, and specific examples thereof include the following.

4,4'-isopropylidenebisphenol, 4,4'-isopropylidenebis (o-methylphenol), 4,4'-secondarybutylidenebisphenol, 4,4'-isopropylidenebisphenol (2-tert-butylphenol) 4,4'-cyclohexylidenediphenol, 4,4'-isopropylidenebis (2-chlorophenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis (6-tert-butyl-)
2-methylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-
Tertiary-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-
Cyclohexylphenyl) butane, 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-diphenolsulfone, 4-isopropoxy-4'-hydroxydiphenylsulfone, 4-benzyloxy-4 '-Hydroxydiphenyl sulfone, 4,4'-diphenol sulfoxide, isopropyl P-hydroxybenzoate, benzyl P-hydroxybenzoate, benzyl protocatechuylate, stearyl gallate, lauryl gallate, octyl gallate, 1,3-bis (4-hydroxyphenylthio) -propane, 1,3-bis (4-hydroxyphenylthio) -2-hydroxypropane, N, N'-diphenylthiourea, N, N'-di (m-chlorophenyl) thiourea , Salicanilide, 5-chloro-salicylanilide, bis- (4- Methyl ester of droxyphenyl) acetic acid, benzyl ester of bis- (4-hydroxyphenyl) acetic acid, 1,3- (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 2,4 '-Diphenolsulfone, 2,2'-diallyl-4,4'-diphenolsulfone, 3,4-dihydroxy-4'-methyldiphenylsulfone, zinc 1-acetyloxy-2-naphthoate, 2-acetyl Zinc oxy-1-naphthonate, zinc 2-acetyloxy-3-naphthoate, α, α-bis (4-hydroxyphenyl) -α-methyltoluene, an antipyrine complex of zinc thiocyanate, tetrabromobisphenol A, Tetrabromobisphenol S and the like.

In order to produce the recording material of the present invention, a leuco dye, a developer and an auxiliary component may be bonded and supported on a support. As the binder in this case, various conventional binders can be appropriately used, and specific examples thereof include the following.

Polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, ethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, acrylamide / acrylate copolymer, acrylamide / acrylate /
Water-soluble polymers such as methacrylic acid terpolymer, styrene / maleic anhydride copolymer alkali salt, isobutylene / maleic anhydride copolymer alkali salt, polyacrylamide, sodium alginate, gelatin, casein, and polyacetic acid Vinyl, polyurethane, polyacrylate,
Emulsions such as polymethacrylic acid esters, vinyl chloride / vinyl acetate copolymers, ethylene / vinyl acetate copolymers, and latexes such as styrene / butadiene copolymers and styrene / butadiene / acrylic copolymers.

When a thermosensitive recording material is obtained according to the present invention, various heat-fusible substances can be used as a heat sensitivity improver, if necessary, and specific examples thereof include the following compounds.

Fatty acids such as stearic acid and behenic acid, fatty acid amides such as stearic acid amide and palmitic acid amide, fatty acid metal salts such as zinc stearate, aluminum stearate, calcium stearate, zinc palmitate and zinc behenate, p-benzyl Biphenyl, terphenyl, triphenylmethane, benzyl p-benzyloxybenzoate, β-benzyloxynaphthalene, phenyl β-naphthoate, phenyl 1-hydroxy-2-naphthoate, methyl 1-hydroxy-2-naphthoate Esters, diphenyl carbonate, dibenzyl terephthalate, dimethyl terephthalate, 1,4-dimethoxynaphthalene, 1,4-diethoxynaphthalene, 1,4-dibenzyloxynaphthalene, 1,2-bis (phenoxy) ethane, 1,2-bi (3-methiphenoxy) ethane, 1,2-bis (4-methylphenoxy) ethane, 1,4-bis (phenoxy) butane, 1,4-bis (phenoxy) -2-butene, 1,2-bis (4-methoxyphenylthio) ethane, dibenzoylmethane, 1,4-bis (phenylthio) butane, 1,4-bis (phenylthio)
-2-butene, 1,2-bis (4-methoxyphenylthio) ethane, 1,3-bis (2-vinyloxyethoxy)
Benzene, 1,4-bis (2-vinyloxyethoxy) benzene, p- (2-vinyloxyethoxy) biphenyl, p-aryloxybiphenyl, p-propargyloxybiphenyl, dibenzoyloxymethane, 1,3-di Benzoyloxypropane, dibenzyl sulfide, 1,
1-diphenylethanol, 1,1-diphenylpropanol, p- (benzyloxy) benzyl alcohol, 1,3
-Diphenoxy-2-propanol, N-octadecylcarbamoyl-p-methoxycarbonylbenzene, N-octadecylcarbamoylbenzene, dibenzyl oxalate, 1,5-bis (p-methoxyphenyloxy) -3
-Oxapentane and the like.

In the case of obtaining a thermosensitive recording material according to the present invention, together with a leuco dye and a developer, if necessary, auxiliary additives commonly used in this type of thermosensitive recording material, such as a filler and a surfactant, are used in combination. can do. In this case, as the filler, for example, other than inorganic fine powder such as calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, surface-treated calcium and silica, etc. Organic fine powders such as urea-formalin resin, methylene / methacrylic acid copolymer, and polystyrene resin. Further, the layer structure may be a single layer or a multilayer, and an over layer, an under layer, and a back layer can be provided as necessary.

The developer in the present invention can also be used as a pressure-sensitive recording material, and a pressure-sensitive recording material using the developer can be easily prepared by a conventionally known method.

〔The invention's effect〕

The recording material of the present invention using the phenolic compound represented by the above general formula (I) or (and) (II) as a color developer has excellent color density and sensitivity, high background whiteness, and storage stability. It is excellent.

〔Example〕

Next, the present invention will be described in more detail by way of examples. All parts and percentages shown below are based on weight.

Examples 1 and 2 and Comparative Examples 1 and 2 The following mixtures were each pulverized in a magnetic ball mill for 2 days to prepare [Solution A], [Solution B] and [Solution C].

[A liquid]

3- (N-methyl-N-cyclohexyl) amino-6
-Methyl-7-anilinofluorane 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts [Solution B] Phenolic compound in Table 1 20 parts 10% aqueous solution of polyvinyl alcohol 20 parts Water 60 parts [Solution C 20 parts of calcium carbonate 20 parts of a 5% aqueous solution of methylcellulose 20 parts of water 60 parts of [solution A] 10 parts, [solution B] 30 parts, [solution C] 30 parts and isobutylene / maleic anhydride copolymer 20% alkali a thermosensitive coloring layer forming liquid by mixing 10 parts of an aqueous solution, which dye attached amount after drying by coating and drying so that 0.5 g / m ² on a high-quality paper having a basis weight of 50 g / m ² a thermosensitive coloring layer After the application, the surface of the layer was calendered so that the surface smoothness became 500 to 600 seconds to prepare a heat-sensitive recording material.

The thermal recording material obtained as described above was printed at a voltage of 13.3 V with a thermal printer of Matsushita Electronic Components Co., Ltd., and the density was measured with a Macbeth densitometer RD-914. Further, the printed portion was left at room temperature for one week, and the occurrence of white powder in the image portion was visually determined. Table 1 shows the above results.

From the results shown in Table 1, it can be seen that the heat-sensitive recording material of the present invention is extremely excellent, having high sensitivity, high background whiteness, and no white powder deposition from the image area.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Haruyoshi Kondo 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (56) References JP-A-62-251184 (JP, A) JP-A Sho 60-42463 (JP, A) JP-A-50-57452 (JP, A) JP-A-2-215581 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) B41M 5/28 -5/34 B41M 5/124-5/165

Claims (1)

(57) [Claims] 1. A recording material utilizing a color-forming reaction between a colorless or light-colored leuco dye and a color developer which forms a color when the leuco dye is brought into contact with the recording material, wherein the general formulas (I) and (II) are used as the color developer. A recording material characterized by using at least one of the phenolic compounds represented by the formula (1). (Wherein R ₁ represents an aryl group or an aralkyl group which may have a substituent, R ₂ represents a divalent saturated or unsaturated hydrocarbon group which may have a substituent, and X represents a lower group. An alkyl group, an alkoxy group, an alkenyl group, or a halogen atom is shown, m represents an integer of 0 to 4, and n represents an integer of 1 to 3, respectively.