JPH0485075A - Recording material - Google Patents

Abstract

PURPOSE:To enhance the color forming properties, white paper preservability, color preservability and chemical resistance of a recording material by adding a specific fluorane compound as an electron donating leuco dye. CONSTITUTION:In a recording material utilizing the color development due to the contact of an electron donating leuco dye and an electron acceptive compound, a fluorane compound represented by formula (I) is used as the electron donating leuco dye. In the formula (I), R1 is a hydrogen atom, an alkyl group or an aryl group, R2 is these groups, an alkoxy group or a halogen atom, R3 is R1 or an acyl group, R4 is R1, an aryloxy group, a halogen atom, an alkylthio group, an arylthio group, a substituted amino group, a cyano group, a nitro group, an acyl group or an acyloxy group, R5 is an alkyl group, an aryl group or a heterocyclic group, a ring A is an aromatic ring which may contain a hetero atom, p is an integer of l-5 and X is a group represented by formula (II) (wherein L<0>, L<2>, L<4> and L<6> are -O-, -NH-, -NHCO- or -CONH-, L<1>, L<3>, L<5> and L<7> are alkylene, aralkylene or arylene and a-h are 0 or 1).

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 chromogenic white paper storage stability, chromogenic body storage stability, and chemical resistance.

(Prior Art) Recording materials using electron-donating colorless dyes and electron-accepting compounds are already well known as pressure-sensitive paper, heat-sensitive paper, light-sensitive pressure-sensitive paper, electric thermal recording paper, heat-sensitive transfer paper, and the like. For example, UK patent Co/4t04t4#, US 13i1%Ff4#
r00j2, 114tJl, 201% Kosho 40.2
J Tatako, Tokukai Akira! 7-/7ri r36, same 60-l co3
j! 6, 40-123! ! I am familiar with 7 etc.

In recent years, as a recording material, research has been intensively carried out to improve properties such as (1) color development degree III and color development sensitivity, and (2) solidity of color formers.

The present inventors investigated the oil solubility, water solubility, partition coefficient, pi(a, polarity of substituents, We have pursued the development of good recording material materials and recording materials by focusing on bone properties such as changes in crystallinity and solubility depending on position and mixing.

(Object of the Invention) Accordingly, the object of the present invention is to provide a recording material using a material that has good color development, blank paper storage stability, color former storage stability, and chemical resistance, and also satisfies other necessary conditions. It is.

(Structure of the Invention) The object of the present invention was achieved by a recording material characterized by containing a fluoran compound represented by the following general formula (1) as an electron-donating colorless dye.

In the above formula, □ is a hydrogen atom, an alkyl group, or an aryl group fs
R2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, a halogen atom, R3 is a hydrogen atom, an alkyl group, an aryl group, an acyl group R4 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, 71
0 gene atom, alkylthio group, arylthio group, substituted amino group, cyano group, nitro group, acyl group, alkoxy group, R5 is an alkyl group, aryl group, heterocyclic group, ring A
contains a heteroatom and is an integer 1 (X is a group represented by the following general formula (■)).

-(Lo)a-(Ll)b-(R2)c-(R3)d-
(L')e-(R5)f-(L')g-(R7)h-(
n) In the above formula, LOR2R4R6 is 10- -NH--NHCO--CONH- -NH80--8O□N)l--COO-10CO--
N)ICON)i--0CON)i--NHCOO--
8--80--802-Co-', Ll, L'' L
' L7B Full*vn, Aralkire/, Arirenl
axh is an integer of O or l)/ (however, b-c+d-e+
f-g=o) is connected to R5 on the L side.

In detail, as R1, Hs -CH-Cn)i2n-1YZ.

3% -Cn R2n -3, -CHQC)l YZ
, nznm2m-1 (0 is an integer from co to io, m is an integer from 1 to j, Y and z are hydrogen atoms, alkyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups,
Six alkylthio groups, halogen atoms, substituted amino groups, cyano groups, nitro groups, acyl groups, trihalomethyl groups, sulfamoyl groups, and heterocyclic residues. ) is preferred.

For the buttocks, R□ is preferably a methyl group, ethyl group, propyl group, butyl group, etc.

In the above formula, the group represented by R2 is preferably an alkyl group, an alknyl group, an alkynyl group, an alkoxy group, or a halogen atom; Atoms are preferred.

In the above formula, the group n represented by 几 is a hydrogen atom, the number of carbon atoms/~
An alkyl group for r is preferable, and a hydrogen atom, methyl group, or ether group is preferable for r.

R4 is preferably a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an alkenyl group, and may also be a substituent such as a halogen atom or an alkoxy group.

7 to 1 R4 can be substituted on the pen/zene ring, and in the case of plural R4, they may be the same or different.

In the above formula, the ring is preferably be/ze/ring, naphthalene/ring, pyridine ring, pyrimidazine ring, i/dol ring, etc., and the bone is preferably be/ze/ring.

When the ring is substituted with the same -l or different substituent nτ,
Substituents include haloken atoms, nitro groups, cyano groups,
An alkoxy group is preferred, and a chlorine atom and a fluorine atom are particularly preferred.

In the above formula, the substituent represented by R5 is preferably an alkyl group, a benzene ring, a naphthalene/ring, a pyridine field, a furan ring, a coumarin ring, etc., and a benzene ring or a naphthalene/ring is preferable.

Another substituent on R5? Substituents include saturated or unsaturated alkyl groups, cycloalkyl groups, aryl groups, hydroxy groups, alkoxy groups, alkylthio groups, aryloxy groups, arylthio groups, halogen atoms,
dialkylamino group, carbonyl group, carboxyl group,
Carboxyl group, carbamoyl group, alkoxycarbonyl group, acyl group, 7-ano group, nitro group, sulfonyl group,
Examples include isocyanate groups and heterocyclic residues.

Particular examples of substituents for R5 include methyl group, ether group, isopropyl M% t-butyl group, K acyl group, methoxymethyl group, phenoxymethyl group, cyclohexyl group, methoxy group, ethoxy group, phenoxymethoxy group, and phenoxyethoxy group. group, phenoxypropoxy group, chloroethoxy group, methylthio group, ethelthio group, phenylthioethoxy group, phenoxy group, phenylthio group, phenoxyethylthio group, acetyl group, acetoxy group, methoxycarbonyl group, cyano group, formyl group, Trifluoromethyl group, diethylamide group, chlorine atom, fluorine atom, etc. are preferred.

Among the 8 groups in general formula (II), 1,11,3L5,
R7 is linear or branched alkylene, aralkylene,
The number of carbon atoms of each arylene is preferably λθ or less, particularly IO or less.

L'' R3R5L is -CH2--(CH2→2, -(C)12)3-<, C
H2)4--(C)12)5-(C)12. )6-
-(CH2)8 and the like may also have a substituent such as an alkyl group, an alkoxy group, or a halogen atom.

Compound of general formula (1) @ Used in all thermal papers * In order to show sufficient sensitivity, the dispersed grain system of the crystals of the compound is preferably less than 0μ, especially Lri/0μ or less. I want it.

When using the compound of the general formula (1,) in a WV recording material, the melting point of the compound is 7 from the viewpoint of storage stability and solvent resistance.
It is preferably 2,000 or more, particularly preferably 13,000 or more.

When the compound of general formula (I) is used as a recording material, it is preferable that R5 be treated with a substituent in order to obtain storage stability and solvent resistance that can withstand use. Although specific examples are shown, the present invention is not limited to these examples.

Note: Electron-donating colorless dyes according to the present invention include conventionally known triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, inodolylphthalide compounds, leucoauramine compounds, and rhodami/lactam compounds. , triphenylmethane compounds, triazene compounds, spiropyra/fluorene compounds, and other compounds.

The specific series of phthalide shots is listed in the U.S. Reissued Patent Specification No. 23, O.
No. λ, US Patent Specification IJcJ, Tari I.

No. iii, No. 3. Data i, iiJ issue, same issue 3゜hiro/
, No. 114, No. 3. ! Ori, No. 7≠, the specific list of fluoranes is listed in U.S. Bone 8 AIIB Book 3゜t≠,
No. 107, No. 3,627,717, No. J, No. 4/
, No. 0/I, No. 3. da 6ko, lko r issue, same number, i,
tri, 3yo issue, vote counting 3. Octopus o, zio number, same number 3
．． the law of nature! No. 571, Specific PIl of Spirodipira/WA
are listed in the U.S. Patent Specifications 3゜7i, rot, and pyridine/pyridine and pyrazine compounds are listed in the U.S. Patent Specifications J, 7
7j, 4L, No. 2, No. 3 of the same. tji, rt issue,
Same No. 3, −months ≦.

No. 311, the specific file of the fluoran compound is a patent application filed in 1973.
/--24'0ri No. t etc. n.

Examples of electron-accepting compounds that can be used in the recording material of the present invention include phenol derivatives, salicylic acid derivatives, metal salts of aromatic carboxylic acids, clay, bentonite, novolac resins, metal-treated novolac resins, and metal complexes. Ran.

These rows are Tokuko Showa O-ta No. 30P and Tokuko Showaji-i.
≠No. 03, JP-A No. 5--l≠O-butsu t3, JP-A No. 4A
I-61110, JP-A-J7-Jtorrt, JP-A-5R-R'Yory, JP-A-Sho! tar 1isrt issue,
rt from JP-A-40-/767-ri No. 5, JP-A-67-ta
It is stated in the number etc.

As a target for electron-accepting compounds, bisphenol A1
Co, Corbis (J-methyl-μm hydroxyphenyl)
Propane, Kotsu + 2-bis(4L-hydroxyphenyl)hebutane, l,l-bis(蓼-hydroxyphenyl)
Butane, /, l-bis(μm hydroxyphenyl)-ruethylbutane, l,l-bis(3-chlorohydroxyphenyl)-ruethylbutane, bis(j-7
Ril-hydroxyphenyl) sulfone, t,y-bis(μm hydroxyphenylthio)-' + '-dioxahebutane, (French-hydroxyphenyl)-(terisopropoxyphenyl)sul*7, u-hydroxy f
AiFil benzyl ester, co,tasihydroxybenzoic acid-β-phenoxyether ester, co,4t dihydroxy7benzoic acid-α-methyl-β-(J-methoxyphenoxidine ethyl ester, l,3-bis(μm hydroxyphenyl) Furonone, rho(λ, 4L dihydroxyphenyl)-rhophenylpropane, J, j-bis(α-
Methylbenzyl] zinc salicylate, etc.

When the recording material of the present invention is used for thermal paper,
It takes the form IIt-, as described in the specification of the Japanese Patent Application No. 4J-J4#, No. 113, 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-soluble polymer aqueous solution of lI# of about O,j to IQ% is generally used.The dispersion is carried out using a ball mill, a sand mill, a horizontal sand mill, an attritor, a colloidal mill, etc.

The ratio of the electron-donating colorless dye to the electron-accepting compound used is preferably between l:lQ and l:/, and particularly preferably between iHj and 2:3. .

At that time, a thermofusible substance can be included in the thermosensitive coloring layer in order to improve the thermal responsiveness. Representative thermofusible substances include aromatic ethers, thioethers, esters, and/or aliphatic amides or ureides.

These IPlls are published in Japanese Patent Application Publication No. 17-17-2011. r
-r70W44, 4i-zr'yry, 6λ-
1Ori 6ri No. 4, No. 3267 Hiro, No. 4J-/
s/u7r, same Aj-JJj5'A/, patent application flat/-
It is described in No. 444c7, No. 37070, etc.

The series of thermofusible substances include phenethyl biphenyl ether, benzyloxynaphthalene, k-benzylbiphenyl% 'l'l jenoxyethane, l, cozy m-
) lyloxyethane, /-phenoxy-2-p-methoxyphenoxyethane, /-p-methoxyphenoxy-2
-0-Chlorphenoxyethane 1'l Cozy p-fluorophenoxy7ethane, l,3-di-p-methoxyphenoxypro/Nin, /, λ-di-p-methoxyphenoxypro/Nin, l-phenoxy- Col-methoxyphenoxypropane, /-p-methoxyphenoxy7ethoxyλ-p-methoxyphenoxyethane, l, cola-p
-methoxyphenylthioethane, p-methane)*dibenzyloxytolylmethane, (≠-methoxybenzyloxy)
-(J-methyl-chlorophenylcomethane, p-chlorobenzyloxy-p-ethoxyphenyl meta/, etc.).

These are used by finely dispersing them simultaneously with an electron-donating colorless dye or simultaneously with an electron-accepting compound. These usage amounts are added at a weight ratio of -20% to 300% with respect to the electron-receptive compound, and bamboo is added at a weight ratio of -20% to 300%. 0 attack or less is preferable
Yes.

Additives may be added to the carbon solution obtained in this manner as necessary to meet various requirements. In terms of additives, in order to prevent the recording head from becoming dirty during recording, oil-absorbing substances such as inorganic additives and polyurea fillers are dispersed in the binder. Fatty acids, metal soaps, etc. are added to increase the strength. Therefore, in general, in addition to electron-donating colorless dyes and electron-accepting compounds that contribute to color development, thermofusible substances, pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, and fluorescent materials are used. Additives such as photodyes, surfactants, etc. are applied onto the support and the recording material is destroyed.

Furthermore, if necessary, a protective layer may be provided on the surface of the heat-sensitive recording layer. If necessary, one or more layers of the embalming layer may be laminated. In order to correct the curl balance of the support, a coating liquid similar to that of a protective layer may be applied to the back surface for the purpose of improving chemical resistance from the back surface. An adhesive may be applied to the back side and a release paper may be further assembled to form a label.

Usually, the electron-donating colorless dye and the electron-accepting compound are dispersed in a binder and applied. Water-soluble binders are generally used, such as lubrication, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropylcellulose, epichlorohydrin-modified polyamide, and ethylene-
Maleic anhydride copolymer, styrene-maleic anhydride copolymer, inbutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivative, casein, upper 2-ten, etc. Garokera nru. For the purpose of imparting water resistance to the binder of Tako et al., a water resistance agent may be added, or an emulsion of a hydrophobic polymer, specifically, a lamp, styrene-butadiene rubber latex, acrylic resin emulsion, etc. may be added.

The obtained thermal image WL is coated on high-quality paper, high-quality paper with an undercoat layer, synthetic paper, plastic film, etc. At this time, the smoothness specified by JIS-II/RI! From the viewpoint of dot reproducibility, it is preferable to use a support that lasts for at least 100 seconds, particularly for at least 100 seconds.

When providing an undercoat layer as the main component of the pigment on the support, all general M-type pigments and inorganic pigments can be used, but in particular, pigments with an oil absorption level specified by JIS-KsiOl can be used.cc / / 00 or more is preferable.
Specific examples thereof include calcium carbonate, barium sulfate, titanium oxide, talc, waxite, kaolin, calcined kaolin, aluminum hydroxide, amorphous silica, urea-formalin resin powder, borietele/resin powder, and the like.

When these pigments are applied to a support, the amount of pigment is more than 0 f/m, preferably more than 1 f/m.

Binders that can be used in the lower layer include water-soluble polymers and water-insoluble binders, and at least 711% of the binders may be used in combination.

Examples of water-soluble polymers include methyl cellulose, carboxymethyl cellulose, hydroquine ether cellulose, and de/
bu/, gelatin, ambia gum, casein, styrene/
- maleic anhydride copolymer hydrolyzate, ethylene-maleic anhydride copolymer hydrolyzate, inbutylene-maleic anhydride copolymer hydrolyzate, polyvinyl alcohol,
Examples include carboxy-modified polyvinyl alcohol and polyacrylamide.

As the water-insoluble binder, synthetic rubber latex or synthetic resin emulsion is generally used, and examples include styrene-butadiene rubber latex, acrylonitrile-butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion. Keranuru.

The amount of binder used is 3 to io for # family.

The weight t% is preferably less than j-10 weight. The 9 layers of undercoat contain wax, anti-fading agent, surfactant, etc.
L.

Pigments used as additives in the present invention include kaolin, calcined kaolin, talc, waxite, diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide,
Zinc oxide, lithopone, amorphous silica, colloidal silica, calcined gypsum, silica, magneum carbonate, sodium oxide, alumina, barium carbonate, barium sulfate, mica, microballoon, urine x-formalin filler, polyester particles, cellulose filler, etc. There are many.

Metallic soaps include higher fatty acid polyvalent gold 114B, PJ, zinc stearate, steari/! l! aluminum,
Calcium stearate, zinc oleate, etc.
Ru.

In the first aspect of the present invention, it is preferable to use a wax having a melting point of 0 to 1 O @ C in view of head matching properties for facsimile machines.

As a wax, the melting point is l10P-/,! 0”C(7
)%, examples include rough-in wax, polyethylene wax, carnauba wax, microcrystalline wax, camphoria wax, montan wax, and fatty acid amide wax.

Among them, preferable are tl bo2fi/wax, microcrystalline wax, montan wax, and fatty acid amide wax, and particularly preferable are par)fin wax, montan wax, and methylolsteramide wax with a melting point of 50 to 10°C. Yes. Wax is used as an electron-donating colorless dye! ~-Qo'x, *%, preferably,
-1so Jido outside.

As a hindered phenol compound, at least v-2
In the layer order, 1 or more of the 6th positions are substituted with branched alkyl groups.
Preferred are phenol derivatives.

Examples of ultraviolet absorbers include cinnamon i1 derivatives, benzophenone derivatives, benztrialyllyphenol derivatives, and α-cyano-β-phenylcinnamic acid fururu0-
Benzotriazolylphenol, O-benzotri7nolyl-p-chlorophenol, O-benzotriazole-λ, Tei-di-t-butylphenol, O-benzotriazolyl-J, San-di-t-octylphenol, etc. Ruru.

Water-resistant agents include water-soluble initial condensates such as N-methylol urea, N-methylol melamine, and urea-formali 7;
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 group'M complex, inbunare/-maleic anhydride copolymer, etc. And so on.

Materials used for the protective layer include polyvinyl alcohol,
Carboxy-modified polyvinyl alcohol, vinyl acetate-acrylamide copolymer, silicon-modified polyvinyl alcohol, starch, modified starch, methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, gelate/
gum arabic, casein, ft-form hydrolyzate of sterene-maleic acid/co-acid, styrene-maleic acid copolymer half ester raw water decomposition product, isobutylene-maleic anhydride copolymer hydrolyzate, polyacrylamide derivatives, polyvinylpyrrolidone , water-soluble polymers such as polystyrene sulfone rubber, alginate/acid ester, and styrene-butadiene rubber latex, acrylonitrile.
Water-insoluble polymers such as butadiene rubber latex, methyl acrylate-butadiene rubber latex, and vinyl acetate emulsion are used.

Pigments, metal soaps, waxes, water-resistant agents, etc. may be added to the protective layer for the purpose of improving matching properties with the thermal head.

lfc, retention N11/: When coating on the thermosensitive coloring layer, a surfactant may be added in order to obtain a uniform protective layer. Examples of the surfactant include sulfoconophosphate-based alkali metal salts, fluorine-containing surfactants, and the like. Specifically, di(n-hexyl)sulfosuccinic acid, di(
Sodium salts such as 2-ethylhexyl sulfosuccinate, ammonium salts, etc. are preferred, but anionic surfactants are not effective.

U.S. Patent No., JOJ, Hiroshi 7
No. 0, same, jO! ! , ≠ No. 71, same.

zos, ULY No., same, j4(f, No. 346, same, 7/2,607, same, 730. Reference No. 56, same,
730.4Cj No. 7, same! , 103, 4tha issue, same J, 4t/1,2!04j, same≠,oio,.

It takes various forms as described in prior patents such as No. 3j. Most commonly, it consists of at least one sheet containing an electron-donating colorless dye and an electron-accepting compound @gold separately.

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

700, 4tj No. 7, same x, zoo, asr No. Riri, No. 26, same/.

Interfacial polymerization method described in 077, etc., or U.S.% * 3+ "3j≠Q1
Learn the methods etc.

In general, electron-donating colorless dyes are mixed together.
jlG [Alkylated 7-thalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, chlorinated) Synthetic oils such as roughin, Vegetable oils such as cotton oil and castor oil, Animal oils, Mineral oils, etc. A coloring agent sheet is obtained by dissolving the coloring agent in a mixture (mixture, etc.), incorporating it into microcapsules, and applying it to paper, high-quality paper, plastic sheet, resin-coated paper, etc.

The primary electron-accepting compound and optional additives are mixed together and dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol, and then used together with pigments to produce paper, plastic sheets, resin-coated sheets, etc. A developer is obtained by applying it to a support such as the following.

The combination of carboxy-modified styrene-butadiene latex and water-soluble polymer as a binder improves light resistance,
It is preferable from the point of view of water resistance. In addition, as a pigment, the average particle size is 2.
．． From the viewpoint of color developing ability, it is preferable to use calcium carbonate having a particle size of less than 60% by weight of the total pigment.

The amount of the electron-donating colorless dye and the electron-accepting dye to be used depends on the desired coating thickness, the form of the pressure-sensitive recording paper, the capsule manufacturing method, and other conditions, and may be appropriately selected depending on the conditions. Determining this fecal dose is easy for one skilled in the art.

(Practice of the Invention) The following is a description, but the present invention is not limited thereto. Unless otherwise specified in practice, weight percentages are 6 pieces.

Example row-1 1) Dissolve 3 parts of a partial sodium salt of polyvinylbenzenesulfonic acid (manufactured by National Starch Co., Ltd., VER8A, TL!00) in 3 parts of water in a capsule containing an electron-donating colorless dye. . Add an aqueous sodium hydroxide solution to this to adjust the pH to 41.0.

On the other hand, the compound w't≠ of specific row (1) of electron-donating colorless dye
.

1% dissolved diisopropylnaphthalene 1ooH? Part of the sodium salt of the polyvinylbenzenesulfone sulfone
The particles were emulsified and dispersed in 100% of an aqueous solution to obtain an emulsion with a particle size of t% and a diameter of .mu. and .theta..mu. Separately, add 6 parts of melamine, 37 parts by weight of formaldehyde aqueous solution@1, and 30 parts of water to 6 parts of water.
The mixture was heated and stirred to obtain a transparent aqueous solution of the initial polymerized product of melamine formaldehyde. Mix this aqueous solution with the above emulsion.

While stirring, the pH was adjusted to 4.0 with an aqueous phosphorus solution, the temperature of the solution was raised to bs'c, and stirring was continued for A#.

This capsule solution was cooled to room temperature I and adjusted to pH 2,011C with an aqueous sodium hydroxide solution.

For this dispersion, 10 parts by weight of polyvinyl alcohol water, 8 parts of coOO and starch particles! All parts of O were added and water was added to adjust the solid content concentration of the microcapsule dispersion.

This 111 liquid k s o y 7 m of base paper is 197
m f) Apply with an air knife coater so that the solid content is coated, and dry to form M capsules 7 containing electron-donating colorless dye.
-I met you.

[lambda] Preparation of electronic response compound sheet 3, z-his(, α-methyl be/zyl 9 zinc salicylate 1 part, calcium carbonate 20 parts, zinc oxide - 20 parts, hexametal y@sodium/part and water 200 parts Disperse with a sand glider to obtain an average particle size of Jμ.Add 10% PVA water to this dispersion.
0 parts and 10 parts (as solid content) of caloxy-modified SBR latex were added in kW's, and water was added so that the solid content St became 0% to obtain a coating liquid. This I! i liquid jQf/l
J on the original paper of H.

The mixture was coated using an air knife coater so that a solid content of 0.097 m 2 was coated in 1 rb, and dried to obtain an electron-accepting compound sheet.

The surface of the microcapsule sheet containing an electron-donating colorless dye is
When the color was developed by stacking it on an electron-accepting compound sheet and applying a load of 4,400 #/aIL2, the developed color showed a deep black hue, indicating good storage stability.

Implementation PI-2 Compound of specific Pl (3), which is coated with electron-donating colorless dye,
Bisphenols, which are electron-accepting compounds, and thermofusible compounds are mixed together in a ball mill with phenoxy (methoxyphenoxy) propane and 5% polyvinyl alcohol (Kuraray PVA101) aqueous solution of 0ft-7OO2 for one day and night. The particles were dispersed to have a volume average particle diameter of t-Jμ. -10,000 calcined kaolin (person n1silax -P J)
IOff Hexamethalin Soda Q, j% soluble l1l1
60t and dispersed with a homogenizer to reduce the dispersed particle size.
It was set as υμ.

Disperse as above and mix each dispersion 1h electron-donating colorless dye dispersion pIisr, electron-accepting compound dispersion gtot, diaryloxyalkane compound dispersion @ / Of, firing Kaori / dispersion - 22t opening, and further A coating solution was obtained by adding Emulshore 4 (2 and +2% 0 (J-ethylhexyl) aqueous solution of sodium sulfosuccinate) of zinc stearin powder.

The basis weight of this coating liquid! Coat with a wire parser on Of/Wt2 high-quality paper so that the dry coating amount is 417 m.
Calendering was performed to obtain a coated paper.

The n7 obtained in the above manner was coated with a coated paper, a Kyocera ■ thermal head (KIT-co/4-rMPD/), and a thermal printing experimental device with a pressure roll of 100Jrf/cxs placed just before the head. While using the pressure roll VW under the conditions of voltage code V, A pulse cycle/(7 ms), print with pulse width f/, 0, and then measure all the prints with Macbeth reflection density system RD-ta/I.The color density is l・
It was 3≠. In addition, the unprinted areas of the resulting color-forming product exhibited good storage stability and chemical resistance.

Practical row-3 A coated paper was obtained in the same manner as in practical row-co except that the compound in row (3) in practical row (3) was replaced with the compound in row (9). When coloring was mixed in the same manner as in Embrace-co, coloring II was obtained.
! Ij was three times. Furthermore, the colored images and unprinted areas obtained exhibited good performance in terms of storage stability and chemical resistance.

Practical-4 Practical row-K concrete P11 (3) chemical gold concrete lpH (
A coated paper was obtained in the same manner as in Practical Example 1, except that the compound of Isu was used. *The color density was 1.3 when I developed the color in the same way as in the process. Darita. In addition, the obtained N9 colored WiJ image and the unprinted area exhibited excellent storage stability and chemical resistance.

Comparison column practical-2 concrete (3) combination! #! A coated paper was obtained in the same manner as in Example C except that J was replaced with λ-anilino-3-methyl-A-N-diethylaminofuran.

Practical - The coloring result [is 1 6 pieces 9.

Also the coloring obtained 11ii The F color fades over time, and the unprinted areas are the background. The following shows the fog.

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, a fluoran compound represented by the following general formula (I) is used as the electron-donating colorless dye. Recording materials characterized by ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) In the above formula, R_1 represents a hydrogen atom, an alkyl group, an aryl group,
R_2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or a halogen atom; R_3 is a hydrogen atom, an alkyl group, an aryl group, or an acyl group; R_4 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, or an aryloxy group ,
A halogen atom, an alkylthio group, an arylthio group, a substituted amino group, a cyano group, a nitro group, an acyl group, an acyloxy group, R_5 may contain an alkyl group, an aryl group, a heterocyclic group, and Ring A may contain a heteroatom. p represents an integer from 1 to 5, and X represents a group represented by the following general formula (II). -(L^0)_a-(L^1)_b-(L^2)_c-
(L^3)_d-(L^4)_e-(L^5)_f-(
L^6)_g-(L^7)_h-(II) In the above formula, L^0, L^2, L^4, and L^6 are -O-, -N
H-, -NHCO-, -CONH-, -NHSO_2-, -SO_2NH-, -COO-, -
OCO-, -NHCONH-, -OCONH-, -NH
COO-, -S-, -SO-, -SO_2-, -CO-
, L^1, L^3, L^5, L^7 are alkylene, aralkylene, arylene, and a to h are integers of 0 or 1 (
However, it represents b-c+d-e+f-g=0) (connected with R_5 on the L^0 side).