JPH05301446A - Recording material - Google Patents

Abstract

PURPOSE:To make the storage stability of a non-image part and an image part excellent, in a recording material using an electron donating leuco dye and an electron acceptive compd., by adding a compd. having a specific structure as the electron acceptive compd. CONSTITUTION:In a recording material using an electron donating leuco dye and an electron acceptive compd., as the electron acceptive compd., at least one compd. represented by formula I (wherein X is H, a halogen atom, a hydroxyl group, a carboxyl group, an alkoxy carbonyl group, an alkyl group, an alkoxy group, an alkyl group, an aryl group, an aralkyl group or a cycloalkyl group, Ar is an arylene group having two or more benzene rings, an arylene group wherein two or more benzene groups are condensed or a bisarylene group connected through a divalent group and R is H, an alkyl group, an aralkyl group or an aryloxyalkyl group) is used. As a result, a recording material excellent in the storage stability of a non-image part and an image part is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material using an electron-donating colorless dye and an electron-accepting compound, such as a pressure-sensitive recording material, a heat-sensitive recording material, and the like, and particularly excellent in color density and color sensitivity. The present invention relates to an image portion and a recording material having excellent storage stability in the image portion.

[0002]

2. Description of the Related Art Recording materials using an electron-donating colorless dye and an electron-accepting compound are pressure-sensitive paper, thermal paper, photosensitive pressure-sensitive paper,
It is already well known as an electrically conductive recording paper and a thermal transfer paper. For example, British Patent 2140449 and US Patent 448.
No. 0052, No. 4436920, Japanese Patent Publication No. 60-239
92, JP-A Nos. 57-179836 and 60-123.
For details, see No. 556 and No. 60-123557.

As a recording material, in recent years, studies have been earnestly conducted to improve characteristics such as (1) color density and color sensitivity (2) storage stability of non-image area and image area. Conventional electron-accepting compounds for an electron-donating colorless dye include bisphenol A, p-hydroxybenzoic acid esters,
Various types such as bis- (4-hydroxyphenyl) sulfone are known, but all have color density, color sensitivity, storage stability of non-image area and image area (weather resistance, chemical resistance, plasticizer resistance). Etc. had some drawbacks. For example,
When bis- (3-phenyl-4-hydroxyphenyl) sulfone was used in a heat-sensitive recording material, the non-image area storability was poor such that the background area was fogged with a marker or a highlighter pen. The present inventors have found that specific compounds are effective in improving these properties.

[0004]

DISCLOSURE OF THE INVENTION The present invention is directed to color density, color sensitivity, storage stability of non-image areas and image areas (weather resistance,
The present invention provides a recording material having good chemical resistance and plasticizer resistance) and satisfying other requirements to be met.

[0005]

The present invention relates to a recording material using an electron-donating colorless dye and an electron-accepting compound, wherein the compound represented by the following general formula (1) is used as the electron-accepting compound. It is a recording material characterized by containing at least one. General formula (1)

[0006]

[Chemical 2]

(In the formula, X is a hydrogen atom, a halogen atom, a hydroxy group, a carboxyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aralkyl group, or a cycloalkyl group, and Ar is a benzene ring. An arylene group having two or more groups, an arylene group in which two or more benzene rings are condensed, or a bisarylene group linked through a divalent group, R is a hydrogen atom, an alkyl group, an aralkyl group, or an aryloxyalkyl group. Represents each group.)

In the general formula (1), the group represented by X is a hydrogen atom, a hydroxy group, a carboxyl group, or a carbon number of 1 to 1.
7 alkoxycarbonyl group, fluorine atom, chlorine atom,
Bromine atom, alkyl group having 1 to 5 carbon atoms, alkoxy group having 1 to 5 carbon atoms, allyl group, aryl group having 7 to 10 carbon atoms, aralkyl group having 7 to 10 carbon atoms, or 5 to 7 carbon atoms
The cycloalkyl group of is preferred.

In the general formula (1), the group represented by Ar is preferably a condensed ring or a divalent group represented by the following general formula (2). General formula (2)

[0010]

[Chemical 3]

(In the formula, Y represents a single bond, an alkylene group having 1 to 10 carbon atoms, a phenylene group, an oxygen atom, a sulfur atom, a carbonyl group or a sulfone group. X represents the same as the above groups.)

In the general formula (1), the group represented by R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom having 7 carbon atoms.
To 20 aralkyl groups or C8-20 aryloxyalkyl groups are preferred.

In the general formula (1), as the group represented by X, a hydrogen atom, a hydroxy group, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a normal propoxycarbonyl group, an isopropoxycarbonyl group,
Normal butyl carbonyl group, isobutyloxy carbonyl group, chlorine atom, methyl group, ethyl group, normal propyl group, isopropyl group, tertiary butyl group, secondary butyl group, methoxy group, ethoxy group, allyl group, phenyl group, benzyl group, Cyclohexyl group, α-
Phenylpropyl group and α-phenylallyl group are preferred.

In the general formula (1), the group represented by Ar is particularly 2,7-naphthylene group, 1,5-naphthylene group,
The anthracenylene group and the group represented by the following general formula (3) are particularly preferable. General formula (3)

[0015]

[Chemical 4]

(Wherein Y is a single bond, a methylene group, an ethylene group, an isopropylidene group, a butylene group, a phenylene group,
It represents an oxygen atom, a sulfur atom, a carbonyl group or a sulfone group. X represents the same as the above-mentioned groups. )

In the general formula (1), as the group represented by R, hydrogen atom, methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, tertiary butyl group, secondary butyl group, isobutyl group are particularly preferable. Group, normal amyl group, isoamyl group, normal hexyl group,
Normal octyl group, benzyl group, paramethylbenzyl group, paraethylbenzyl group, paranormalpropylbenzyl group, paraisopropylbenzyl group, methoxybenzyl group, chlorobenzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, phenoxyethyl group , Methoxyphenoxyethyl group, chlorophenoxyethyl group,
Methylphenoxyethyl group, 1-methyl2-phenoxyethyl group, 1-methyl-2- (methoxyphenoxy) ethyl group, 1-methyl-2- (methylphenoxy) ethyl group, 2-naphthoxyethyl group, 1-naphthoxyethyl group, A 1-methyl-2- (2-naphthoxy) ethyl group is preferred.

Specific examples of the compound represented by formula (1) are shown below, but the present invention is not limited thereto.
Further, the following structural formula also means its hydrate.

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

The melting point of the compound represented by the general formula (1) is
It can be controlled by including water or an organic solvent in the crystal. For example, the compound of specific example (17) usually has a melting point of 195 to 196 ° C., but when 2 molecules of water are added as water of crystallization, it shows a melting point of 100 ° C. Further, when it is used as a heat-sensitive recording material, it shows good image chemical resistance. As the electron-donating colorless dye used in the present invention, conventionally known triphenylmethanephthalide-based compounds, fluoran-based compounds, phenothiazine-based compounds, indolylphthalide-based compounds, leukoauramine-based compounds, rhodamine-lactam-based compounds, Various compounds such as triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds are known.

Specific examples of the phthalides include US Reissued Patent Specification No. 23024 and US Patent Specification No. 3491111.
Nos. 3,491,112, 3,491,116 and 3,509,174, and specific examples of fluoranes are US Pat. Nos. 3,624,107 and 3,627,787.
No. 3641011, No. 3462828, No. 3
681390, 3920510, and 3959.
No. 571, specific examples of spiro dipyrans are US Pat. No. 3971808, and pyridine compounds and pyrazine compounds are US Pat. Nos. 3775424 and 3853.
No. 869, No. 4264318, and specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989. Examples thereof will be given below, but the electron donating colorless dye used in the present invention is not limited to these.

3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3,3-bis (p
-Dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindole -3-yl)
Phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-
Bis (1,2-dimethylindol-3-yl) -6-
Dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide.

3- (2-Ethoxy-4-diethylaminophenyl) -3- (1-normaloctyl-2-methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-Normaloctyl-2-methylindol-3-yl) -4-azaphthalide, 3,3-bis (1-normaloctyl-2)
-Methylindol-3-yl) phthalide, 3,3-bis (2-phenylindol-3-yl) -6-dimethylaminophthalide, 3-p-dimethylaminophenyl-
Triarylmethane dyes such as 3- (1-methylpyrrol-3-yl) -6-dimethylaminophthalide, 4,
4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl-leuco auramine, N-
Diphenylmethane dyes such as 2,4,5-trichlorophenylleuco auramine, and thiazine dyes such as benzoyl leuco methylene blue and p-nitrobenzoyl leuco methylene blue.

3-methyl-spiro-dinaphthopyran, 3
-Ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho (6'-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran and other spiro dyes , Rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (o-chloroanilino) lactam and the like. 3-dimethylamino-7-methoxyfluorane, 3-methoxy-6-diethylaminofluorane, 3
-Diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3- (N- Ethyl-p-toluidino) -7-methylfluorane, 3-diethylamino-7-N-acetyl-N-methylaminofluorane, 3-diethylamino-7-N-methylaminofluorane.

3-Diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-N-methyl-
N-benzylaminofluorane, 3-diethylamino-
7-N-chloroethyl-N-methylaminofluorane,
3-diethylamino-7-N-diethylaminofluorane, 2-phenylamino-3-methyl-6- (N-ethyl-p-toluidino) fluorane, 2- (p-toluidino) -3-methyl-6- (N -Ethyl-p-toluidino) fluorane, 2-anilino-3-methyl-6-diethylaminofluorane.

2-anilino-3-methyl-6-dibutylaminofluorane, 2- (2-carbomethoxy-phenylamino) -6-diethylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-) N-isoamylamino) fluorane, 2-anilino-3-methyl-6-
(N-cyclohexyl-N-methylamino) aminofluorane, 2-anilino-3-methyl-6-pyrrolidinofluorane, 2-anilino-3-methyl-6-piperidinoaminofluorane, 3-diethylamino- 6-methyl-
7-xylidinofluoran.

2- (o-chlorophenylamino) -6-
Diethylaminofluorane, 2- (o-chlorophenylamino) -6-dibutylaminofluorane, 2-anilino-3-methyl-6- (N-ethyl-N-tetrahydrofurfurylamino) fluorane, 2-anilino-3- Methyl-6- (N-methyl-N-n-propylamino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-N-isobutylamino) fluorane.

2-anilino-3-methyl-6- (N-methyl-Nn-hexylamino) fluorane, 2-anilino-3-methyl-6- (N-ethyl-Nn-hexylamino) fluorane , 2-anilino-3-methyl-6
-(N-ethyl-N-cyclopentylamino) fluorane, 2-anilino-3-methyl-6-N-ethyl-N-
[3- (p-Ethylphenoxy) propyl] aminofluorane, 2-anilino-3-methyl-6-N-propyl-N- [3- (p-methoxyphenoxy) propyl] aminofluorane, 2-anilino- 3-methyl-6-N-
Propyl-N-3-ethoxypropylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-
Fluorane dyes such as 3-ethoxypropylaminofluorane.

The electron-donating colorless dye used in the present invention is, of course, not limited to these dyes, and two or more dyes may be used in combination. The electron-accepting compound according to the present invention is a conventionally known phenol derivative, salicylic acid derivative, metal salt of aromatic carboxylic acid,
It can be used in combination with compounds such as acid clay, bentonite, novolac resin, metal-treated novolac resin, and metal complex. Examples of these are JP-B-40-9309 and 45-14039.
No. 56-140483 and 48-5151.
0, 57-210886, 58-87089.
No. 59-112286, No. 60-76795, No. 61-95988, and the like.

Examples of these include bisphenol A, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) heptane, 1,1-bis (4- Hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)
-2-ethylhexane, 1,1-bis (3-chloro-4)
-Hydroxyphenyl) -2-ethylbutane, bis (3
-Allyl-4-hydroxyphenyl) sulfone, 1,7
-Bis (4-hydroxyphenylthio) -3,5-dioxaheptane.

(4-hydroxyphenyl)-(4-isopropoxyphenyl) sulfone, 4-hydroxybenzoic acid benzyl ester, 2,4-dihydroxybenzoic acid-
β-phenoxyethyl ester, 2,4-dihydroxybenzoic acid-α-methyl-β- (3-methoxyphenoxy) ethyl ester, 1,3-bis (4-hydroxyphenyl) propane, 2- (2,4-dihydroxy) Examples thereof include phenyl) -2-phenylpropane and zinc 3,5-bis (α-methylbenzyl) salicylate.

When the recording material of the present invention is used for thermal paper, it is disclosed in JP-A-62-114989 and JP-A-62-244.
It takes the form as described in the specification of 883. Specifically, the electron-donating colorless dye and the electron-accepting compound are pulverized and dispersed in a dispersion medium to a particle size of 10 μm or less, preferably 3 μm or less. The dispersion medium is generally 0.5
A water-soluble polymer aqueous solution having a concentration of about 10 to 10% is used, and dispersion is performed by a ball mill, a sand mill, a horizontal sand mill,
It is performed using an attritor, colloidal mill, or the like.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably 1:10 to 1: 1 by weight, more preferably 1: 5 to 2: 3. At that time, a thermofusible substance may be contained in the thermosensitive coloring layer in order to improve the thermal response. Typical examples of the heat-fusible substance include aromatic ethers, thioethers, esters and / or aliphatic amides or ureides.

Examples of these are disclosed in JP-A-58-57989,
58-87094, 61-58789, 62.
-109681, 62-2132674, 63-
No. 151478, No. 63-235961, Japanese Patent Application No. 1-
Nos. 4447 and 1-307070.

Examples of heat-fusible substances are phenethyl biphenyl ether, benzyloxynaphthalene, benzyl biphenyl, 1,2-diphenoxyethane, 1,2-
Di-m-tolyloxyethane, 1-phenoxy-2-p
-Methoxyphenoxyethane, 1-p-methoxyphenoxy-2-o-chlorophenoxyethane, 1,2-di-
p-fluorophenoxyethane, 1,3-di-p-methoxyphenoxypropane, 1,2-di-p-methoxyphenoxypropane, 1-phenoxy-2-p-methoxyphenoxypropane, 1-p-methoxyphenoxyethoxy- 2-p-methoxyphenoxyethane, 1,2-di-p-methoxyphenylthioethane, p-methoxybenzyloxytolylmethane, (4-methoxybenzyloxy)-(3-methyl-4-chlorophenyl) methane, p
-Chlorobenzyloxy-p-ethoxyphenylmethane and the like.

These are used at the same time as the electron-donating colorless dye or at the same time as being finely dispersed at the same time as the electron-accepting compound. The amount of these used is 20% or more and 30 with respect to the electron-accepting compound.
It is added in a weight ratio of 0% or less, especially 40% or more and 150%
The following are preferred. If necessary, additives are added to the coating liquid thus obtained in order to meet various requirements. As an example of the additive, an oil absorbing substance such as an inorganic pigment or polyurea filler is dispersed in a binder in order to prevent the recording head from being soiled at the time of recording, which further enhances the releasability of the head. For fatty acids,
Metal soap or the like is added. Therefore, in general, in addition to the electron-donating colorless dyes and electron-donating compounds that are directly used for color development, heat-fusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers, defoamers, conductive agents, fluorescent dyes, surface active agents An additive such as an agent is applied on the support to form a recording material.

Further, if necessary, a protective layer may be provided on the surface of the thermosensitive recording. Two or more protective layers may be laminated if necessary. A coating liquid similar to the protective layer may be applied to the back surface for the purpose of correcting the curl balance of the support or improving the chemical resistance from the back surface. An adhesive may be applied to the back surface, and release paper may be further combined to form a label.

Usually, the electron-donating colorless dye and the electron-accepting compound are dispersed and applied in a binder. As the binder, a water-soluble binder is generally used, and polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride. Examples thereof include salicylic acid copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein, gelatin and the like. Further, for the purpose of imparting water resistance to these binders, a water resistant agent is added, or a hydrophobic polymer emulsion, specifically,
Styrene-butadiene rubber latex and acrylic resin emulsion can also be added.

The obtained heat-sensitive coating liquid is applied to high-quality paper, high-quality paper having an undercoat layer, synthetic paper, plastic film and the like. At this time, it is particularly preferable to use a support having a smoothness of 500 seconds or more, particularly 800 seconds or more as defined by JIS-8119, from the viewpoint of dot reproducibility. As the pigment in the case of providing an undercoat layer containing a pigment as a main component on the support, all general organic or inorganic pigments can be used, but in particular,
Oil absorption specified by JIS-K5101 is 40cc / 10
It is preferably 0 g or more, and specifically calcium carbonate, barium sulfate, titanium oxide, talc, wax stone, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, urea formalin resin powder, polyethylene resin powder and the like. Can be mentioned. When these pigments are applied to a support, the amount of pigment is 2 g / m ² or more, preferably 4 g / m ^2.
m ² or more.

As the binder used in the undercoat layer,
Examples thereof include water-soluble polymers and water-soluble binders, and the binders may be used alone or in combination of two or more. As the water-soluble polymer, methyl cellulose, carboxymethyl cellulose, hydroxytyl cellulose, starches, gelatin, gum arabic, casein, styrene-maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, Examples thereof include polyvinyl alcohol and polyacrylamide.

As the water-soluble binder, synthetic rubber latex or synthetic resin emulsion is generally used.
Examples thereof include styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. The amount of binder used is 3 for pigments.
-100% by weight, preferably 5-50% by weight. Wax, decoloring inhibitor, surfactant, etc. may be added to the undercoat layer.

Examples of the pigment used as the additive of the present invention include kaolin, calcined kaolin, talc, wax, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, lithopone, amorphous silica and colloidal. Examples thereof include silica, calcined stone, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, microballoons, urea-formalin filler, polyester particles, and cellulose filler.

Examples of the metal soap include higher fatty acid polyvalent metal salts such as zinc stearate, aluminum stearate, calcium stearate and zinc oleate. Further, in the present invention, it is preferable to use a wax having a melting point of 40 to 120 ° C. together from the viewpoint of the head matching property with respect to the facsimile. The wax having a melting point of 40 to 120 ° C. is preferably paraffin wax, polyethylene wax, carnauba wax, microcrystalline wax, candelia wax, montan wax, and fatty acid amide wax, and particularly, paraffin having a melting point of 50 to 100 ° C. Wax, montan wax and methylol stearamide are preferred. The amount of wax used is 5 to 200% by weight, preferably 20 to 150% by weight of the electron-donating colorless dye.

As the hindered phenol compound, a phenol derivative in which one or more of at least 2-position or 6-position is substituted with a branched alkyl group is preferable. UV absorbers include cinnamic acid derivatives, benzophenone derivatives,
Benzotriazole phenol derivatives such as butyl α-cyano-β-phenylcinnamate, o-benzotriazole phenol, o-benzotriazole-p-chlorophenol, o-benzotriazole-2,4-di-t-
Butylphenol, o-benzotriazolyl-2,4-
There are di-t-octylphenol and the like.

As the waterproofing agent, N-methylol urea,
Water-soluble initial condensates such as N-methylol melamine and urea-formalin, dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic crosslinking agents such as boric acid and borax,
Examples include blending heat treatment of polyacrylic acid, methyl vinyl ether-maleic acid copolymer, isobutylene-maleic anhydride copolymer and the like. Materials used for the protective layer include polyvinyl alcohol, carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer,
Silicon modified polyvinyl alcohol, starch, modified starch, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, gelatins, gum arabic, casein, styrene-maleic acid copolymer hydrolyzate, styrene-maleic acid copolymer half ester hydrolyzate,
Isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivative, polyvinylpyrrolidone, water-soluble polymers such as sodium polystyrene sulfonate and sodium alginate, and styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene Water-insoluble polymers such as rubber latex and vinyl acetate emulsion are used.

Further, pigments, metal soaps, waxes, water-proofing agents and the like may be added to the protective layer for the purpose of improving matching with the thermal head. Further, when the protective layer is coated on the thermosensitive coloring layer, a surfactant may be added to obtain a uniform protective layer. As the surfactant, a sulfosuccinic acid-based alkali metal salt or a fluorine-containing surfactant is used. Specifically, sodium salts such as di- (n-hexyl) sulfosuccinic acid and di- (2-ethylhexyl) sulfosuccinic acid, ammonium salts and the like are preferable, but anionic surfactants are effective.

When used for pressure sensitive paper, US Pat.
No. 05470, No. 25054571, No. 250548
No. 9, No. 2548366, No. 2712507, No. 2
No. 730456, No. 2730457, No. 310340
It can take various forms as described in prior patents such as No. 4, No. 3418250 and No. 4010038. Most commonly it consists of at least a pair of sheets containing separately an electron donating colorless dye and an electron accepting compound.

Regarding the method of manufacturing capsules, US Pat.
No. 800457, No. 2800458, a method utilizing coacervation of hydrophilic colloid sol, British Patent Nos. 867797, 950443, and 9
89264, 1091076 and the like.

Generally, an electron-donating colorless dye is used alone or as a mixture, and a synthetic oil such as a solvent (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, chlorinated paraffin, etc .; cotton oil,
A color-developing sheet by dissolving it in vegetable oil such as castor oil; animal oil; mineral oil or a mixed oil thereof, including it in microcapsules, and coating it on paper, high-quality paper, plastic sheet, resin-coated paper, etc. To get

Further, the electron-accepting compound and, if necessary, additives are dispersed alone or in a mixture in a binder such as styrene-butadiene latex or polyvinyl alcohol, and together with the pigment, paper, plastic sheet, resin coated paper, etc. A color developer sheet is obtained by applying to the support.

As the binder, it is preferable to use a carboxy-modified styrene-butadiene latex in combination with a water-soluble polymer from the viewpoint of light resistance and water resistance. Further, as the pigment, it is preferable to use calcium carbonate having an average particle size of 5.0 μm or less in an amount of 60% by weight or more based on all pigments in terms of color developing ability.

The use amount of the electron-donating colorless dye and the electron-accepting compound depends on the desired coating thickness, the form of the pressure-sensitive recording paper, the capsule manufacturing method, and other conditions, and may be appropriately selected according to the conditions. It is easy for a person skilled in the art to determine this usage amount.

[0060]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited thereto. In Examples, unless otherwise specified, weight% is expressed.

Example 1 2-anilino-3-methyl- which is an electron-donating colorless dye
6-N-methyl-N-normal propylaminofluorane, the compound of the specific example (1) which is an electron-accepting compound, and 2-naphthyl-benzyl ether which is a heat-fusible compound 20 g each and 100 g of 5% polyvinyl alcohol A (Kuraray PVA105) aqueous solution was dispersed in a ball mill for a whole day and night to have a volume average particle diameter of 3 μm. On the other hand, 80 g of calcined kaolin (Anisilex-93) was dispersed with a homogenizer together with 160 g of a 0.5% solution of sodium hexametaphosphate.

Each dispersion was dispersed as described above, and electron-donated.
Colorless dye dispersion 5 g Electron-accepting compound dispersion 10 g,
Diaryloxyalkane compound dispersion 10 g, calcined oil
Mix Orin dispersion at a ratio of 22g and add stearin.
Zinc acid emulsion 4 g and 2% (2-ethylhexyl
5) Add 5 g of an aqueous solution of sodium sulfosuccinate
I got a coating liquid. Weigh this coating liquid at 50 g / m²On fine paper
Dry coating amount is 6g / m ²With a wire bar
The coated paper was obtained by applying cloth and calendering.

The coated paper obtained as described above was used as a thermal head (KLT-216-8MPD, manufactured by Kyocera Corp.).
1) and with a thermal printing experimental apparatus having a pressure roll of 100 kg / cm ² immediately before the head, a head voltage of 24
While using a pressure roll under the conditions of V and a pulse cycle of 10 ms, printing was performed with a pulse width of 1.0 and the print density was measured with a Macbeth reflection densitometer RD-918. The color density was 1.38. In addition, the image portion that developed black with a fluorescent pen or the like was not erased at all, and the non-image portion on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-2 Example-2 except that the compound of Specific Example (1) which is the electron-accepting compound of Example-1 was replaced with the compound of Specific Example (2).
A coated paper was obtained in the same manner as in 1. When color was developed in the same manner as in Example-1, the color density was 1.35. In addition, the image portion that developed black with a fluorescent pen or the like was not erased at all, and the non-image portion on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-3 Example-3 was repeated except that the compound of Specific Example (1) which was the electron-accepting compound of Example-1 was replaced with the compound of Specific Example (3).
A coated paper was obtained in the same manner as in 1. When color was developed in the same manner as in Example-1, the color density was 1.36. In addition, the image portion that developed black with a fluorescent pen or the like was not erased at all, and the non-image portion on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-4 Coated paper in the same manner as in Example-1 except that the compound of Specific Example (1) which is the electron-accepting compound of Example-1 was replaced with the compound of Specific Example (17). Got When color was developed in the same manner as in Example-1, the color density was 1.34. Also,
The image area that developed black with a fluorescent pen was not erased at all, and the non-image area on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-5 A coated paper in the same manner as in Example-1 except that the compound of Specific Example (1) which is the electron-accepting compound of Example-1 was replaced with the compound of Specific Example (13). Got When color was developed in the same manner as in Example-1, the color density was 1.34. Also,
The image area that developed black with a fluorescent pen was not erased at all, and the non-image area on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-6 A coated paper was prepared in the same manner as in Example-1 except that the compound of Specific Example (1) which was an electron-accepting compound of Example-1 was replaced with the compound of Specific Example (25). Got When color was developed in the same manner as in Example-1, the color density was 1.33. Also,
The image area that developed black with a highlighter pen was not erased at all, and the non-image area on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-7 Coated paper in the same manner as in Example-1 except that the compound of Specific Example (1) which is the electron-accepting compound of Example-1 was replaced with the compound of Specific Example (20). Got When color was developed in the same manner as in Example-1, the color density was 1.32. Also,
The image area that developed black with a highlighter pen was not erased at all, and the non-image area on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-8 Coated paper in the same manner as in Example-1 except that the compound of Specific Example (1) which is the electron-accepting compound of Example-1 was replaced with the compound of Specific Example (21). Got When color was developed in the same manner as in Example-1, the color density was 1.33. Also,
The image area that developed black with a highlighter pen was not erased at all, and the non-image area on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-9 2-anilino-3 which is the electron-donating compound of Example-1
A coated paper was prepared in the same manner as in Example 1 except that 2-anilino-3-methyl-6-N-dibutylaminofluorane was used instead of -methyl-6-N-methyl-N-normalpropylaminofluorane. Obtained. When color was developed in the same manner as in Example-1, the color density was 1.32. In addition, the image portion that developed black with a fluorescent pen or the like was not erased at all, and the non-image portion on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Example-10 1) Preparation of Capsule Sheet Containing Electron Donating Colorless Dye 5 parts of polyvinylbenzenesulfonic acid partial sodium salt (National Starch VERSA, TL500) are dissolved in 95 parts of water. An aqueous sodium hydroxide solution was added to this to adjust the pH to 4.0. On the other hand, as an electron-donating colorless dye, 2-anilino-3-methyl-6-N-methyl-N-
100 parts of diisopropylnaphthalene in which 4.5% of normal propylaminofluorane was dissolved was used as a 5% aqueous solution of a partial sodium salt of polyvinylbenzenesulfonic acid 10
The emulsion was dispersed in 0 part to obtain an emulsion having a particle size of 4.0 μ in diameter.

Separately, 6 parts of melamine, 11 parts of 37% by weight formaldehyde aqueous solution, and 30 parts of water were heated and stirred at 60 ° C. to obtain a transparent aqueous solution of melamine formaldehyde prepolymer. This aqueous solution was mixed with the above emulsion. While stirring, the pH was adjusted to 6.0 with a phosphoric acid aqueous solution, the liquid temperature was raised to 65 ° C., and stirring was continued for 6 hours. The capsule solution was cooled to room temperature and adjusted to pH 9.0 with an aqueous sodium hydroxide solution.

To this dispersion, 200 parts of a 10% by weight aqueous solution of polyvinyl alcohol and 50 parts of starch particles were added, and water was added to obtain a solid component concentration of 2 in the microcapsule dispersion.
A 0% solution was prepared. This coating solution was applied to an original paper of 50 g / m ^{2 with} an air knife coater so that a solid content of 5 g / m ² was applied and dried to obtain an electron-donating colorless dye-containing capsule sheet.

2) Preparation of electron-accepting compound sheet 14 parts of the compound of the specific example (17), 80 parts of calcium carbonate
 , Zinc oxide 20 parts, sodium hexametaphosphate 1 part
And a water dispersion of 200 parts with a sand grinder
10% was added to this dispersion which was dispersed to have an average particle size of 3μ.
100 parts of PVA aqueous solution and carboxy modified SBR latte
X 10 parts (as solid content) was added, and the solid content concentration was
Water was added to 20% to obtain a coating liquid. Apply this coating solution to 5
0 g / m ²5.0g / m on the base paper²Solids of
Electron acceptability by coating with an air knife coater and drying
A compound sheet was obtained.

The surface of the capsule sheet containing the electron-donating colorless dye is superposed on the electron-accepting compound sheet, and 400 kg / cm 2.
^When a load of ² was applied for color development, the color hue was dark black. In addition, the image portion that developed black with a fluorescent pen or the like was not erased at all, and the other performances (weather resistance, plasticizer resistance, etc.) also showed good performance.

Example-11 The compound of Specific Example (17) (melting point 195 to 196 ° C.), which is the electron-accepting compound of Example-4, was added to the compound of Specific Example (17) by crystallization water (melting point 100 ° C.). A coated paper was obtained in the same manner as in Example 4 except that When color was developed in the same manner as in Example 4, the color density was 1.24. In addition, the image portion that developed black with a fluorescent pen or the like was not erased at all, and the non-image portion on a white background did not develop black (fog due to the solvent). Regarding other resistances (weather resistance, plasticizer resistance, etc.), good performance was exhibited and no fog in the non-image area, discoloration, and discoloration of the image area were not shown.

Comparative Example-1 Example 1 was repeated except that the compound of the specific example (1) which was the electron-accepting compound of Example-1 was replaced with 1,3-bis (4-hydroxyphenylsulfonylmethyl) benzene. A coated paper was obtained in the same manner as in 1. When color was developed in the same manner as in Example-1, the color density was 1.33. When a fluorescent pen was applied in the same manner as in Example-1, the image area was not decolored, but the non-image area on a white background was colored black and was fogged by a solvent.

Comparative Example-2 Except that the compound of the specific example (1) which is the electron-accepting compound of Example-1 was replaced with 1,3-bis [3- (4-hydroxyphenylsulfonyl) propoxy] benzene. A coated paper was obtained in the same manner as in Example-1. When color was developed in the same manner as in Example-1, the color density was 1.35. When a fluorescent pen was applied in the same manner as in Example-1, the image area was decolored, the non-image area on a white background was also colored black, and it was fogged by a solvent.

[0080]

As is clear from the results of the "Examples", the recording material of the present invention is a recording material having high sensitivity and excellent weather resistance and chemical resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shunsaku Higashi 200 Onakazato, Fujinomiya City, Shizuoka Prefecture Fuji Photo Film Co., Ltd.

Claims (1)

[Claims] 1. A recording material using an electron-donating colorless dye and an electron-accepting compound, which contains at least one compound represented by the following general formula (1) as an electron-accepting compound. And recording material. General formula (1) (In the formula, X is a hydrogen atom, a halogen atom, a hydroxy group,
A carboxyl group, an alkoxycarbonyl group, an alkyl group, an alkoxy group, an allyl group, an aryl group, an aralkyl group, or a cycloalkyl group, and Ar is an arylene group having two or more benzene rings and an arylene in which two or more benzene rings are condensed. R is a hydrogen atom, an alkyl group, an aralkyl group, or an aryloxyalkyl group, each of which is a bisarylene group linked through a group or a divalent group. )