JPS6251477A - Recording material - Google Patents

Abstract

PURPOSE:To enhance a color forming property, raw preservability and the stability of developed color image, in a recording material utilizing a phenome non forming a color upon the contact of a achromatic dye with an electron acceptable compound, by using a specific fluorane derivative as the achromatic dye. CONSTITUTION:As a achromatic dye, a fluorane derivative, which has a halogen atom at the 3-position thereof and an amine residue at the 6-position thereof and of which phthalide part is substituted with a halogen atom, is used. By this method, developed color density and color forming sensitivity are improved and the generation of fog is suppressed and the fastness of a developed color material after color development can be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and in particular to a recording material using an electron-donating colorless dye and an electron-accepting compound that have improved color development, shelf life, and stability of colored images. related to recorded materials.

(Prior Art) Recording materials using 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, electrically conductive heat-sensitive recording paper, and the like.

For example, British patent 2i4Aouu, US patent φ≠10
0!2, same! Hiro 34ri 20. Tokuko Showa 10-23, Octopus 2
, JP-A-17-/7-136, tO-/-3. ! t
He is familiar with J&, 40-/, 2J, 117, etc.

The performance that a recording material should have is (1) sufficient color density and color development sensitivity, (2) no fogging, (3) sufficient fastness of the color material after color development, (
4) Appropriate color hue and suitability for copying machines (5) S
/N ratio should be high, and (6) the color former should have sufficient chemical resistance, but currently there is no product that completely satisfies these requirements.

Especially in recent years, as recording systems have become faster and demands have become more diverse,
Research is being carried out to improve these characteristics. For example, attempts have been made to use various additives to improve color development, color development speed, and stability both raw and over time. However, for the coloring reaction caused by contact between a colorless dye and an electron-accepting compound, methods that use additives that do not directly contribute to the reaction result in fogging, changes in performance over time, or reduction in effectiveness. Therefore, these means are not necessarily preferable as means for improving the performance of recording materials.

The present inventors have developed a concept completely different from the method of using these additives in combination, namely, for each of the electron-donating colorless dye and the electron-accepting compound, their oil solubility, water solubility, partition coefficient, and pKa substitution. We have pursued the development of good materials for recording materials and recording materials by focusing on characteristics such as the polarity of the group, the position of the substituent, and changes in crystallinity and solubility when mixed.

(Objective of the Invention) Therefore, the object of the present invention is to provide a recording material using a material that has good color development properties, shelf life, and stability of colored images, and also satisfies other necessary conditions.

(Structure of the Invention) An object of the present invention is to use a specific fluoran derivative, that is, a halogen atom at the 3-position, as a colorless dye in a recording material that utilizes the phenomenon in which a colorless dye is colored when it comes into contact with an electron-accepting compound. This was achieved by using a colorless dye having an amine residue at the 6-position and in which the phthalide moiety was substituted with a halogen atom.

From the viewpoint of providing a black color, fluoran derivatives further having a substituted amino group at the 2-position are most preferred.

The general formula is as follows.

In the formula, R1 is a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group; R3 is a hydrogen atom, a saturated or unsaturated alkyl group having 1 to 1 carbon atoms, an aryl group, an alkoxy group, a thioalkoxy group. , phenoxy group or thiophenoxy group R4 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a thioalkoxy group, an amino group or a substituted amino group, and X1Y represents a chlorine atom or a fluorine atom.

R1 and R2 and R2 and R3 are bonded to each other and are saturated or unsaturated! or may form a 7-membered ring. n represents / or ko.

More specifically, R1 is a hydrogen atom, a halogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, an inobutyl group, an amyl group,
Isoamyl group, cyclohexyl group, chloropropyl group,
Alkyl groups such as phenoxyethyl group, cyanoethyl group, benzyl group, dimethylamino group, diethylamino group,
Represents a group selected from acetamino group, methoxy group, ethoxy group, β-ethoxyethoxy group, phenoxy group, etc.

R1 and R2 are combined! A ring consisting of a carbon atom or a t-membered carbon atom and a nitrogen atom may be formed.

Preferred substituents for R2 and R3 include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, isobutyl group, amyl group, isoamyl group, hexyl group, cyclohexyl group, J, J-dimethylhexyl group, J, ! -dimethylbutyl group, λ-ethylhexyl group, octyl group, dodecyl group, cetyl group, octadecyl group, imprenyl group, cinnamyl group, allyl group, crotyl group, cyclopentagenyl group, cyclohexenyl group, dodecenyl group, benzyl group, 7enethyl group, isopropylbenzyl L-r-)-
+cyaethyl group, phenylpropyl group, λ-13- or ≠-phenylbutyl group or phenoxybutyl group, R2 is a hydrogen atom, a halogen atom, a cyano group, a carbonyl group, an alkoxycarbonyl group, an oxa group, a thioxa group, a carbamoyl group, N-[Number of carbon atoms that may have a substituted carbamoyl group, ureido group, sulfamoyl group, N-substituted sulfamoyl group, aryl group, etc.! to lt alkyl group, β-phenoxyethyl group, β-butoxypropyl group, β-benzyloxyethyl group, β or γ-phenoxybutyl group, chloropropyl group, acetoxyethyl group, β-acetylaminoethyl group, cyanoethyl group basis,
Alkyl groups such as glycidyl group, furfuryl group, 2- or Hiro-pyridylethyl group, allyl group, crotyl group, β-methacrylamidoethyl group, lower alkyl groups as mentioned above, alkoxy group, fluorine atom, chlorine atom, acylamino represents an optionally substituted phenyl group, naphthyl group or quinolyl group.

R2 and R3 are bonded to each other to form a saturated or unsaturated term such as a pyrrolidine ring, pyrrolidine ring, morpholine ring, inquinoline ring, isoindole ring, benzazepine ring, indole ring, imidazole ring, carbazole ring, or acridine ring. may be formed.

Preferred examples of R4 include the substituents exemplified for R2, thiophenoxy group, diarylamino group, kantadecyl group, acylamino group, alkylamino group, arylamino group, alkoxy group, maleimide group, methylamine group, and ethylamino group. , β-ethoxyethylamino group, chloroethylamino group, cyanoethylamino group, β-methacryloxyethylamine group, p-vinylbenzoylamine 7 groups,
benzylamino group, phenylureido group, p-dodecylphenylureido group, o-toluidino group, stearylureido group, nonylureido group, nonylthioureido group,
β-phenokydiethylamine group, β-butoxyethylamino group, anilino group, chloroanilino group, β-phenylureidoethyl group, γ-phenylureidopropyl group,
Examples include toluenesulfonamide group, hydroxyl group, and acylamino group.

In particular, as mentioned above, it is preferable that <R4 is located at the 2-position of the fluoran ring and is a substituted amino group.

trowel, R8 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or an acyl group which may have a substituent as described for R2, R9 is a hydrogen atom, a substituent as described for R2, independently of R8; Represents an alkyl group or an aryl group which may have a group, R8 and R9 are bonded to each other, and R2 and R
When 3 is combined to form a ring, a term as described above may be formed.

n represents l or ko.

Particularly preferred compounds are shown in the following general formula.

In the general formula (II), R11 is an alkyl group having 1 to t carbon atoms, a substituted alkyl group, R12 is an alkyl group having 1 to 1 carbon atoms, a substituted alkyl group, a cycloalkyl group, R16 is a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group having 1 or less carbon atoms, R17 is a hydrogen atom, an acyl group, a substituted alkyl group, or R1
1 and R12 are mutually bonded to form piperazine, piperidine,
Morpholine, pyrrolidine or hexamethyleneimine 7 may also be formed.

Particularly preferred specific examples are as follows.

Coanilino 3-chloro t-diethylamino-Hiro'
-Chloro and/or (the same applies hereinafter) -chlorofluorane, λ-o-1 luidino-3-chloro a-N-ethyl-N-amylamino-l'-chloro or! '-Chloro fluorane, -1anilino 3-chloro 6-dietheraminohiro'-fluoro or F'ij'-fluorofluorane, λ-β-ethoxyethyl 7mi/-3-chloro-
4-diethylamino-sin'-chloro or ut'-chlorofluoran, co-β-phenoxyethylamino-3-chloro6-diethylamino≠'-fluoro or! '-fluora-fluoran, λ-p-chloroanilino-3-chloro-t-diethylamino-μ'-chloro or t'-chlorofluoran, λ-0-toluidino-3-chloro6-
Diimprobylamino-l' or! '-ri1: Io fluorane, col-chloroanilino-3-chlorobu-N-
Petit Truijinoke'or! 'Dichloroluorane, coated siidino-3-chloro-6-dinithylamino J'
-ut'-chlorofluorane, -17-nilino-3-chloro-6-dinithylamino-4c/, 11-dichlorofluorane, notluidino-3-chloro-3', or t'-sulofluorane. Moreover, these colorless dyes are already well-known triphenylmethane7.
Can be used in combination with various compounds such as talide compounds, fluoran compounds, phenothiazine compounds, indolylphthalide compounds, leucoauramine compounds, rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, and spiropyran compounds. Able to assemble recording materials.

In this case, it is preferable to use the above-mentioned colorless dye in an amount of 1014 or more, preferably 1014 or more, preferably 4 or more, from the viewpoint of improving properties. Some examples of such colorless dyes used in combination include triarylmethane compounds such as 3
, 3-bis(p-dimethylaminophenyl)-t-dimethylaminophthalide (crystal violet lactone), 3.3-bis(p-dimethylaminophenyl)
Phthalide, 3-(p-dimethylaminophenyl)-j-
(/, j-dimethylindol-3-yl)phthalide,
3-(p-dimethylaminophenyl)-3-(nomethylindol-3-yl)7talide, etc., and diphenylmethane compounds include 4', l-bis-dimethylaminobenzhydrin benzyl ether, N -halophenyl-leucoauramine, N-214' l j-)
+7 Chlorophenyl leukoolamine, etc., and quinanthene compounds include rhodamine-B-anilinolactam and rhodamine (p-nitroanilino)9? Tam,
Rhodamine B (D-chloroanilino)lactam, Co-benzylamino-t-diethylaminofluorane, Co-anilino-t-diethylaminofluorane, Co-anilino 3-methyl-4-diethylaminofluorane, Co-anilino 3-methyl-t-cyclohexylmethylaminofluorane, J- o-chloroanilino-6-diethylaminofluorane, J-m-chloroanilino-o-diethylaminofluorane,! -(3,4A-dichloroani IJ/) -4-diethylaminofluorane, Co-octylamino-4-diethylaminofluorane, Co-hexylamino-4-diethylaminofluorane, λ
-m-)+770 lomethelanilino-4-diethylaminofluorane, coptylamino-3-chloro-t-diethylaminofluorane, -1-ethoxyethylamino-3-chloro-4-diethylaminofluorane, '-p-
Chloroanilino 3-methyl-4-dibutylaminofluoran, co-anilino 3-methyl-4-dioctylaminofluoran, 2-anilino-3-chloro-6-diethylaminofluoran, co-phenylamino-6-diethylaminofluoran , co-anilino 3-methyl-
6-cyphenylaminofluorane, 2-7enyl t-
diethylaminofluorane, co-anilino 3-methyl-+-N-ethyl-N-isoamylaminofluorane,
2-anilino-3-methyl-! -chloro-t-diethylaminofluorane, 2-anilino-3-methyl-6-diethylamino-two-methylfluorane, λ-anilino 3-methoxy 4-dibutylaminofluorane, λ-〇-chloroanilino A-dibutylaminofluoran Oran,'
-p-Chloroanilino 3-ditokitoxy-N-ethyl-N-isoamylaminofluorane, co-chloroanilino 4-p-7' thylanilinofluoran, co-anilino, 4-lino 3-pentadecyl-6- Diethylaminofluorane, λ-anilino 3-ethyl-1
-dibutylaminofluorane, co-anilino 3-methyl-san',! ′-dichlorofluorane, co. -Toluidino-3-methyl-4-diisopropylamino-1,z
'-dimethylaminofluorane, your = +))-
J-x,yb-6-N-y-□-8:3-methyl-4-
N-Ethyl-N-r-methoxy y-isoamylaminofluorane, 2-anilino-propylaminofluorane, co-anilino-3-1chloro-a-N-
Examples of ethyl-N-isoamylaminofluorane include thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue. Examples of spiro compounds include 3-methyl-spirodi-t7 topyran and 3-ethyl- spiro-dinaphthopyran,
3.3'-Cyclolosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methylnaf)-
(J-methoxy-benzo)spiropyran, 3-propyl-spiro-dibenzopyran, and the like.

Electron-accepting compounds that provide color upon contact with colorless dyes include inorganic and organic Lewis and Brønsted acids. Phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, acid clay, bentonite, novolac resins, metal-treated novolac resins, ≠-tert-butylphenol, p-phenylphenol, ≠-hydro-medium sidiphenoxide, α-su7tol , β-naphthol, hexyl-l-hydroxybenzoate, x,
J'-dihydroxybiphenyl, 2,2-bis(4
A-hydroxyphenyl)furopane (bisphenol A
), 4'f4''-isopropylidene bis(2-methylphenol), /I/-bis-(3-chloro-Hiro-hydroxyphenyl)cyclohexane, /, l-bis(3-chloro-Hiro-hydroxyphenyl) -2-ethylbutane,
φ, μ'-Secondary-isooctylidene diphenol, Guteft-octylphenol, France, μ'-@
e (-7'-tylidene diphenol, ≠-p-methylphenylphenol, 4C,4c'-(twinteridene diphenol, μ, 3'-methylcyclohexylidene diphenol, 4c'-dihydroxycyphere sulfide, l,≠-bis-φ'-hydroxycumylbenzene, l,3-bis-φ'-hydroxycumylbenzene, 4Ctl-f obis(t-tert-butyl-3-methylphenol), 4A, l-dihydroxydiphenylsulfone , hydroquinone monobenzyl ether, μm
Hydroxybenzophenone, cottadihydroxybenzophenone, polyvinylbenzyloxycarbonylphenol, coe"+4"-)lihydroxyinzophenone, co, co/, 4c, 4Ll-tetrahydroxybenzophenone, μm dimethyl hydroxyphthalate, μm hydroxybenzoin Methyl acid, λ.

μ, Hiro'-trihydroxydiphenylsulfone/, j-
Bis-p-hydroxyphenylpentane, /, bis-p-hydroxyphenoxyhexane, tolyl g-hydroxybenzoate, l-hydroxybenzoic acid α-phenylindyl ester, phenylpropyl l-hydroxybenzoate, 7-enethyl g-hydroxybenzoate , p-chlorobenzyl g-hydroxybenzoate, p-chlorobenzyl g-hydroxybenzoate, benzyl hydroxybenzoic acid ester, di-hydroxybenzoic acid RL
1m-chlorobenzyl ester, g-hydroxybenzoic acid β-7enethyl ester, ≠-hydroxy-2',
φ′-dimethyl diphenyl sulfone, β-7enethyl orselinate, cinnamyl orselinate, orselic acid-〇-chloro d-phenoxyether ester, 0-ethylphenoxyethyl orselinate, o-phenylphenoxyethyl orselinate , m-phenylphenoxyethyl orcelinate, 2. ≠-dihydroxybenzoic acid-
β-3'-t-7'thyl-triple-hydroxyphenoxyethyl ester, /-t-7'thyl-p-hydroxyphenylsulfonyloxybenzene, μmN-benzylsulfamoylphenol, co-dihydroxybenzoin Acid-p-methyl benzyl ester, co-dihydroxybenzoic acid-β-phenoxyethyl ester, 2
．． Hiro-dihydroxy-4-methylbenzoic acid benzyl ester, bis-l-hydroxyphenylacetate methyl, ditolylthiourea,! , l-diacetyldiphenylthiourea, 3-phenylsalicylic acid, J-cyclohexylsalicylic acid, 3. ! - tertiary butylsalicylic acid,
3. j-di-dodecylsalicylic acid, J-methyl-! -Benzylsalicylic acid, j-phenyl-! -(α,α-dimethylbenzyl)salicylic acid, 3. Aromatic carboxylic acids such as j-di(α-methylindyl)salicylic acid, co-hydroxy-/-benzyl-3-naphthoic acid, 3,Z-di-cyclopentadienylsalicylic acid, noceraphenylphenol-formalin resin, para- Organic color developers such as phenolic resins such as butylphenol-acetylene resin, salts of these organic color developers and polyvalent metals such as zinc magnesium, aluminum, calcium, titanium, manganese, tin, and nickel, and hydrogen chloride, Hydrogen acid such as hydrogen bromide and hydrogen iodide, boric acid,
Inorganic acids such as halides such as silicic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, aluminum, zinc, nickel, tin, titanium, boron, etc., acid clay, activated clay, atta/ξ guide, bentonite, colloidal silica, Inorganic color developers such as aluminum silicate, magnesium silicate, zinc silicate, tin silicate, zinc rhodan, zinc chloride, iron stearate, cobalt naphthenate, nickel, e-oxide, ammonium nitrate, oxalic acid, maleic acid, tartaric acid, citric acid , aliphatic carboxylic acids such as conolic acid and stearic acid, benzoic acid,
paratertiary butylbenzoic acid, heptalic acid, gallic acid,
One or more of these are used.

When these colorless dyes and electron-accepting compounds are applied to recording materials, they are used in the form of fine dispersions or fine droplets.

For use with pressure sensitive paper, U.S. Patent No. 2. jOj, 17
No. 70, same, 10! , Hiroshi 71, same λ.

! 01, ≠r, same λ, j≠r, Jbu6, same 2.
7/ko, No. 107, same, 730, ≠yo No. 6, same No. 2
, 730. μ37, 3103≠Oμ, 3. ≠
It, λ! It can take various forms as described in prior patents such as No. θ and No. 1-010031. Most commonly they consist of at least one pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

A method of manufacturing capsules is described in a US patent.

100,! No. 77, same! , 100, 1fiJ-
A method using coacervation of a hydrophilic colloid sol described in No. 1, British Patent No. 7,7F7, No. 9
10.41Cj No. t, No. 2617, same I.

Examples include the interfacial polymerization method described in U.S. Patent No. 1,074, and the method described in U.S. Pat.

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; Vegetable oils such as cotton oil and castor oil; Animal oils; Mineral oils and mixtures thereof)
After dissolving it in microcapsules,
A color forming agent sheet is obtained by coating it on a support such as paper, high-quality paper, plastic sheet, resin-coated paper, or the like.

In addition, the electron-accepting compounds described below, alone or in combination, or together with other electron-accepting compounds, are dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and the pigments described below are used to produce paper, plastic sheets, and resin-coated paper. A developer sheet is obtained by coating a support such as the following.

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 copying 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, the electron-donating colorless dye and the electron-accepting compound have a molecular weight of less than ioμ, preferably 3
It is used after being crushed and dispersed to a particle size of μ or less. As a dispersion medium, it is generally 0.1 to i.

An aqueous solution of a water-soluble polymer having a concentration of about 10% is used, and dispersion is carried out using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloid mill, etc.

The ratio by weight of the electron-donating colorless dye to the electron-accepting compound used is preferably between 1:10 and 1:l, and particularly preferably between 1:j and 2:3. At that time, fatty acid amide, acetoacetanilide, diphenylamine,
Nitrogen-containing organic compounds or compounds like penzamide, carbazole, etc.

3-di-m-tolylbutane, a-fluorobenzoyldurene, chloroindiylmesitylene, 4t.

Hiro'-dimethylbiphenyl, or carboxylic acid esters such as dimethyl inphthalate, diphenyl 7-talate, dimethyl terephthalate, methacryloxybiphenyl, etc., or polyether compounds such as di-m
-tolyloxyethane, β-phenoxyethoxyaninol, l-7dinoxyJ-p-ethylphenoxyethane, bis-β-(p-methoxyphenoxy)ethoxymethane, l-2'-methylphenoxyco'-ethyl Phenoxyethane, /-tolyloxy-2-p-methylphenoxyethane, 't2-diphenoxyethane, /, Hiro-diphenoxybutane, bis-β-(D-ethoxyphenoxy)ethyl ether, l-phenoxy λ-p -chlorophenoxyethane, /-2'-71tylphenoxy-λ-Hiroshi"-ethyloxyphenoxyethane, /-4!
It is preferable to use a compound with a melting point of 7z 0 (, -1so 'C) such as '-methylphenoxy-J-1'-fluorophenoxyethane. It will be done.

In particular, it is preferable to disperse the colorless dye at the same time from the viewpoint of preventing fogging. These usage amounts are added at a weight ratio of 20 ft or more and JOOqb or less with respect to the electron-accepting compound,
Particularly preferred is pos or more/10% or less.

Additives are further added to the coating liquid thus obtained in order to meet various requirements.

Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder in order to prevent the recording head from becoming dirty during recording, and also to improve releasability from the head. For this purpose, fatty acids, metal soaps, etc. are added. Therefore, in addition to colorless dyes and electron-accepting compounds that directly contribute to color development, additives such as pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, and surfactants are used. is applied onto a support to form a recording material.

Specifically, pigments such as kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined gypsum, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, and sulfuric acid are used as pigments. Barium, mica, microballoon, urea-formalin fluoride, polyethylene noticle,
Cellulose-filler etc. Particle size 0. /Naishi/! Selected from μ. Examples of waxes include paraffin wax, carboxy-modified paraffin wax, cownaparow wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

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

These are dispersed and applied in a binder.

Binders are generally water-soluble, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and imbutylene-anhydride. Examples include maleic acid copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and gelatin. In addition, in order to impart water resistance to these binders, water-resistant agents (gelling agents, cross-linking agents) are added, or emulsions of hydrophobic polymers, specifically styrene-butadiene rubber latex, acrylic resin emulsions, etc. You can also add

The coating liquid is applied onto base paper, high-quality paper, synthetic paper, plastic sheet, or neutral paper at a thickness of about 1 to 10 y/m 2 .

Further, on the surface of the coating layer, 00-2~. It is also possible to provide a protective layer with a thickness of about 2μ to improve resistance.

In addition, when used for thermal paper, OLS co, 2λ1tri
Issue, same xiiorz+, Tokko Akira! Various embodiments described in Koko O/442 etc. can be taken. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

For example, the electrically conductive thermal paper is disclosed in Japanese Patent Application Laid-Open No. 2003-2001-2-/J4L-Hiroshi.
It is manufactured by the method described in o-4Arri No. 30 and the like. Generally, a coating liquid in which a conductive substance, a basic dye mainly composed of the fluoran derivative of the present invention, and an electron-accepting compound are dispersed together with a binder is applied to a support such as paper, or
The electrically conductive thermal paper of the present invention is produced by coating a support with a conductive substance to form a conductive layer, and then coating thereon blood in which a colorless dye, an electron-accepting substance, and a binder are dispersed. In addition, using the thermofusible substance mentioned earlier,
Sensitivity can also be improved.

For example, the light-sensitive and pressure-sensitive paper is JP-A-77-/7? rJt et al. Generally silver iodobromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives,
A photopolymerization initiator such as a benzophenone derivative and a polyfunctional monomer such as a crosslinking agent such as a polyallylated compound, poly(meth)acrylate, or poly(meth)acrylamide are used together with a colorless dye and optionally a solvent to form a polyether urethane,
A synthetic resin wall, such as polyurea, is encapsulated within the capsule. After imagewise exposure, the colorless dye in the unexposed area is brought into contact with a color developer and colored, and was developed by the present inventors.

The above-mentioned fluoran derivatives can be synthesized by combining several known unit operations.

For example, it is synthesized by reacting the indicated benzoylbenzoic acid derivative with the indicated phenol derivative. (Re is a hydrogen atom or an alkyl group) The reaction is carried out at a temperature of -70C to 0C for about 1 to 10 hours. In this case, it is advantageous to use acidic condensing agents such as sulfuric acid, fuming sulfuric acid, polyphosphoric acid, phosphorus oxychloride, and the like. Small amounts of phthalide are usually produced as by-products.

Next, a specific example of synthesis of the fluoran derivative according to the present invention will be shown.

Synthesis Example 1 Co-7nilino-3-chloro-6-dinithylamino μ′
-10 in a flask fitted with a chlorofluorane stirrer
Weigh out 0ml of sulfuric acid and /jib of fuming sulfuric acid. -11'-Hydroxy-zhen'-diethylaminobenzoylderchlorobenzoic acid 0. 0.10 rmol of l1moltohiro-anilino-3-chloro-anisole was added sequentially, and the mixture was heated from room temperature to
Stirred at 4tO0C for 11 hours.

Separation was performed according to a conventional method to obtain the desired product having a melting point of ivy to 19λ0C. This compound is Rodan Zinc, 3°! -D-alpha-methylbenzylsalicylate When contacted with zinc or activated clay, a black phase was exhibited.

Synthesis example λ Co7nilino3-chloro-bu-diethylamino! ′
-In place of the benzoic acid derivative in Synthesis Example 1 of chlorofluoran, Coλ'-hydroxy-φ'-diethylamino-benzoyl-! '-chlorobenzoic acid was used.

The desired product was obtained in the same manner as in Synthesis Example 1.

Melting point lλco~lcolo°C0 (Examples of the Invention) Examples are shown below, but the present invention is not limited to these Examples.

Example 1 (1) Preparation of sample λ-anili/-J-methyl-6-dietheraminoμ'
-Chlorofluorane 29X2-anilino-J-chloro-
6-diethylaminofluorane l.

10 il of JP and/-phenoxy-λ-p-ethylphenoxyethane were dispersed to an average particle size of λμ using a sand mill with a 3.6% aqueous solution of polyvinyl alcohol (polyvinyl alcohol, polymerization degree: 1000) using a sand mill.

On the other hand, /, /-4"-hydroxyphenyl-≠"-hydroxy-J"-allylphenylcyclopentane 101 and /-phenoxy-col-ethylphenoxyethane 7
P″t-j*Polyvinyl alcohol aqueous solution/009 is dispersed in a ball mill for a day and night. After mixing this thoroughly, add Joshia Kaolin-20 and fine particle silica to disperse well, and then create a NONO-FINE WAX EMULSION! O% dispersion (Middle East oil and fat Cellosol ÷ 4!-
ko r) p.

IP was added to prepare a coating liquid.

The coating liquid is applied onto neutral paper having a basis weight of toy/rn" so that the solid content coating amount is O, zy/m", and ≦Q
After drying at 0C for 1 minute, press OKeW/Tande Sue/'?
- A coated paper was obtained by calendering.

Coated paper is heated by facsimile with energy of 31 mJ/
When the color was developed by heating at m'' and the color density was determined, it showed /00 with a Macbeth reflection densitometer.

The obtained recording material had no fog during raw storage and had excellent stability over time. On the other hand, the obtained colored image was clear black and showed good resistance to chemicals, sunlight, etc.

Example 3 Preparation of sample 3 (1) Color developer coated sheet A Rodan zinc was coated on high-quality paper with a top basis weight so that it was 1/2 p/m".

(2) Color developer coated sheet B: 1 part of light calcium carbonate, 31 parts of aluminum hydroxide (Showa Denko H-30), 1 part of styrene-α-methylstyrene copolymer. r part and 3. j-di-α-methylbenzylsalicylate mixed with 1.2 parts of zinc, io parts of zinc oxide, 0.2 parts of euhydroxy-μm butoxybenzophenone
1 part, sodium hexametaphosphate/part was dispersed in 200w1 of water, and then treated with a sand mill to obtain an average particle size of 3 parts.
A dispersion of μ was obtained. Add to this 2 parts of polyvinyl alcohol,
Carboxy-modified SBR latex (4cry), Q part and 10 parts water were added and stirred well. This is the basis weight 4'/P
/m2. (7) As solid content on acid-free paper! .

-2y/rn2.

(3) Colorless dye-coated paper λ-7 Nilino 3-methyl-4-diethylamino-Hiro'
-Chlorofluorane 0. /! 2-anilino-3-methyl-t-diethylamino-! '-Chlorofluorane 0
．． 2 parts and 2-anilino-3-methyl-6-sibutylaminofluorane O0λm, 2 parts of ethyl acetate, 3 parts of l-phenyl-/-xylylethane, tolylene diisocyanate and trimethylolzolonogne (J:/ ) adduct 0.
7 parts and propylene oxide of ethylenediamine (
l:≠) 002 parts of adduct were added and dissolved.

The solution thus obtained was emulsified and dispersed at 200C in 2 parts of water containing 2.6 parts of polyvinyl alcohol.

Let it be tμ. Next, add 100 parts of water and while stirring, add 100 parts of water.
Encapsulation is performed by heating for 0°C to 70°C. What is the average particle size? , 6 songs with lμ. The microcapsule dispersion thus obtained was coated on synthetic paper with a basis weight of 1P/2 in a coating weight of 1P/m2.

The thus obtained capsule-coated surface and the developer-coated sheet or B were placed facing each other and pressurized. A black image was very quickly obtained on the developer-coated surface of the pressurized area.

This black image was clear and highly concentrated, and showed excellent discoloration or fading even when exposed to sunlight.

Claims (1)

[Claims] In a recording material that utilizes color development due to contact between an electron-donating colorless dye and an electron-accepting compound, the colorless dye has a halogen atom at the 3-position, an amine residue at the 6-position, and a phthalide moiety. A recording material characterized by using a fluoran derivative substituted with a halogen atom.