JPH0226783A - Recording material - Google Patents

Abstract

PURPOSE:To enhance the stability of a developed color image by using a specific high-molecular leuco dye as an electron donating leuco dye in a recording material utilizing the color development by the contact of the electron donating leuco dye with an electron acceptive compound. CONSTITUTION:As an electron donating leuco dye, a high-molecular leuco dye by polycondensation is used. This high-molecular leuco dye by polycondensation is formed by condensing a leuco dye having two or more condensable substituents in the molecule thereof alone or condensing the same with other leuco dye having two or more condensable groups in the molecule thereof. As an example of condensation reaction, a combination of a hydroxyl group, an amino group and/or a halogen atom and a carboxyl group or a combination of an ester group, acid halide of a carboxyl group and/or an isocyanate group is designated. As the leuco dye becoming a raw material, a leuco dye having triarylmethane in the fundamental skeletal thereof is pref. from the aspect of good handling in synthesis and compounds represented by formulae I-IV (wherein rings A-C are an aryl group, R is a 1-30C divalent group, X is a group necessary for forming a 5- or 6-membered ring having a hetero atom and n is an integer of 2-300) are pref.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a recording material, and more particularly to a recording material with improved stability of colored images.

(Prior Art) Recording materials using both an electron-donating colorless dye and an electron-accepting compound are already well known as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, current-carrying heat-sensitive recording paper, heat-sensitive transfer paper, and the like. For example, British patent λl≠o4L Hirohiro, US patent Hirohiro 10012%
Same≠Ko36riλO1 Special Publication Showa 60-23992, Japanese Patent Publication Showa J
7-/75PIj Otsu, same & 0-/23j 6, same 40-
/23! ! I am familiar with 7 etc.

The performance that a recording material should have is (1) sufficient color density and color development sensitivity, (2) no occurrence of turnip IJ, and (3) sufficient fastness of the color material after color development. , (4) Appropriate color hue and suitability for copying machines, +
518/N ratio is high, (6) the color former has sufficient chemical resistance, and (easily exposed to organic solvents), but currently no product has been obtained that completely satisfies these requirements. .

Particularly in recent years, with the diversification of requirements for recording systems, research has been intensively conducted to improve these characteristics. There are particularly strong demands regarding (3) for these mulch color recording materials.

Conventionally, diphenylmethane compounds, triphenylmethane compounds, phthalide compounds, leucomethylene blue compounds, and the like have been known as compounds that develop a blue to blue-purple color. However, each of these compounds has drawbacks.

For example, 3,3-bis(p-dimethylaminophenyl)
-6-Dimethylaminophthalide (i.e., crystal violet lactone) develops quickly and exhibits a deep blue color, but the light resistance of the colored image is extremely poor. 3,7-bis(dimethylamino)-, a leucomethylene blue compound
Although 10-benzoylphenothiazine (i.e., benzoyl leucomethylene blue) has extremely excellent light fastness in its color images, it has the disadvantage that color development is very slow and color development with organic color developers is very poor.

The present inventors investigated the oil bath property, bath solubility in water, partition coefficient, p K a, polarity of substituent, position of substituent, and mixing of each of the electron-donating colorless dye and the electron-accepting compound. We have pursued the development of good recording material materials and recording materials by focusing on characteristics such as changes in crystallinity and solubility.

(Objective of the Invention) Therefore, the object of the present invention is to provide a recording material using a sound material, which has good stability of a colored image and satisfies other necessary conditions.

(Structure of the Invention) An object of the present invention is to provide a recording material that utilizes color development through contact between an electron-donating colorless dye and an electron-accepting compound, in which a polymeric colorless dye obtained by polycondensation is used as the electron-donating colorless dye. This was achieved by using recording materials that are characterized by convenient use.

The polymeric colorless dye produced by polycondensation of the present invention is a colorless dye having two or more condensable substituents in the molecule, or a colorless dye condensed with a compound having two or more condensable substituents in the molecule. It shows a colorless dye.

The above-mentioned polycondensation reaction refers to a polymer production reaction in which one or more molecules undergo repeated condensation reactions via active hydrogen atoms.

Examples of condensation reactions include hydroxy groups, amino groups and
or a combination of a halogen atom and a carboxyl group, an ester group, an acid halide of a carboxyl group and/or an incyanato group, a combination of a benzophenone derivative and an aromatic hydrogen atom, a halogen atom and an alkali metal of a phenolic hydroxy group and/or a carboxyl group. Examples include reactions that form new amide bonds, ester bonds, ureido bonds, urethane bonds, acid anhydrides, ether bonds, C--C bonds, etc. by combining salts.

The colorless dye used as a raw material is preferably a colorless dye having triarylmethane as a basic skeleton from the viewpoint of ease of handling during synthesis.

Preferred compounds of the present invention are shown in general formulas (I) to (■).

(I) (n) (Ill) (1'/) In the above formula, %B%C is an aryl group, and 几 is the number of carbon atoms/
to 30 divalent groups, X represents a group having at least one heteroatom or a group necessary to form a R-membered ring, and n represents a number from 2 to 300.

The aryl group represented by ring A%B and C in the above formula represents a phenyl group, a naphthyl group, or a heteroaromatic group which may have a substituent.

Among B, aniline residue, indole residue, phenol residue, aminophenol residue, pyrrol residue, carbazole residue, phenothiazine residue, etc. are preferable for the ring.

Rings A and B are aniline residues from the viewpoint of synthetic handling,
Indole residues and aminephenol residues are particularly preferred. The amino group of the aniline residue and the aminophenol residue is preferably at the -position with respect to the bonding position of the aniline residue.

Furthermore, rings A and B may be bonded via a heteroatom such as an oxygen atom or a sulfur atom.

Among the If substituents represented by R in the above formula, the number of carbon atoms/force C
)30t7) Alkylene and alkenylene are preferred, and these are -CO2--802--8Q--8-0--Co
--0CO2--NHCONH--NHCO2--CO
NH--CHoH-T: may be linked.

Among the groups represented by -X- in the above formula, R,a Ra -N -RbRa
Wb Ra Preferably (Ra and Rb are hydrogen atoms and alkyl groups.

All aryl groups and acyl groups), particularly -COO-, are preferred.

In general formulas (I) to (IV), more specifically, %B to the ring
Preferably within.

In the above formula, R1,2,6 are hydrogen atoms, alkyl groups, aryl groups, R3,5 are hydrogen atoms, alkyl groups, alkoxy groups, halogen atoms, nitro groups, or substituted amino groups, and R4 is hydrogen atoms, alkyl groups , an aryl group, Y is -CO2-
1SO2--S-0--8o--CO--OCO2- -NHCONH-1-NHCO2--CON)l--N
-(R and 7 represent a hydrogen atom, an alkyl group, an aryl group, or an acyl group.) Represents gold.

In addition, an alkyl group represents a saturated, unsaturated, or cyclofurkyl group, and these are an aryl group, an alkoxy group, an aryloxy group, and an acyloxy group.

It may contain substituent groups such as halogen atoms, acylamino groups, aminocarbonyl groups or cyan groups.

Among the substituents represented by R1,2 in the above formula, a hydrogen atom, an alkyl group having 1 to 1 carbon atoms, and an aryl group having 6 to 2 carbon atoms are preferred, and these include a halogen atom, an alkoxy group, an aryl group, It may be substituted with an aryloxy group, an alkyl group, an acyl group, a cyano group, a hydroxy group, a furfuryl group, or the like.

R1,2 is particularly preferably an alkyl group having from / to r carbon atoms.

R2 and R2 are bonded to each other to form a positive or r-membered ring, such as piperidine, morpholine, pyrrolidine, piperazine,
A ring such as hexamethyleneimine, caprolactam, or indole may be formed.

group, morpholino group, N-ethylpiperidino group, dibutylamino group, N-ethyl-h-ynylamino group, N-
Ethyl-N-isobutylamino group, N-ethyl-N-benzylamino group, cyamylamino group, diethylamino group, dioctylamino group, N-ethyl-N-tetrahydrofurfurylamino group, dibenzylamino group, N-ethyl-N -(4-methylphenyl)amine group and the like.

Among the substituents represented by R3,5 in the above formula, a hydrogen atom, an alkyl group having 1 to 72 carbon atoms, and a carbon atom number / to /
Preferred are alkoxy groups of λ, chlorine atoms, bromine atoms, nitro groups, mono- or hashialkylamine groups having from 72 carbon atoms, and monoacylamino groups having from 7 to 72 carbon atoms.

``35 is a hydrogen atom, a methyl group, an ethyl group, a butyl group, a methoxy group, an ethoxy group, an octyloxy group,
Chlorine atom, bromine atom, nitro group, N-methylamino group,
N-ethylamino group, N, N-dimethylamino group 7 groups, N,
Examples include N-diethylamino group, N,N-dibutylamino group, and acylamino group.

Among the substituents represented by R4 in the above formula, a hydrogen atom, an alkyl group having a carbon atom number of / to /λ, and an aryl group having a carbon number of 2 to /2 are preferred.

Examples of R4 include a hydrogen atom, a methyl group, and a phenyl group.

Among the substituents represented by R6 in the above formula, a hydrogen atom, an alkyl group having a carbon atom number of / to /l, a carbon atom number of 2 to 7.2
Aryl groups are preferred, and these include halogen atoms, alkoxy groups, aryl groups, allyloxy groups, alkyl groups,
It may be substituted with an acyl group, cyano group, hydroxy group, furfuryl group, etc.

R6 is a hydrogen atom, methyl group, ethyl group, n-butyl group, 1so-butyl group, 1so-amyl group, 0-hex7. It/g, n-octyl group, λ-ethylhexyl group, n-dodecyl group, stearyl group, phenoxyethyl group, hydroxyethyl group, cyanethyl group, phenyl group,
μm methoxyphenyl group etc. are included.

Among the substituents represented by R in the above formula, -CI)R2(-Z -CpHZ qji7,'9H
2Q ”'-Cp'R2Q' ) r ZCpI(2
Those represented by q- are preferred.

Here, p, p' q, q' are integers from / to 30, and r
is 0- j (7) All integers, Z is -CO2--8O2-
-S--0-1SO--CO--0CO2--NHCQ
NH-NHCO2CONL (represents --CHOH-).

Preferred examples of CpH2q, Cp'H2q' include +cH2-)-2, +CH2+4. (-CH2
vinegar. , -(-C)(2+1o, etc.).

Y is preferably in the meta position with respect to the amine group. Further, Y is preferably - from the viewpoint of synthetic handling.

Inside ring C is preferred. R8 is selected from the groups shown for R3.

m represents an integer from / to 2; R9 represents 10--S-"1O-N-; Rlo is selected from the groups shown in 7. Y is as described above.

Furthermore, in ring C is preferable from the viewpoint of cost.

Next, specific examples of the colorless dye of the present invention will be shown, but the present invention is not limited thereto.

In the present invention, it is preferable from the viewpoint of color development that the composition contains 1 wt% or more, preferably 11 wt% of the above-mentioned units.

In addition, these natural color dyes are already well known, such as lutriphenylmethane phthalide thread compounds, fluoran compounds,
Recording materials can be produced in combination with various compounds such as phenothiazine compounds, indonorphthalide compounds, leucoolamine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluoran compounds. It can also be assembled.

In this case, it is preferable to use the above-mentioned colorless dye in an amount of ≠θ% or more from the viewpoint of improving properties.

Regarding these, for example, specific examples of phthalides are listed in Patent Specification No. 23. θλ≠, U.S. Patent Specification No. 3
．． 4'? /, No. 171, No. 3. ≠ri No. 71772, same No. J, 4'ri/, // Otsu No. and same No. 3,302. /7
No. 4L, specific examples of fluorans are given in U.S. Patent Specification 'f No. 3.
．． 62≠, No. 707, same No. j, 1, 27.717,
Same No. 3, 61t/, 0//, Same No. 3. ≠Otoko, rko♂
No. 3. t♂/, No. 390, No. 31, 20, 31
No. 0, No. 3. More than that! No. 77, specific examples of spiropyrans can be found in US Patent Specification @3. Def/? or, pyridine-based and pyrazine-based compounds are described in U.S. Patent Specification Reference g3.
77jt, ≠2da, 3rd. lr! Specific examples of fluorene compounds are described in Japanese Patent Application No. 3゜227, Same No.≠, No. 2 Hirotsu, No. 3/r, and Japanese Patent Application No. 0912, etc.

Electron-accepting compounds that impart color upon contact with colorless dyes include common compounds such as phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins, metal complexes, etc. may be used in combination. Examples of these are Tokko Akihiro No. 0-9302, Tokko Sho 4Lj-/≠037, and Tokko Sho! 2-14 LOtAIE, Tokukai Sho≠Ryo-J/
J10, Tokukai Sho! 7-2IOrrI, issue, JP-A-Sho sr.
-! 70♂ri issue, Tokukai Shojter//ko♂2 issue, Tokukai Sho6
0-/747ri! No. RR, etc. from Japanese Patent Publication No. 2003-120003. In particular, combinations with salicylic acid derivatives and phenol derivatives are preferred.

When these are applied to recording materials, they are used in the form of fine dispersions or fine droplets, or in the form of films.

Furthermore, in this case, various additives well known in the field of recording materials and polymer resins, such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, and fluorescent dyes, may be added. , surfactants and other additives are used.

For use with pressure sensitive paper, U.S. Patent No. R, T.

t, No. 1170, same j, ! Or, ILt7/
No. λ.

60! ,≠t ri issue, same co, j≠♂, 366 issue, same 2.7
/2. j07, 2.730.4114, 2.7
30. u! No. 7, No. 3,103,410, No. 3. ≠
/r, No. 210, same≠,oio,.

As described in prior patents such as No. 31, various forms can be obtained. It most commonly consists of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

A method for manufacturing capsules is described in US Patent λ.

A method fully utilizing the coacervation of hydrophilic colloidal sol described in Foo, 4T67, U, 100, tAjr, British Patent No. 167.777, British Patent No. 5#0
, 1. t#J issue, same m, 21. ZA issue, same/.

θri/, 071. The interfacial polymerization method described in US Pat. No. 3,103. There are methods described in ≠Oa issue.

The capsule wall material is preferably a synthetic resin-based wall material, for example, a polyurethane and/or polyurea-based material, or a melamine resin-based material.

In general, electron-donating colorless dyes are used alone or in combination as solvents (alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, alkylated terphenyl, etc.).
Synthetic oils such as chlorinated paraffin, cotton oil, vegetable oils such as mustard oil, animal oils, mineral oils, or mixtures thereof, etc.) are dissolved in a bath, and this is incorporated into microcapsules to produce paper, high-quality paper, plastic sheets, A coloring agent sheeter is obtained by applying VC such as resin-coated paper.

Since the coloring agent of the present invention has good bath-disintegrability with respect to synthetic oils such as alkylated naphthalene, alkylated diphenyl, and alkylated diphenyllucan, it has the advantage that it can be used in combination with paraffinic oils having low solubility.

In addition to the electron-donating colorless dye, ultraviolet absorbers, antioxidants, and the like may be added as additives to the microcapsules. In particular, from the viewpoint of improving the stability of the electron-donating colorless dye in the capsule before use and the coloring of the capsule, benzo)II azole-based external radiation absorbers, hindered amine-based antioxidants, hindered phenol-based antioxidants, It is preferable to add an aniline antioxidant, a quinoline antioxidant, or the like.

In addition, an electron-accepting compound and optionally additives may be dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and used together with the pigment described below to produce paper, plastic sheets, resin-coated paper, etc. A developer sheet is obtained by coating the support.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be used depend 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 depending on the conditions. It is easy for one skilled in the art to determine this amount to use.

When used in thermal paper, it takes the form as described in Japanese Patent Application Laid-open No. 1983-1999-1 Hirohiro 7r, Japanese Patent Application No. 62-2 Hirohiro, trJ specification, etc. 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. As the dispersion medium, a water bath polymer solution having a concentration of about 0.5 to 10% is generally used, and dispersion is carried out using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloidal mill, or the like.

The ratio of the electron-donating colorless dye to the electron-accepting compound to be used is preferably between /:10 and /:/, and particularly preferably between /:j and 3. At that time, it is preferable to use a thermofusible substance in combination. These are used in finely dispersed form at the same time as the electron-donating colorless dye or simultaneously with the electron-accepting compound. These are added at a weight ratio of 20% or more and 300% or less based on the electron-accepting compound, particularly preferably 0% or more/60% or less.

Additives may be added to the thus obtained coating liquid as necessary to meet various requirements. Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder to completely prevent stains on the recording head during recording, and also to improve releasability from the head. For this reason, fatty acids, metal soaps, etc. are added. Therefore, in general, in addition to electron-donating colorless dyes and electron-accepting compounds that directly contribute to color development, thermofusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers,
Additives such as antifoaming agents, conductive agents, fluorescent dyes, and surfactants are coated onto the support to form the recording material.

Furthermore, if necessary, a film-retaining layer may be provided on the surface of the heat-sensitive recording layer. The protective layer may be laminated in three or more layers, if necessary. Further, a coating liquid similar to that of a protective layer may be applied to the back surface in order to correct the curl balance of the support or to improve chemical resistance from the back surface. An adhesive may be applied to the back side and a release paper may be further added to form a label.

Usually, the electron-donating colorless dye and the electron-accepting compound are dispersed in a binder and applied. Binders are generally water-bathable, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, and ethylene-
Maleic anhydride copolymer, styrene-maleic anhydride copolymer.

Examples include inbutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin. Furthermore, for the purpose of imparting total water resistance to these binders, a water-resisting agent may be added, or an emulsion of a hydrophobic polymer, specifically, gold such as styrene-butadiene rubber latex or acrylic resin emulsion, may be added. The coating liquid is spread onto base paper, high quality paper, synthetic paper, plastic sheet, resin coated paper or neutral paper.

Examples of thermofusible substances include JP-A Sho Jl-37riri, JP-A Sho! 1-4709, as disclosed in Hiroshi et al. Examples of such compounds are phenethyl biphenyl, cobenzyloxynaphthalene, ≠-benzylbiphenyl, di-m-
) lyloxyethane, β-phenoxyethoxyanine, l-phenoxy-λ-p-ethylphenoxyethane, his-[β-(p-methoxyphenoxy7)ethoxycomethane, /-(λ-methoxyphenoxy )−λ−(≠−
Ethyloxyphenoxy)ethane, 7.2-diphenoxyethane%/, Hiro-diphenoxybutane, bis-[β-
(p-methoxyphenoxy)ethyl]ether, /-phenoxy-up-chlorophenoxyethane, /-(l
/L-methylphenoxy)-2-(Hiro-fluorophenoxy)ethane, /-phenoxy-λ-p-methoxyphenylthioethane, /,λ-bis(p-methoxyphenylthio)ethane S/-)lyloxy-2- Examples include ether compounds such as p-methoxyphenylthioethane, stearamide, methylene bisstearamide, stearanilide, behenic acid amide, stearic acid aniside, and stearyl urea.

Pigments include kaolin, calcined kaolin, talc, waxite, cane earth, calcium carbonate, aluminum hydroxide,
Magnesium hydroxide, zinc oxide, lithopone, amorphous glue, colloidal silica, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica.

Microballoons, urea-formalin filler polyester/(-ticles, cellulose fillers, etc.) are used.

Examples of the metal soap include polyvalent metal salts of higher fatty acids, such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate.

Examples of waxes include paraffin wax, carboxy-modified rough-in wax, carnauba wax, microcrystalline wax, polyethylene wax, polystyrene wax, higher fatty acid esters, amides, and the like.

As the hindered phenol compound, at least 2
Alternatively, a phenol rust conductor in which 7 or more of the 6 positions are substituted with a branched alkyl group is preferable. For example, /, /, 3-tris(λ-methyl-≠-hydroxy-t-t-butylphenyl)butane%/1/, 3-)lis(2-ethyl-≠
-Hydroxy-5-t-butylphenyl)butane,
/, 3-tris(3,j-di-t-butyl-≠-hydroxyphenyl)butane, / , / , 3-tris(2-
Methyl-≠-hydroxy-t-t-butylphenyl)propane, ≠,≠-butylidenebis(ot-t-butyl-3
-Methylphenol, Hiro, Hiro-thiobis(3-methyl-
A-t-butylphenol), Kot-1 methylene bis(
&-t-archru≠-methylphenol), “+=nymethylenebis6-t-butyl-≠-ethylphenol), octadecyl-j-(j,j-di-t-butyl-≠
-hydroxyphenyl)propionate, /, 3. j-
Trimethylco, ≠, Otsu-tris (3,!-G-t-
-7thiru≠-hydroxybenzyl)benzene, tetrakis[methylene-3-(3,j-di to monobutyl≠-
Hydroquine phenyl)propinate comethane, λ, 2.
Examples include t,t-tetramethyl-≠-piperidinyl sebacate.

The amount of the hindered phenol compound to be used is preferably 200% to 200% relative to the electron-accepting compound, and more preferably 1% to 100%.

Examples of ultraviolet absorbers include cinnamic acid derivatives, benzophenone derivatives, benzoylphenol derivatives, etc. For example, α-cyano-β-phenyl cinnamic acid, butyl, 0-benzotriazolylphenol, 0-benzoylphenol, etc. Examples include triazolyl p-talolophenol, O-benzotriazolyl-X, U-t-butylphenol, O-penzotrianelyluco, Hiroshi-t-t-octylphenol, and the like.

Water-resistant agents include water-soluble initial meshes such as N-methylol urea, N-methylol melamine, and urea-formalin;
Examples include blend heat treatment of dialdehyde compounds such as glyoxal and glutaraldehyde, inorganic crosslinking agents such as boric acid and borax, polyacrylic acid, methyl vinyl ether-maleic acid copolymer, isobutylene-maleic anhydride copolymer, etc. .

Materials used for the protective film layer include polyvinyl alcohol,
Carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, gelatins, gum arabic, casein, styrene-maleic acid copolymer hydrolyzate, Styrene-maleic acid copolymer half ester hydrolyzate, inbutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivative, polyvinylpyrrolidone, polystyrene sodium sulfonate,
Water bathable polymers such as alginate, and water-insoluble polymers such as styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion are used.

In addition, pigments, metal soaps, waxes, waterproofing agents, etc. may be added to the protective layer for the purpose of improving matching properties with the thermal head.

Further, when coating the protective layer on the thermosensitive coloring layer, a surfactant may be added to obtain a uniform protective layer. As the surface oil agent, sulfosuccinic acid-based alkali metal salts, fluorine-containing surfactants, etc. are used. Specifically, G (
Sodium salts or ammonium salts such as n-hexyl)sulfosuccinic acid and di(niethylhexyl)sulfosuccinic acid are preferred, but anionic surfactants are effective.

The electrically conductive thermal paper is manufactured, for example, by the method described in JP-A-KOKAI Hiroshita//, 34L Hirokata, JP-A-5O-AT-30. Generally, blood in which a conductive substance, an electron-donating colorless dye, and an electron-accepting compound are dispersed together with a binder is applied to a support such as paper, or a conductive substance is applied to the support to form a conductive layer, and then a conductive layer is formed on the support. The electrically conductive thermal paper is manufactured by coating a coating liquid gold in which an electron-donating colorless dye, an electron-accepting compound, and a binder are dispersed. Note that the sensitivity can also be improved by using the thermofusible substance described above in combination.

Photosensitive and pressure sensitive paper is manufactured, for example, by the method described in JP-A-67/79131. Generally silver bromide,
Photopolymerization initiators such as silver bromide, silver behenate, Michler's ketone, benzoin derivatives, and benzophenone derivatives and polyfunctional monomers such as crosslinking agents such as polyallyl compounds, poly(meth)acrylates, and poly(meth)acrylamides are used as electron-donating colorless dyes. And if necessary, it is encapsulated in a capsule of synthetic resin such as polyether urethane or polyurea together with a bath agent. After being imaged, the rice layer is colored by bringing it into contact with an electron-accepting compound using an electron-donating colorless dye at the base of the rice layer.

Synthesis examples of the electron-donating colorless dye according to the present invention are shown below, but the invention is not limited thereto.

Synthesis example> Compound of specific example (1) Anhydrous vinegar tRO, / jμ, acetonitrile 10rrtl
Weigh and mix at 610C for 3 hours. The reaction mixture is poured into water and hydroxide is added.) The mixture is made alkaline with an aqueous solution of II ium, extracted with acetic acid ester, dried over magnesium sulfate, and the solvent is distilled off to obtain the desired product.

From GPC Hiroki Nki (Examples of the Invention) All examples are shown below, but the present invention is not limited thereto. % is weight % unless otherwise specified. represent.

■) Preparation of capsule sheet containing electron-donating colorless dye Part of polyvinylbenzenesulfone, W in sodium field (
Manufactured by National Starch, VER8A%TLj00)!
Dissolve part ' in hot water and cool. A sodium hydroxide aqueous solution was added to this to adjust the pH to 0. - Electron-donating colorless dyeing Rk3 shown in the blade notch. 7,700 parts of diisopropyl naphthalene bath-dissolved at 7,700 parts was emulsified and dispersed in 100 parts of a 100% aqueous solution of the partial sodium salt of polyvinylbenzenesulfonic acid to obtain an emulsion having an electronic size of diameter≠ and θμ. Separately, 6 parts of melamine, 37% by weight formaldehyde water bath solution//part, 30 parts of water were heated and stirred with stirring for 30 minutes, and then a transparent aqueous solution of melamine-formaldehyde prepolymer was prepared.

This water bath solution was mixed with the above emulsion. While stirring, the pH was adjusted to 6.0 with a 2M phosphoric acid bath solution, the temperature of the solution was raised to 6°C, and stirring was continued for 6 hours. The capsule liquid was cooled to room temperature and adjusted to pH 2.0 with a sodium hydroxide water bath.

To this dispersion, 200 parts of a 10% by weight polyhinyl alcohol water bath solution and JO parts of starch particles were added and water was added to prepare a solution of a microcapsule dispersion with a solid content concentration of 20%.

This rr liquid? /m2 base paper was coated with an air knife coater so that the solid content was 31/m2, and dried to obtain a capsule sheet containing an electron-donating colorless dye.

21% Preparation of child-accepting compound sheet 3. ! 10 parts of -bis-α-methylbenzylsalicylic acid zinc salt was added to 20 parts of l-isopropylphenyl-λ-phenylethane and the mixture was mixed. This was mixed with 50 parts of gold λ% polyvinyl alcohol water bath solution and 0.1 part of 70% dodecylbenzenesulfonic acid trienolamine salt water bath solution and emulsified so that the average particle size was 3 μm.

Next, 10 parts of calcium carbonate and 20 parts of zinc oxide.

After mixing a dispersion of sodium hexametaphosphate/part and 200 parts of water with the above emulsion, 100 parts of a 10% PVA water bath solution and 70 parts of carboxy-modified SBR latex (as solid content) were added as a binder. Water was added so that the solid content concentration was 20% to obtain % blood (A).

Next, a dispersion consisting of 70 parts of the color developer, 20 parts of Jilton clay, 60 parts of calcium carbonate, 20 parts of zinc oxide, 1 part of sodium hexametaphosphate, and 200 parts of water was ground in a sand grinder until the average particle size was 3 μm. It was dispersed like that.

Add 6 parts of 10% PVA aqueous solution and 10% PVA to this dispersion.
10Q parts of an aqueous solution and 70 parts (as solid content) of carboxy-modified SBR latex were added and water was added so that the solid content became 20% to obtain a liquid (B).

Coating liquid (A) and coating liquid (B) are mixed in a ratio of 1:1 in terms of color developer, and jO? / m2 of base paper was coated with an air knife coater so that the solid content of J, O77 m2 was coated.
It was dried to obtain a color developer sheetra.

On the surface of the electron-donating colorless dye-containing microcapsule sheet,
Layered on electron-accepting compound sheet AOOkg/m2
When a load was applied, all of them quickly turned reddish-purple to blue-green. The obtained image had excellent light resistance and plasticizer resistance, and in particular, there was almost no decrease in image density even when the image was held in a transparent polyvinyl chloride film and irradiated with light.

(Example/~1It) The coloring agent used is as follows.

Examples / Compound Examples of Specific Example (1) Co Specific Examples (1z Compound Example 3 Mixture Example of 7/3 (coulometric ratio) of the compound of Specific Example (2) and crystal violet lactone ≠ Compound of Specific Example Q3 and 3-(Hiro-diethylamino-2-
ethoxyphenyl) -J -(/ -n-octyl-
372 (coulometric ratio) mixture of 2-meflindol-3-yl)-≠-azaphthalide Example j Compound 20 of Specific Example 111? % Zinc-accepting compound ←β-p-methoxyphenoxy7zinc salicylate 20f,
Stearamide, a thermofusible substance, LO? 'f(
1009 5% polyvinyl alcohol (Clan PVk/
Oj) Disperse with water bath liquid in a ball mill for a day and night 1
The volume average particle diameter was set to 3μ.

On the other hand, calcined kaolin (Anisllex-VJ) 10?
O1j% of sodium hexametaphosphate 1 part/40? Disperse with a homogenizer.

Each dispersion gold dispersed as above, electron-donating colorless dye dispersion! ? , Electron-accepting compound dispersion 107, Stearic acid amide dispersion? , 22 tons of calcined kaolin dispersion, and 22 tons of zinc stearate emulsion.
A? and 2% sodium (2-ethylhexyl)sulfosuccinate water Mαj1 were added to obtain a coating liquid. On this coating, the basis weight! rO? /m2 of high-quality paper.
/m2 using a wire bar, and calendering was carried out to obtain coated paper.

The coated paper is Fujitsu Ltd. high-speed facsimile IJPF-20.
When color was developed using 00f, a back image was obtained. This image had high density and excellent light resistance and heat resistance.

Patent applicant: Fuji Photo Film Co., Ltd. Displaying 11 items Showa 6311'- Special application number 17! #j7 4. Subject of amendment: "Detailed description of the invention" column of the specification 5. Contents of correction “Detailed description of the invention” in the specification The following amendments will be made.

(1) Line 76 of page Hiroshi of the specification "Aromatic hydrogen atom" "Aromatic hydrogen atom" and correct it.

(2) Substitute the description under "" on page 7, line 73 of the specification. Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (5)
20) Fuji Photo Film Co., Ltd., 106 Tokyo; (Corrected to 40ii12537 3 J, No. 30 Keiji Photo Film Co., Ltd., Tokyo Head Office, 2-1-126 Nishi-Azabu, Miyakominato-ku.

(3) Line r of page 36 of the specification "o, ojμ" "0.OjM" and correct it.

(4) Page line of specification tube 3 "o, /zμ" "Q, 75M" and correct it.

Claims (1)

[Claims] A recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, characterized in that a polymeric colorless dye produced by polycondensation is used as the electron-donating colorless dye.