JPS6394878A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material having high stability of coloring performance, raw storage performance and coloring image being produced where the coloring portion has light absorption in near infrared zone, by providing a coating layer containing a specific donor colorless dye and a specific acceptor compound onto a neutral paper. CONSTITUTION:A fluoran derivative having an anilino group at 2-position and a substituted an amino group at 6-position and a fluoran derivative having substituted amino group are employed as a donor dye, while a phenol derivative and/or a salicylic acid derivative is employed as an acceptor compound. Furthermore, calcium carbonate and/or zinc oxide are crushed and dispersed into a dispersion medium and employed. A recording material having a coating layer containing these four components on a neutral paper has a coloring portion where the light absorption is in the near infrared zone, a sufficient coloring density and stable coloring matter, thereby it is scarcely subjected to fading due to long time irradiation of light, heating or humidifying, thus enabling long term storage of a record.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and in particular, a recording material having a color-forming portion absorbing light in the near-infrared region and having improved color-forming properties, shelf life, and stability of colored images. This invention relates to a recording material using an electron-donating colorless dye and an electron-accepting compound.

(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, UK patent 2/4t011≠7, US patent μ≠1
00jj2, samej≠362. ! 01 special public service 1986-23,
Octopus, 2, JP-A-37-/79. za36, same 6θ-/2
3,336, 60-/23,337, etc.

The properties that a recording material should have are (1) sufficient color density and color development sensitivity, (2) no formation of IJ 'Ir, and (3) sufficient fastness of the color material after color development. (4) Appropriate color hue and suitability for copying machines (
(5) A high S/N ratio, and (6) sufficient chemical resistance of the coloring body, but at present there is no product that completely satisfies these requirements.

In particular, heat-sensitive recording materials have the disadvantage that capri is caused by solvents and the like, and the color formers are discolored and faded by oils, fats, chemicals, and the like. Therefore, water-based ink, oil-based ink, light pen, ink, adhesive,
When it comes into contact with stationery and office supplies such as glue and diazo developer, or cosmetics such as hand cream and emulsion, the white parts develop color or the colored parts change color and fade, significantly reducing the product value. The present inventors have investigated the oil solubility,
Pursuing the development of good materials for recording materials and recording materials by focusing on characteristics such as solubility in water, partition coefficient, polarity of pKa substituents, position of substituents, and changes in crystalline solubility when mixed. I've done it. Furthermore, in recent years, there has been a desire to develop recording materials that absorb in the near-infrared region.

(Objective of the Invention) Therefore, the object of the present invention is to provide a recording material which has good coloring properties, shelf life, and stability of colored images, and in which the coloring portion absorbs light in the near-infrared region.

(Structure of the Invention) The object of the present invention has been achieved by a recording material in which a coating layer containing the following components is provided on neutral paper.

(a) Fluoran derivative having an anilino group at the 2-position and a substituted amine group at the 6-position fb) Fluoran derivative having a substituted amine 7 group (c
1 Phenol derivative and/or salicylic acid derivative fdl Calcium carbonate and/or zinc oxide Among the fluoran derivatives according to the present invention, those represented by the following general formula (1) are preferred, (wherein R1, R2, and R3 are carbon numbers/~ 10 alkyl group, R4 is a hydrogen atom! An alkyl group with carbon number/~g, and X represents an alkyl group with carbon number/~g or chlorine atom.) In the above general formula (]), R1 and R2 The alkyl group represented by may have a complete ring structure or may have a substituent. In the above general formula (1), compounds in which X is a methyl group or a chlorine atom are particularly preferred. Examples of these colorless to light-colored electron-donating dye precursors include, but are not limited to, manure compounds.

No-anilino-3-methyl-ot-dimethylaminofluorane, 2-anilino-3-methyl-ot-hemethyl-P
(-Ethylminofluorane, 2-anilino-3-methyl-hemethylbenzene(+ SO-propyl)aminofluorane, 2-anilino-3-methyl-6-hemethyl-hebenthylminofluorane, 2-anilino-
3-Methyl-6-hemethyl-17-chlorohexylaminofluorane, -1-anilino-3-methyl-6-diethyl-minofluorane, 2-anilino-3-chloro-6-
Dimethyl minofluorane! -Methyl-Ethyl-Heiso-Methylaminofluorane,
2-anilino-3-methyl-A-N-methyl-heiso-remylaminofluorane, 2-anilino-3-chloro-
6-Dinithyl-minofluorane, no-anilino-3-chloro-,5--A-N-menaluhethylaminofluorane, λ-
Anilino 3-chloro-6-hemethyl-(iso
-propyl) minofluoran, -nilino-3-chloro-4-N-methyl-hehenthylaminofluoran, no-anilino-3-amino-6-hemethyl-he-cyclohexyl-minofluoran, no-anilino-3-methyl-2- One ethyl hepentylaminofluorane! -1-li/-3-chloro 4-N-ethylhopentyl-minofluorane, 2-(p-methylanilino)
-3-Methyl-O-dimethyl-minofluorane, no(
p-methylanilino)-3-methyl-6-diethylminofluorane, 2-(p-methylanilino)-3-
Methyl-6-hemenaluh-ethylaminofluorane, 2-(p-methylanilino)-3-methyl-6-hemethyl-he(iso-propyl)minofluorane, no(p-methylanilino)-3-methyl-6- To
Methyl-hepentylaminofluorane! -(p-
methylanilino)-3-methyl-A-N-methyl-N-
Cyclohaki/ruaminofluorane, no(p-methylanilino)-3-methyl-6-N-ethylhopentyl-aminofluorane, -1(p-methylanilino)-3-
Aminofluorane 1,2-(p
-methylanilino)-3-chloro-6-dinithylaminofluorane, 2-(p-methylanilino)-3-chloro-&-N-methylheethylminofluorane, 2-
(p-methylanilino)-3-chloro-6-he-methyl-(iso-propyl)aminofluorane, --(
p-methylanilino)-3-chloro-6-hemethyl-hepentylaminofluorane 1.2-Cp-methylanilino)-3-chloro-6-hemethyl-hepentylaminofluorane, 2-(p-methylanilino )-3-Chloro-A-N-ethyl-bentylaminofluorane, 2-anilino-3-meth-6-hemethyl-hefurylmethyl-monofluorane, -1-anilino-3-ethyl-6-he Examples include methyl-hefurylmethylaminofluorane, which may be used alone, but may also be used in combination of two or more for tone adjustment and IE during fading of colored images.

The following general formula (It) of the fluorene derivative according to the present invention
11. stomach.

The groups represented by X and Y in the above general formula (n) represent amine residues ~, and Z represents a hydrogen atom or a substituted amino group.

... A- has at least 7 heteroatoms and is a group necessary to form j or 611tk, for example ... CO...
・He=C-5-,...0-COO-.

RI selected from T-1 COR1...He CO-He-2...He C0-0- R2R1 Covers with a neutral group. (R, is a hydrogen atom or an alkyl group (2 represents an alkyl group or an acyl group) In the above formula,
Among the amine residues represented by , Y or Z, secondary amine residues are preferable [-<, especially secondary amine residues having a number of carbon atoms from ≠ to /B.

Some examples include diethylamino group, dipropylamino group, dibutylamino group, ethylisobutylimino group, ethylisoamylamine group,
Examples include a ethyl-cyclohexyl-termino group, a di-termyl-termino group, a diethylamino group, a dioctyl-termino group, and an ethyl-tetrahydrofurfurylamine group.

Next, specific examples of the fluorene derivative according to the present invention will be shown.

−? - Riff) [In the above compound examples, R3, R4, R5 and R6 represent an alkyl group having /2 to /2 carbon atoms.] These electron-donating colorless dyes are similar to other triphenylmethane phthalide compounds, fluoran compounds. , phenothiazine compounds, indolyl 7-thallide compounds, leucoolamine compounds,
It may be mixed with various compounds such as rhodamine lactam compounds, triphenylmethane compounds, triazene compounds, and spiropyran compounds.

Specific examples of phthalides are from the US Department of Reissued Patent Specifications, 23.
No. 0.2μ, US Patent Specification Letter 3. Geta l.

No. 777, same No. 3. ≠9/, //2 No. 3, No. 3/
, //lr issue and the same no. 3. Specific examples of fluoranes include U.S. Patent Specification Letter 3゜Lμ, No. 707, No. 3, A, No. 27.717, No. 3,6≠/, 0
// issue, same number 3. ≠622g, 2g No. 3 and 6
A'/, No. 30, U.S. Patent Specification Letter 3.9.20. !
;/θ No., US Patent Specification Letter 3. Specific examples of spiropyrans can be found in U.S. Patent Specification Letter 3. 7/1
g0g, pyridine-based and pyrazine-based color-forming compounds, U.S. Patent Specification Letter 3, 774, ≠ 2 and U.S. Patent Specification Letter 3, 774, 2
1A.

It is described in the 3/♂ issue etc.

Among the phenol derivatives according to the present invention, the following general formula (1)
Preferably, the expression is 21~.

In the above general formula (1), R1 and R2 may be the same or different, and include a hydrogen atom, an alkyl group, an alkoxy group,
R3 represents an aryl group, an arylnulfonyl group, an alkoxycarbonyl group, or a halogen atom; R3 represents a hydrogen atom or a group represented by the following general formula (TV);

In the above formula (IV), %R1 and R2 are based on the above general formula (1)
R4 represents the same as R1 and R2 in , and R4 represents a divalent group having 7.2 carbon atoms or S02.

Among the compounds represented by the above general formula (1), R3=)l
When R1 and R2 are a hydrogen atom or an alkoxycarbonyl group, and when R3 is a group represented by general formula 1), R4
is a carbon atom number 3 to /, 20 alkylene group, carbon atom number j
A cycloalkylene group having ~7 carbon atoms, an aralkylene group having g~/2 carbon atoms, and so2 are preferred.

In the above general formula, the alkyl group represents a saturated or unsaturated alkyl group or a cycloalkyl group, and these groups have a substituent such as an aryl group, an alkoxy group, an aryloxy group, a halogen atom, or a cyan group. You may do so. Some examples include μm phenylphenol, bisphenol sulfone, p-phenylsulfonylphenol, p-IJ sulfonylphenol, bis(3-vinyl-≠-hydroxyphenyl)sulfone 1,2. ．． 2-His(3-hinyl≠-hydroxyphenyl)propane, bis-3-originyl hydroxyphenyl sulfone, hexyl-t-hydroxybenzoate, j,, 2'-dihydroxyhyphenyl, 2.2
-bis(4t-hydroxyphenyl)propane, 4t,
4t'-isopylidenehis(,2-methylphenol)
, /, /-bis-(3-chloro-j-hydroxyphenyl)cyclohexane, /, /-bis(3-10 rho≠-
Hydroxyphenyl)-2-ethylbutane p, l
l'-Secondary octylidene diphenol,
≠, ≠'-5eC-butylidene diphenol, ≠-p-
Methylphenylphenol, ≠, ψ'-isopentylidene diphenol, ≠, v'-methylcyclohexylidene diphenol, ≠, 4t'-dihydroxydiphenyl sulfide, /, ≠-bis(1,t'-hydroxycumyl) Benzene, /, 3-his-(q'-hydroxycumyl)benzene, ≠, ri'-thiobis(lr-tert
-butyl-3-methylphenol), ≠, q'-cyhydroxydiphenylnurfone, hydroquinone monobenzyl ether, g-hydroxybenzophenone 1.2.1
%-Dihydroxybenzylphenol, polyvinylbenzyloxyphenol, ≠, t/l' -
Trihydroxybenzophenone, 2. ．． 2', ≠, ≠'
-tetrahydroxybenzophenone, dimethyl t-hydroxyphthalate, ≠-methyl hydroxybenzoate, 2°≠, ≠'-trihydroxydiphenylsulfone, /9.
3-his-p-hydroxyphenylpentane, /, 6-
P-Hydroxybenzoic acid 7-hexane, ≠-Hydroxyamne, tolyl sicoate, q-Hydroxybenzoic acid α-phenylbenozyl ester, ≠-Phenylpropyl hydroxybenzoate, ≠-Phenethyl hydroxybenzoate, ≠
-Hydroxybenzoic WR-p -chlorobenzyl, ≠-
Hydroxybenzoic acid-p-methoxybenzyl, j-hydroxybenzoic acid benzyl ester, ≠-hydroxybenzoic acid 82-m-chlorobenzyl ester, ≠-hydroxybenzoic acid β-7enethyl ester, ≠-hydroxy,
x', lIL'-dimethyldiphenyl sulfone, β-phenethyl oroseinate, nnnamyl oriseinate,
Orserin H-o-chlorophenoxyethyl ester,
0-ethylphenoxyethyl orseinate, 0-phenylphenoxyethyl orselineate, m-phenylphenoxyethyl orseline-1-1-2+4'-dihydroxybenzoic acid-β-3'-t-7'thyl- ≠′-hydroxyphenoxyethyl ester, /-1-butyl-Hiroshi-p-hydroxyphenylsulfonyloxybenzene,
≠− Hebenzyl sulfate moylphenol,! ,q−
dihydroxybenzoic acid-p-methylbenzyl ester,
2. Examples include ≠-dihydroxy-7-benzoic acid-β-phenox7-ethyl ester, noukudihydroxy-6-methylbenzoic acid benzyl ester, methyl his-t-hydroxyphenylacetate, and the like.

Among the salicylic acid derivatives according to the present invention, the following general formula (V)
Those represented by are preferred.

In the above formula, R is a hydrogen atom, an aryl group, or an alkyl group 2
, X represents an alkyl group, an alkoxy group or a halogen atom, M represents an n-valent metal atom, and n represents an integer of / to 3.

The alkyl group is a saturated or unsaturated alkyl group or a cycloalkyl group. The aryl group may be a phenyl group, a naphthyl group, or -/g- represents a heteroaromatic ring group, and these include an alkyl group, an alkoxy group, an aryoloxy group, a halogen atom, a nitro group, cyano group, substituted carbamoyl group, substituted sulfuryl group, substituted amino group, substituted oxycarbonyl group, msoxysulfonyl group, thioalkoxy group, arylsulfonyl group or one group has a substituent such as phenyl group. Tomoyo (
・.

Among the substituents represented by R in the above formula, a hydrogen atom, a phenyl group, and an alkyl group having 7 to 2 carbon atoms are preferable,
Among the substituents represented by , aluminum, magnesium, and calcium are preferred.

Among the substituents of the alkyl group and alkoxy group represented by .2
An alkoxy group, )10 atoms, or an alkoxydicarbonyl group is preferred (2).

From the viewpoint of water insolubility, the salicylic acid derivative according to the present invention preferably has a total number of carbon atoms/μ or more, particularly preferably 76 or more. These may be used in the form of metal salts,
It is also possible to use gamma, ie, zinc oxide, coexisting in the dispersion to cause salt formation, adsorption, or double decomposition sounds in the dispersion.

Next, a specific example will be shown.

Cupentadecylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3゜j-di-1-methylsalicylic acid, 3. j-di-dodecylsalicylic acid, 3
-Methyl-j-benzylsalicylic acid, 3-phenyl-3
-(α,α-dimethylbenzyl)salicylic acid, 3,3-
Di(α-methylbenzyl)salicylic acid, 3. j-ji-
t-octylsalicylic acid, j-tetradecylsalicylic acid, j-hexadecylsalicylic acid, j-octadecylsalicylic acid, 3-α-(p-α-methylbenzylphenyl)
Ethylsalicylic acid, cudodecyloxysalicylic acid, t
-tetradecyloxysalicylic acid, j-hexadecyloxysalicylic acid, ≠-β-phenoxyethoxysalicylic acid, g-β-p-tolyloxyethoxysalicylic acid, ≠
-β-p-ethylphenoxyethoxysalicylic acid, ≠
-β-p-methoxyphenoxyethoxosalicylic acid, q
-β-p-ethoxyphenoxy7ethoxysalicylic acid, ≠
-β-m-tolyloxyethoxysalicylic acid, ≠-β-
〇-Tolyloxyethoxysalicylic acid, V-(do-phenoxyoctyloxy)salicylic acid, etc. These may be used alone or in combination.

The recording material according to the present invention has a color-forming part that absorbs light in the near-infrared region, has a sufficient color density, and is extremely stable, with almost no discoloration or fading even with long-term light irradiation, heating, or humidification. ? Since it does not cause any damage, it is especially advantageous in point 5B for long-term preservation of records. Furthermore, when used in a heat-sensitive recording material, there is no drawback that uncolored areas develop color due to solvents, etc., or color-forming bodies change color or fade due to oils, fats, chemicals, etc., so it has near-ideal performance as a recording material.

When used in thermal paper, the electron-donating colorless dye and the electron-accepting compound are mixed in a dispersion medium at /θμ, preferably L<3.
The particles are pulverized and dispersed to the following particle size (7).As the dispersion medium, a water-based polymer aqueous solution with a concentration of about 0.3 to 10 mm is generally used, and the dispersion is carried out using a ball mill, sand mill, horizontal sand mill, This can be done using an attritor, colloid mill, etc.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably between /:10 and /:/, and particularly preferably between /:j and 2:3. On the other hand, separately from the electron-donating colorless dye and the electron-accepting compound, calcium carbonate and/or zinc oxide are pulverized and dispersed in a dispersion medium. The amount of calcium carbonate and/or lead oxide used is '0. ．． It is preferably 5 to 20 times (weight ratio), particularly preferably 7 to 70 times. A thermofusible substance may be included in the thermochromic layer to improve its thermal responsiveness.

As an example of a preferable thermofusible substance, the following general formula (IV) is used.
A compound represented by ~l) is obtained.

-,2,2- To R5 To HCO R2 (Vll) 几6cONH-R7 (■) In the formula, R1 to ■t4 are respectively a phenyl group, a benzyl group, and a lower alkyl or rhodan substituted product thereof R5 and R6 each represent an alkyl group having 72 or more and 2≠ or less carbon atoms, an oxymethyl group, or a hensyl group, and R7 represents hydrogen or a phenyl group.

In addition, when the phenyl group or benzyl group represented by R1-R4 in general formulas (1) to (Ml) is substituted with a lower alkyl group, the number of carbon atoms is 1 or more and 3 or less, preferably 7 or more and 3 or less. be. When substituted with a halogen atom, fluorine is preferred. Also, the formula (Vl
), R4' represents hydrogen or a hydroxyl group.

i) In the formula, A and B are oxygen atoms or sulfur atoms, and R8 is 2
It represents a valent group, preferably an alkylene group, an alkylene group having a carbonyl group, an alkylene group having a halogen atom, an alkylene group having an unsaturated bond, and more preferably an alkylene group or an alkylene group having an ether bond.

Also X, Y, Z.

X', Y', and Z' may be the same or different and represent a hydrogen atom, a halogen atom, an alkyloxycarbonyl group, or an aralkyloxycarbonyl group.

The compounds of the general formulas (IV) to (I) have a melting point of 70°C.
The temperature at the touch point is preferably 0°C or more/and 30°C or less. Specifically, benzyl p-benzyloxybenzoate (mp
, / / 9 °C), β-naphthylbenzyl ether (m
p, 10j0C), stearyl phosphoric acid amide (m p,
/Og'C), palmitic acid amide (mp, 10
3°C), Hephenyl phosphoric acid amide (mp, 2°C), Hester phosphoric acid urea (mp, //θ°C), β-
Naphthoic acid phenyl ester (mp, 9.2'C), /
-Hydroxy-2-naphthoic acid phenyl ester (mp
, 5', 2 °C), β-naphthol (p-10 lobenzyl) ether (mp, //3 °C), β-naphthol (p
-methylbenzyl) ether (mp, 94°C), α-naphthylhensyl ether (mp, 76°C), /.

≠-methanethiol-p-methylphenyl ether (m
p,'F3℃),/,4'-F11/! 7
Diol-p-methylphenyl ether (mp, 93°
C), stearic acid esteramide (mp, 106-709°C
)-, 2J- /, ≠-butanediol-p-isopropylphenyl ether (mp, lid °C), /, goubutanediol-p
-t-ofzal phenyl ether (mp, 97°C), 2
-phenoxy-/-p-triluoxyeta/(mp
, 1011"C), /-phenoxy-,2-(47-nitylfe/xy)ethane (mp, 10A'C), /-phenoxy-no(j-chlorophenoxy)ethane (mp
, 77°C), /, q-methanediol phenyl ether (rn p .

diethylene glycol-his(gumethoxyphenyl)ether (mp, /0/'C)
), p-ethylphenoxyacetic acid henzylamide (mp.

? 4t’c), phenylacetic acid hensylamide (mp.

/, 240C), etc.

The thermofusible substances listed in 7i1 may be used alone or in combination, and in order to obtain sufficient 7c thermoresponsiveness, the amount of the thermofusible substance in electron-accepting compound 1 should be 70 to 70%. It is preferable to use 200% by weight, even more preferable! The new number of uses is 20-73
01 and end chi.

Mix the dispersion obtained in step 12 in an appropriate ratio as shown in step 2.
Additives are further added to the combined coating fluid 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. Therefore, fatty acids, metallic phosphorus, etc. are added. Therefore, in addition to colorless dyes and electron-accepting compounds that contribute to color development, pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, surfactants, hindered phenols, etc. are generally used. Additives are applied onto the support to constitute the recording material.

Specifically, pigment and 1 to 1 kaolin, calcined kaolin,
Talc, limestone, aluminum hydroxide, magnesium hydroxide, calcined stone wax, warp strength, magnesium carbonate, titanium oxide, alumina, barium carbonate, barium sulfate, mica, microballoon, urea-formalin filler,
A particle size of polyethylene or cellulose filler is selected from those having a particle size of 0.7 to 5 μm. Waxes and 1. Examples include paraffin wax, carboxy-modified paraffin wax, carnauba wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters.

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

As hindered phenol, at least 2 sho 6
A phenol derivative in which seven or more positions are substituted with a branched alkyl group is preferred.

For example, /, /-vinu(,2-methyl-guhydroxy-,5-t-butylphenyl)butane, ha/ , 3
-1-Lis(3-methyl-guhydroxy-J-1-butylphenyl)butane, His(,2-hydroxy-3-
t-butyl-j-methylphenyl)methane, his(,7
-methyl-q-hydroxy-3-1-butylphenyl)
Nurphyto etc.

These are dispersed and applied in a binder.

Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride. Examples include copolymers, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, and seratin. In addition, water-resisting agents (gelling agents, cross-linking agents) are added to these binders for the purpose of imparting water resistance, and 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 paper, or neutral paper at a thickness of about 2 to 10 f/m''.

Furthermore, the coating surface layer may contain a water-soluble or water-dispersible polymer compound such as polyhinyl alcohol, hydroxyethyl starch, or epoxy-modified polyacrylamide, and a crosslinking agent. 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, QL8.2.2.2za3
No. 8'/, same, 2/101311. Tokuko Showa 32-. 20
Various aspects described in 7≠2 etc. can be taken. Alternatively, operations such as preheating, humidity control, or stretching of coated paper may be added prior to recording.

<Examples of the Invention> Examples will be shown below, but the present invention is not limited only to these examples.

Example/ 2-anilino-3-methyl-6-N-ethyl-he-isorylaminofluorane, which is an electron-donating colorless dye
2-anilino-3-chloro-6-diethyl, minofluorane gy and 3'.

6'-bisdiethylminospiro=3-diethylminospiro(isobenzofuran-/,9'-fluorene)-3'-
On≠, the electron-accepting compound μ-β-p-methoxyphenoxyethoxyzinc salicylate, 2oy, the thermofusible substance 2-benzyloxynaphthalene 10y and stearic acid intermediate/399 100y each % polyvinyl alcohol (Kuraray PVA/03) aqueous solution in a ball mill overnight to reduce the volume average particle size to 3.
It was set as μ. On the other hand, the mixture of carbonate and zinc oxide is 0.3% solution of sodium hexametaphosphate/1
．． It was dispersed together with Of using a homogenizer.

After dispersing each dispersion as described above, 3 electron-donating colorless dye dispersions, 10P1 electron-accepting compound dispersions, 1 thermofusible substance dispersion, 2 calcium carbonate and zinc oxide dispersions,
A coating liquid was obtained by mixing in a ratio of 2y- and further adding an emulsion of zinc stearate≠1 and an aqueous solution of 2% (,!-ethylhexyl)sodium sulfosuccinate 3y. This coating liquid was dried on high-quality paper with a basis weight of 3097 m'', applied with a wire bar to a coating weight of 69/m'', dried in an oven at 30°C for 3 minutes, and calendered to obtain coated paper. Ta.

When the image was colored using Fujitsu's high-speed facsimile FF-2000, a black image was obtained. This colored image had light absorption in the near-infrared region. Furthermore, when filter paper was impregnated with ethanol and castor oil and superimposed on the colored surface of the recording paper obtained by the above method, no fogging in the white area or decolorization (discoloration) in the colored area was observed. Ta.

On the other hand, when the obtained coated paper was stored under high temperature (60° C., 30% RH) and high humidity (≠0° C. 10% RH) conditions for 2 hours, almost no fogging occurred.

Examples 2 to j The following compounds were used in place of the electron-accepting compounds in Examples. Coated paper was obtained in the same manner as in Example.

'JM Example, 2 Benzyl p-hydroxybenzoate, Example 3 /, ≠-Bis(p-hydroxycumyl)benzene Example ≠ Bis(3-vinyl-Hiro-hydroxyphenyl)sulfone' 4m Example J/, / -Bis p-hydroxyphenylcyclohexane and -β-p-methoxyphenoxyethquine Color images of the mixture of equal weights of salicylic acid each had light absorption in the near-infrared region, and there was little fog.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1985/February μ Date 1, Incident Indication 1986 Poetry Request No. 2≠091
No. 2, Title of the invention Recording material 3, Relationship to the case of the person making the amendment Address of the applicant for the license 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the amendment ``Claims'' column of the specification; Column 5 of "Detailed Description of the Invention", Contents of Amendment 1) The entire statement of the scope of claims is amended as shown in the attached sheet.

2) ≠ page, 2nd line "Fluoran" "Fluorene" and correct it.

a) Page +, 7th line from the bottom "R3" Delete.

4) Page 6, line 6 from the bottom After "Rukyl group," "R3" Insert.

5) Page 30, μth line from the bottom r-j'-J -j-J and correct it.

6) On page 30, in the first line from the bottom, "on" is followed by "[General formula of the compound example on page 70/], R3""R
4"R5"R6=C2H5 compound]" is inserted.

1/- "Attachment" Claim (a) A fluorane derivative having an anilino group at the 2-position and a substituted amine group at the 6-position, (b) A fluorene derivative having a lid-substituted amine group, (
A recording material characterized in that a coating layer containing c) a phenol derivative and/or a salicylic acid derivative, and (d) calcium carbonate and/or zinc oxide is provided on neutral paper.

One piece -

Claims (1)

[Scope of Claims] (a) A fluoran derivative having an anilino group at the 2-position and a substituted amino group at the 6-position, (b) A fluoran derivative having a substituted amino group, (c)
A recording material characterized in that a coating layer containing a phenol derivative and/or a salicylic acid derivative, (d) calcium carbonate and/or zinc oxide is provided on neutral paper.