JPS6277980A - Recording material - Google Patents

Abstract

PURPOSE:To provide a fluoran derivative excellent as a dye precursor for a black color forming recording material, by incorporating a fluoran derivative having a diarylaminophenyloxy residue as a substituent group. CONSTITUTION:This recording material comprises a fluoran derivative having a diarylaminophenyloxy residue as a substituent group. Among such fluoran derivatives, one that has a diarylaminophenyloxyalkylamino group as a substituent group at 2- or 1- and 6-position is preferred. The fluoran derivative is a colorless or light-colored crystal, is highly soluble in organic solvents, and rapidly forms a black color on making contact with an electron-acceptive substance. A general method of producing a thermal recording paper employing a dye precursor comprises mixing the dye precursor, the electron-acceptive substance and a heat-fusible substance, in a sufficiently finely ground state, into a liquid obtained by dissolving or dispersing a binder in a solvent or dispersant, and applying the resultant liquid material to a base such as a paper, a plastic sheet and a resin-coated paper, followed by drying.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application of the Invention The present invention relates to a recording material containing a novel fluoran derivative.

The fluoran compound according to the present invention is an extremely useful compound particularly as a dye precursor for single-layer recording materials such as pressure-sensitive paper, thermal paper, and electrically conductive thermal paper.

It is a compound that can be applied to photosensitive recording sheets, ultrasonic recording sheets, electron beam recording sheets, electrostatic recording sheets, ball inks, crayons, etc.

<Prior Art> The use of various fluorane derivatives as dye precursors for all pressure-sensitive or thermal papers is already well known and is described in US Pat. λj, Ko 32 specification, West German Patent Publication (OLS) No. 29.2zλ.

Specification No. 127, Special Publication Sho J-/-3♂2≠! No. specification,
British patent λ/'tO≠≠R, US patent≠, HirofO, 0
No. 32, U.S. Patent Publication, ≠ 36,220, Special Publication Show 1.0
-23.922, Tokukai Sho! 7-/7ri,za36,%
JP-A-60-/23.114, JP-A-60-/λj,
No. 117, etc.

However, these known fluoran derivatives have drawbacks such as the fluoran compound itself being unstable in the atmosphere and the color images produced therefrom having poor fastness to light, moisture, etc.

<Objective of the Invention> Accordingly, an object of the present invention is to provide all novel fluorane derivatives which are particularly excellent as dye precursors for black color recording materials.

<Structure of the Invention> The object of the present invention has been achieved by a recording material containing a fluoran derivative having diarylaminophenyloxy residue as a substituent.

Among the fluoran derivatives having a diarylaminophenyloxy residue as a substituent of the present invention, the diarylaminophenyloxyalkylamino group at the 2nd or l and 2nd positions
Those having it as a substituent at the position are preferred.

Among these, those represented by the following general formula (1) or (II) are particularly preferred.

R1 and R5 in the above general formulas (1) and (I[) are,
An alkyl group, cycloalkyl group, aralkyl group, or aryl group IRz, which may be the same or different and may be substituted with a halogen atom, an alkoxy group, an aryloxy group, or a heterocycle, is a hydrogen atom, an alkyl group, an alkoxy group , aryl group or halogen atom gold, R3 and R4 may be the same or different and may be substituted with hydrogen atom, halogen atom, alkoxy group, aryloxy group or heterocycle, alkyl group, alkyl group or halogen atom , an alkoxy group, an aryloxy group, a cyano group, a nitro group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a substituted amino group, an alkoxycarbonyl group, or an aryl group that may be substituted with an alkoxysulfonyl group. and Ar' may be the same or different, and each group t-1z, z' may be a hydrogen atom, an alkoxy group, an aryloxy group or an atom, n represents an integer from / to j, rndO or/.

In the above general formulas (1) and (II), among the substituents represented by R1 and R5, a chlorine atom, a fluorine atom, an alkoxy group, an aryloxy group, a pyridyl group, a tetrahydrofuryl group, a pyridine-substituted alkoxy group, or a tetrahydrofurfuryl group. Number of carbon atoms that may be substituted with oxy group/-
It is an alkyl group having j to 7 carbon atoms, a cycloalkyl group having j to 7 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, and an alkyl group having 6 to 7 carbon atoms which may be substituted with a chlorine atom, a fluorine atom, an alkyl group, or an alkoxy group. 12 aryl groups are preferred. Among the substituents represented by R2, a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, an aryl group having 6 to 2 carbon atoms, and a chlorine atom are preferred. Among the substituents represented by R3 and R4, even if substituted with a hydrogen atom, a chlorine atom, a fluorine atom, an alkoxy group, an aryloxy group, a pyridyl group, a tetrahydrofuryl group, a pyridine-substituted alkoxy group, or a tetrahydrofuryloxy group Good number of carbon atoms/~l? alkyl groups having 7 to 12 carbon atoms, chlorine atoms, fluorine atoms, alkoxy groups, aryloxy groups, cyano groups, nitro groups, acyl groups, sulfonyl groups, carbamoyl groups, sulfamoyl groups, substituted amine 7 groups , an aryl group having 6 to 2 carbon atoms which may be substituted with an alkoxycarbonyl group or an alkoxysulfonyl group is preferred. Among the substituents represented by Ar and Ar', an aryl group having 6 to 10 carbon atoms which may be substituted with a chlorine atom, an alkyl group, an alkoxy group or an acyl group is preferred. Among the substituents represented by 2, hydrogen atoms, number of carbon atoms l
-B is preferably an alkoxy group, an aryloxy group having 6 to 10 carbon atoms, a chlorine atom or a fluorine atom.

The fluorane derivative according to the present invention has the advantage of being colorless to light-colored crystals, having high solubility in organic solvents, and rapidly developing a black color when it comes into contact with an electron-accepting substance. The developed dye is significantly more stable than dyes produced from existing color formers, and hardly ever discolors or fades even when exposed to light, heat, or humidification for long periods of time, making it especially advantageous in terms of long-term preservation of records. . In addition, the coloring agent has excellent stability and does not deteriorate or discolor even after long-term storage.
It has sufficient coloring ability and has near-ideal performance as a coloring agent for recording materials such as pressure-sensitive paper and thermal paper.

Representative examples of the fluoran derivatives according to the present invention include the following compounds.

1) 2-anilino-3-methyl-A-N-ethyl-N-
β-m-diphenylaminophenoxyetheraminofluorane 2) 2-anilino-3-chloro-+-N-ethyl-N-
β-m-diphenylaminophenoxyethylaminofluorane 3) 2-anilino-3-ethoxy-4-N-butyl-N
-β-m-diphenylaminophenoxyethylaminofluorane 4)2-)Siidino-3-chloroA-N-ethyl-N
-β-p-diphenylaminophenoxyethylaminofluorane 5) λ-0-chloroanilino a-N-isoamyl-N
-β-m-diphenylaminophenoxyethylaminofluorane 6) 2-anilino-3-methyl-+-H-γ-m-diphenylaminophenoxyaminofluorane 7) 2-anilino-3-methyl-4-N- Ethyl-N-
β-m-diphenylaminophenoxyethylamino-j
' -methoxyfluorane8) 2-anilino-3-chloro-a-N-ethel-N-
β-m-diphenylaminophenoxyethylamino-j
'-Phenoxyfluorane9) Co-β-m-diphenylaminophenoxyethylamine-3-chloro-6-dinithylaminofluorane10) 2-β-m-diphenylaminophenoxydiethylamine-3-chloro-4-N-ethyl -N-Amylaminofluoran/11) 2-β-m-diphenylaminophenoxyethylamino-3-methyl-&-N-ethyl-N-tetrahydrofur 7-rifaminofluorane 12) 2-β-m-diphenyl Aminophenoxyethylamine-3-chloro-j-N-ethyl-N-β-pyridyl (2) Ethylaminofluorane 13) 2-β-m-diphenylaminophenoxyethylamino-3-chloro-6-dinitylamine! '-Methoxyfluorane and the like can be used alone, in combination, or in combination with other color formers.

<Method for Synthesizing Fluoran Compound> Next, a method for synthesizing the fluoran derivative according to the present invention will be described.

The fluoran derivative according to the present invention can be synthesized by various methods, but the following three are typical synthesis methods.

Synthesis method 1: A condensation reaction of 2-(2-hydroxy-Hiro-diaryaminophenoxyalkyl-substituted aminobenzoylbenzoic acid, a Hiro-alkoxyaniline derivative, and the presence of a Kl catalyst).

Synthesis method 2: A condensation reaction of 2-(2-hydroxy-Hiro-substituted aminobenzoyl)benzoic acid and a Hiro-diarylaminophenyloxyalkyl-substituted amine phenol derivative in the presence of an acid catalyst.

Synthesis method 3: 2-Amino-4-@substituted aminofluorane and diarylaminophenyloxyalkyl halide or sulfone It are reacted in the presence of a solvent and/or additives as necessary to add a substituent to the 2-position amine group. What to introduce.

etc.

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

Pressure-sensitive paper using the dye precursor of the present invention is disclosed in US Pat.
ri Oj, 1A70, same λ,! 01. ≠No. 71, No. 2
, 301, ≠t, same λ, j≠r.

JTT No., No. 772.607, No. 730, No. 730, No. 2,730. Hiroj No. 7, same No. 7! , 11/r
, No. 260, etc., it can take various forms. That is, the synthesis of solvents (alkylated naphthalene, alkylated diphenyl, styrene dimer, diphenylalkane, alkylated terphenyl, chlorinated) ξ roughin, etc. using the above dye precursors alone or in combination, or together with other dye precursors. Oils: vegetable oils such as soybean oil and castor oil; animal oils: mineral oils; mixtures thereof, etc.) and dispersed in a binder or contained in microcapsules, and then processed into paper, plastic sheets, resins. It is obtained by applying it to a support such as coated paper.

The dye precursor of the present invention particularly has the advantage of being soluble in the above-mentioned solvents at high concentrations.

The amount of the dye precursor to be used varies depending on the desired coating thickness, the form of the pressure-sensitive paper, the capsule manufacturing method, and other conditions, and may be appropriately selected depending on the conditions. When a dye precursor is encapsulated in a capsule, coacervation of a hydrophilic colloid sol as described in U.S. Pat. Specification No. 147゜727, same No. 9μ
The interfacial polymerization methods described in Specification No. 3, No. 1.09/, and No. 076 can be used.

Next, a general method for producing thermal paper using the dye precursor of the present invention will be described.

The binder is dissolved or dispersed in a dispersion medium, and the dye precursor, electron-accepting substance, and thermofusible substance (used when the dye precursor or electron-accepting substance does not melt at the desired temperature) It can be obtained by thoroughly grinding and mixing the mixture, applying it to a support such as paper, plastic sheet, resin-coated paper, etc. and drying it. When preparing a liquid mixture, all the components may be mixed and pulverized simultaneously from the beginning, or they may be combined in appropriate combinations, pulverized and dispersed separately, and then mixed.

7- The coating liquid may be incorporated into the support.

Furthermore, an opacifying agent may be added and mixed during mixing.

The amounts of each component constituting the thermal paper are: 7 to 2 parts by weight of the dye precursor, -4 parts by weight of the electron-accepting substance, and 3 to 3 parts of the thermofusible substance.
0] i parts, pigment 0 to 71 parts by weight, binder 7 to 75 parts
parts by weight and 20 to 300 parts by weight of the dispersion medium (solvent).

As the dye precursor, one or more of the fluoran R conductors of the present invention may be used in combination, or a compound known as a coloring agent for pressure-sensitive paper such as crystal violet lactone or a fluoran derivative may be used with the fluoran derivative of the present invention. They may be used in combination. Among the electron-accepting substances mentioned at the beginning of the text, M organic acids or metal salts thereof are particularly preferred.

Water is most desirable as the dispersion medium (solvent).

Examples of binders used in the present invention include styrene-butadiene copolymers, alkyd resins, acrylamide copolymers, vinyl chloride-vinyl acetate copolymers, styrene-maleic anhydride copolymers, synthetic rubbers, gum arabic, polyvinyl alcohol, and hydroxyethyl cellulose. You can mention many things.

Particularly in relation to the dispersion medium (solvent), water-soluble binders such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, and carboxymethyl cellulose are desirable.

The thermofusible substances include erucic acid, stearic acid, behenic acid, nilumitenic acid, stearamide, behenic acid amide, stearanilide, stearic acid toluide, N-myristoyl-p-anisidine, N-myristoyl-p-anisidine, N-myristoyl-p-anisidine,
-myristoyl-p-phenetidine, l-methoxycarbonyl-≠-N-stearyllupamoylbenzene,
N-octadecylurea, N-hexadecylurea, N
, N'-cytotecylurea, phenylcarbamoyloxydodecane, p-t-butylphenolphenoxyacetate, p-phenylphenol-p-chlorophenoxyacetate, <z, 4! ' -isopropylidene bismethoxybenzene, β-phenylethyl-p-phenyl phenyl ether, λ-p-chlorobenzyloxynaphthalene, -1penzyloxynaphthalene, l-benzyloxynaphthalene, 2-phenoxyacetyloxynaphthalene/, Phthalic acid diphenyl ester, /-hydroxy-ninaphthoic acid phenyl ester, nibenzoyloxina 7-talene, p-benzyloxybenzoic acid hensyl ester, hydroquinone acetate, etc. are used.

These substances are colorless solids at room temperature, and have a sharp melting point at temperatures suitable for reproduction heating temperatures, that is, around 70 to 600C! It is a substance that These are substances that dissolve at least one, preferably both, of the dye premonomer and the electron-accepting substance in a molten state.

In order to fully manufacture the electrically conductive thermal paper using the dye precursor sound of the present invention, JP-A-2007-100000 is disclosed.
The method disclosed in can be used as a reference.

That is, a conductive substance, a dye precursor, an electron-accepting substance, and a binder are all suspended or dispersed in a dispersion medium such as water, and the conductive substance is coated on a support such as paper. It can be obtained by coating on a support to form a conductive layer, and then coating thereon with a dye precursor and an electron-accepting substance, all binders, dispersed in water or the like. The temperature at which both the dye precursor and the electron-accepting substance are preferred (generally 70~/JO'
If it does not melt in C), a thermofusible substance that melts at a preferred temperature and dissolves at least one of the dye precursor or electron-accepting substance can be added.

By doing so, the sensitivity to Joule heat caused by energization can be adjusted.

As the electron-accepting substance and the thermofusible substance, the same substances as those described in the method for producing thermosensitive recording paper can be used.

In order to produce a recording medium using the dye precursor of the present invention, Tokusho 3g-2≠/1rlr1 Tokusho ≠! -1ors
o, Tokko Showa 41! -/32jlr, Special Public Sho ≠ Tar 20 Hiro, Special Public Sho ≠ Tar 62/2, Special Public Sho ≠ 2-2r Hiro ≠, Special Public Opening Section 7-J / 4 / Evening, Special Public Opening Section 1-. 32!3
2, JP-A Sho≠7-2227, JP-A Sho ≠2-/3j417
, Japanese Patent Publication No. 5 o-roix O1 Japanese Patent Publication No. 0-173/7,
The present invention can be used instead of dye precursors such as lactone compounds, lactam compounds, spiropyran compounds, carbinol compounds, ethylene compounds, leucoauramine compounds, and oxazine compounds used in JP-A Showa Q-/2tλ21 etc. It is manufactured by using all the fluorane derivatives.

Other recording materials are also produced by using the fluorane derivatives of the invention in place of conventional dye precursors.

<Examples of the Invention> Example 1 7 parts (parts by weight, the same shall apply hereinafter) of Ni-anilino-3-chloro-N-ethyl-N-β-m-diphenylaminophenoxyetheraminofluoran, which is the dye precursor of the present invention. ) Totally alkylated naphthalene dissolved in lj part. This solution was added to 10 parts of water in which 1 part of gelatin and ≠ part of gum arabic had been dissolved, and was emulsified with vigorous stirring.
After forming oil droplets of ~6μ, 2JO parts of water were added. Add acetic acid little by little to bring the pH to about ≠ to cause coacervation, create a wall of gelatin and gum arabic around the oil droplets, add formalin to raise the pH,
Hardened the walls.

The microcapsule dispersion thus obtained was applied to paper and dried. This paper is treated with acidic organic matter, phenolic resin, ≠
, ≠′-improviride/diphenol, 3. j-di(α-titylbenzyl)zinc salicylate, p-hydroxybenzoic acid benzyl ester, zinc p-toluenesulfonate, 2. When pressure was applied to the paper coated with λ'-methylenebis-p-chlorophenol alone or with a mixture thereof, a black image was instantaneously obtained. This image had high density and excellent light resistance and heat resistance.

Example 2 Ni β-m-diphenylaminophenoxyethylamine-3-chloro-6-dinithylaminofluoran J which is the dye precursor of the present invention.
A polyvinyl alcohol aqueous solution and 70 parts of water were mixed and ground in a ball mill for t hours to prepare a complete dispersion. The particle size after milling was approximately 2.5 microns. (Component A) On the other hand, 30 m of bisphenol A, 30 parts of stearic acid anilide, 730 parts of a 70-functional polyvinyl alcohol aqueous solution, and 11 parts of water were mixed and ground using a sand mill to prepare a dispersion. The particle size of the insoluble material after pulverization was approximately 2 microns. (Component B) Next, 5 parts of component A and j0 parts of component B were mixed, applied to paper, and dried to obtain thermal paper.

This thermal paper turned black when heated with a thermal pen or the like. Further, when this thermal paper was overlapped with the original image and heated with a thermal copying machine, a black copy image was obtained. The resulting next-color image was very stable against light, and even when the image was irradiated with an ultraviolet lamp for one hour, there was almost no change in either hue or density.

Claims (1)

[Claims] A recording material characterized by containing a fluoran derivative having a diarylaminophenyloxy residue as a substituent.