JPS62233286A - Recording material - Google Patents

Abstract

PURPOSE:To obtain good color developing properties, shelf stability in raw, and stability of coloring image, by containing a hydroxyphenyl sulfone derivative having a specific substituting group as an electron accepting compound. CONSTITUTION:As an electron accepting compound, a recording material contains a hydroxyaryl sulfone derivative having an aryloxy alkyloxy group as a substituting group, as shown by a formula I. In the recording material, a sufficient coloring density is obtained, and the coloring dyestuff is so remarkably stable as to be almost prevented from the discoloring and fading due to long-time light-irradiation, heating or moistening, thus allowing a long-term storage of recording, and the problems of the coloring in a non-coloring part due to a solvent, etc. and the discoloring and fading of the coloring body due to fats and oils, or chemicals, etc. are eliminated. Therefore, the recording material has ideal performances as an electron accepting compound for recording material.

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 2. i4cmtAu ri, US patent ψψ
70012, same tAlt34ri 20. Tokuko Akiru 0-23
,Y22. '% Kaisho 17-t7? , 135 tO-/ko J, jj&, 60-/ko 3. ! - I am familiar with 17 etc.

The performance that a recording material should have is (2) sufficient color density and color development sensitivity; (2) no fogging;
(3) The fastness of the colored material after coloring is sufficient; (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.

In particular, the development of heat-sensitive recording materials has been remarkable in recent years, but heat-sensitive recording materials have drawbacks such as fogging due to solvents and the like, and discoloration and fading of coloring bodies due to oils, fats, chemicals, etc. Therefore, when it comes into contact with stationery and office supplies such as water-based ink, oil-based ink, fluorescent pen, ink, adhesive, glue, diazo developer, or cosmetics such as no/de cream and milky lotion, the white part may develop color. Or,
The coloring part of the coloring part was discolored and the product value was significantly impaired.The present inventors investigated the oil bathability, water solubility, partition coefficient, Focusing on characteristics such as the polarity of the pKa substituent, the position of the substituent, and changes in crystalline solubility when mixed, efforts have been made to develop good materials for recording materials and recording materials.

(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) The object of the present invention has been achieved by a recording material characterized by containing a hydroxyarylsulfone derivative having an aryloxyalkyloxy group as a substituent as an electron-accepting compound.

Preferred examples of the compounds according to the present invention include compounds represented by the following general formula.

λ X In the formula, Ar represents an aryl group, X represents a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom, and m and n represent integers.

Note that the alkyl group represents a saturated or unsaturated alkyl group or a cycloalkyl group, which has a substituent such as an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acylamino group, an aminocarbonyl group, or a cyano group. Even if you do (.

In addition, the oryl group represents a phenyl group, a naphthyl group, or a heteroaromatic ring group, and these include an alkyl group, an alkoxy group, an aryloxy group, a), a rogen atom, a nitro group,
It may have a substituent such as a cyan group, a substituted carbamoyl group, a substituted sulfamoyl group, a substituted amino group, a substituted oxycarbonyl group, a substituted oxysulfonyl group, a thioal=rji-cy group, an arylsulfonyl group, or a phenyl group.

Among the substituents represented by Ar in the formula, the number of carbon atoms is 6 to 2λ
Of the substituents represented by An alkoxy group, a chlorine atom and a fluorine atom are preferred.

Among the substituents of the aryl group represented by Ar, an alkyl group having /, /2 carbon atoms, an aralkyl group having 7 to III carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a phenyl group, or an alkoxy group A carbonyl group is preferred.

Preferred examples of the aryl group represented by "A" include phenyl group, tolyl group, ethylphenyl group, propylphenyl group, ; group, 7enethylphenyl group, cumylphenyl group, xylyl group, dipheneterphenyl group, methoxyphenyl group, ethoxyphenyl group, benzyloxyphenyl group, octyloxyphenyl group, dotesyloxyphenyl group, chlorophenyl group, fluorophenyl group, phenylphenyl group group, hexyloxycarbonylphenyl group, benzyloxycarbonylphenyl group, dodecyloxycarbonylphenyl group, naphthyl group,
Examples include methylnaphthyl group and chloronaphthyl group.

The substitution position is preferably the ortho, meta or nu-position with respect to the phenolsulfonyl group, and the no-position is particularly preferred.

The sulfone derivative according to the present invention preferably has a total number of carbon atoms of 1 or more, particularly preferably 20 or more, from the viewpoint of water insolubility.

The recording material using the sulfone derivative according to the present invention has sufficient color density, and the developed dye is extremely stable, and hardly discolors or fades even with long-term light irradiation, heating, or humidification, so it is suitable for long-term storage of records. This is particularly advantageous from this point of view. In addition, when used in heat-sensitive recording materials, there is no drawback that uncolored areas develop color due to solvents, etc., or the colored body discolors or fades due to oils, fats, chemicals, etc., making it ideal as an electron-accepting compound for recording materials. It has similar performance.

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

l-Hydroxyphenyl-μ'-β-phenoxyethoxyphenylsulfone, l-hydroxy-3-chloro-φ
'-β-phenoxyethoxyphenyl sulfone, μm hydroxy-3-methylphenyl-μ'-β-phenoxyethoxyphenyl sulfone, ≠-hydroxy-3-propylphenyl-g/-β-phenoxyethoxyphenyl sulfone, ≠- Hydroxy-3-isopropylphenyl-g/-β-phenoxypropoxyphenylsulfone, ≠-hydroxy-7phenyl-μ'-β-phenoxypropoxyphenylsulfone, μmHydroxyphenyl-≠'-r-phenoxypropoxyphenylsulfo/,
l-hydroxyphenyl-2'-β-phenoxyphenyl sulfo/, μm hydroxyphenyl-ψ′-β-tolyloxyethoxyphenyl sulfo/, μm hydroxyphenyl-μ′-β-P-methoxyphenoxyethoxyphenyl sulfone, μm hydroxy Phenyl-μ/-p
-Methylmercaptophenoxyethoxyphenyl sulfone, φ-hydroxyphenyl-φ/-P-ethylmercaptophenoxyethoxyphenyl sulfone, ≠lyhydroxyphenyl-j'-δ-P-methoxyphenoxybutoxyphenyl sulfone, and the like.

These may be used alone or in combination.

In addition, these electron-accepting compounds are used in combination with well-known electron-accepting compounds such as salicylic acid derivatives, phenol derivatives, phenolic resins, and acid clay. Tertiary butylphenol, Hiro-phenylphenol, Hiro-hydroxydiphenoxide, α-naphthol, β-naphthol, hexyl-Hiro-hydroxybenzoate, u, 2'-dihydroxybiphenyl, 2.2-bis(μm hydroxyphenyl) fluorophore/ (Bisphenol A), 4C,4
u -inviridene bis(2-methylphenol), i
, i-bis-(3-chloro-μm hydroxyphenyl)
Cyclohexane, /, /-bis-methylcyclohexylidene diphenol, ≠.

Hiro'-dihydroxydiphenyl sulfide, '1a-
Bis(≠'-hydroxycumyl)benzene, benzyloxycarbonylphenol %'l''jμ'-trihydroxybensiphenone, 2.2'.

μ, μ′-tetrahydroxybenzophenone, μ-dimethyl hydroxyphthalate, methyl l-hydroxybenzoate, 2.4c, 4C′-)lyhydroxydiphenylsulfone, 1. Terbis-p-hydroxyphenyl ester, 1,6-bis-p-hydroxyphenoxyhexane, l-hydroxybenzoic acid tolyl, Hiro-hydroxybenzoic acid α-phenylbenzyl ester, μm hydroxybenzyl
/ Ank Kaori Ml -y enylprobyl, μm phenethyl hydroxybenzoate, Hiro-hydroxybenzoic acid-p-
Chlorobenzyl, J-hydroxybenzoic acid-p-methoxybenzyl, μm hydroxybenzoic acid benzyl ester, ψ-hydroxybenzoic acid-m-chlorobenzyl ester, μm hydroxybenzoic acid β-phenethyl ester,
μm hydroxy-2', ≠'-dimethyldiphenyl sulfone, β-7 enetel orcellinate, cinnamyl olicellinate, orcellin e-o-chlorophenoxyethyl ester.

0-ethylphenoxyethyl orselinate, 0-phenylphenoxyethyl orselinate, m-phenylphenoxyethyl orselinate, co.

μm dihydroxybenzoic acid-β-J'-t-duty-μ'-hydroxyphenoxyether ester, t-t-
Methyl-μmp-hydroxyphenylsulfonyloxybenzene, ≠-N-pendylsulfamoylphenol, 2. ≠-Dihydroxyamne S, fragrance W1. - p-methylbenzyl ester, 2. ≠-dihydroxybenzoic acid-
β-phenoxyethyl ester, co≠-dihydroxy-6-methylbenzoic acid benzyl ester, bis-l-hydroxyphenylacetate methyl, ditolylthiourea, ψ
g/-Diacetyldiphenylthioflair, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3, tertiary-tertiarybutylsalicylic acid, 3°! -didodecylsalicylic acid, 3-methyl-! -i/dylsalicylic acid, 3-phenyl-j-(α.

α-dimethylbenzyl)salicylic acid, 3. J--G (
α-Methylbenzyl)salicylic acid, 2-hydroxy-7
- aromatic carboxylic acids such as benzyl-3-naphthoic acid,
3. Tajinicyclo is ntashenyl salicylic acid, μ-β
- p-Methoxyphenoxyethoxysaccharide or zinc salt, para-butylphenol-acetylene position (power β, etc.) Organic color developers such as phenolic resins, and these organic color developers such as zinc, magnesium, aluminum, etc.
Salts with polyvalent metals such as calcium, titanium, manganese, tin, and barium, and hydrohalic acids such as hydrogen chloride, hydrogen bromide, and hydrogen iodide, boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid, and peroxide. Chlorine modified, aluminum, zinc, nickel,
Inorganic acids such as halides such as tin, titanium, boron, acid clay, activated clay, attapulgide, bentonite, colloidal silica, aluminum silicate, magnesium silicate, zinc silicate, tin silicate, zinc rhodan, zinc chloride, iron stearate, naphthene Inorganic color developers such as cobalt, nickel peroxide, and ammonium nitrate; aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, and stearic acid; benzoic acid, paratertiary butylbenzoic acid, and phthalic acid. , gallic acid, etc. are used.

Electron-donating colorless dyes according to the present invention include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucoolamine compounds, rhodamine lactam compounds, and triphenylmethane compounds. There are various compounds such as triazene-based compounds, spiropyran-based compounds, and triarylmethane-based compounds.
3゜3-bis(p-dimethylaminophenyl)-1-dimethylaminophthalide (i.e. crystal violet lactone), J, J-bis(p-dimethylaminophenyl)phthalide, j-(p-dimethylaminophenyl)- 3
-(/,J-dimethylindo-A/ -,J-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(
2-methylindol-3-yl) phthalide, etc., and diphenylmethane compounds include ≠, q'-bis-dimethylaminobenzhydrin benzyl ether, N
-Halophenyl-leucoauramine, N-2, 蓼.

! -trichlorophenylleucoolamine, etc., and xanthine compounds include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, 2-
Dibenzylamino-O-diethylaminofluorane, co-anilino-diethylaminofluorane, 2-anilino-3-methyl-6-diethylaminofluorane, no-anilino-3-methyl-6-cyclohexylmethylaminofluorane, no-0-chloroanilino -6-diethylaminofluorane 7.2-m-chloroanilino-6-diethylaminofluorane, 2-(39μm dichloroanilino)-A-diethylaminofluorane, λ-octylamino-t-diethylaminofluorane, 2- Dihexylamino-t-diethylaminofluorane, λ-m-trifluoromethylanilino-6-diethylaminofluorane, λ-butylamino-3-chloro-6-diethylaminofluorane, 2-ethoxyethylamino-3-chloro-6- diethylaminofluorane, -2-p-chloroanilino-3-methyl-6-sibutylaminofluorane,
λ-anilino 3-methyl-6-sioctylaminofluorane, λ-anilino 3-chloro≦-diethylaminofluoran, 2-diphenylamino-ot-diethylaminofluoran, λ-anilino 3-methyl-6-siphenylamino Fluoran, 2-phenyl-6-diethylaminofluoran, 2-anilino-3-methyl-AN
-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-y-chloroo-6-') ethylaminofluorane, no-anilino-3-methyl-4-diethylamine-7-methylfluorane, λ- Anilino 3-methoxy t-diptylaminofluorane, λ-o-chloroanilino-6-cyptylaminofluorane, λ-p-
Chloroanili/-J-ethoxy-6-N-ethyl-N-
Isoamylaminofluorane, λ-0-chloroanilino A-p-butylanilinofluorane, λ-゛anilino 3-pentadecyl-6-diethylaminofluorane,
λ-anilino 3-ethyl-6-dibutylaminofluorane, coaerino-3-methyl-μ', j/-dichlorofluoran, 2-o-)cyidino-3-methyl-t-
Diisopropylamino-g/, 5/-dimethylaminofluorane, co-anilino-3-ethyl-
N-ethyl-N-ynamylaminofluorane, λ-anilino 3-methyl-AN-ethyl-N-r-methoxypropylaminofluorane, co-anilino 3-chloro-+-N-ethyl-N-ynamylamino Examples of fluorane include thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue. Examples of spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3, 3/-cyclolosebirodinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)spiropyran, 3-pyropyl-spiro-dibenzobilane, trisdimethylaminofluorene lactone, and the like.

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.

When used with pressure sensitive paper, U.S. Patent No. 2.50! ,μ7
No. 0, same 2. Tao Yu, lA7/issue, same λ.

! 0ri, ψrri, same 2. Tahiro, 31. A, same! ,
7/2,507, 2,730. ≠jt issue, same number 2,
730. Kou No. 37, No. 3103tAOv, No. J, 9
No. 111.2jO, same aot003. It can take the form of Keyana, as described in prior patents such as No. R.

Most commonly they consist of a pair of sheets containing separately an electron-donating colorless dye and an electron-accepting compound.

For methods of manufacturing capsules, see U.S. Pat.
A method using coacervation of a hydrophilic colloid sol described in British Patent No. 71,7,727 and British Patent No. 910. tAu
J No. 219, 21a4L, Id.

Examples include the interfacial polymerization method described in U.S. Pat.

In general, electron-donating colorless dyes are used singly or in combination to provide solvent resistance (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 or mixtures thereof, etc.)
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, MBnFf coated paper, etc.

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. Obtain a color developer sheet by coating it on a support such as.

The amounts of the electron-donating colorless dye and the electron-accepting compound to be used depend on the desired fabric 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, a water-soluble polymer aqueous solution having a concentration of about 0% to 0% is generally used, and the dispersion is carried out using a ball mill, sand mill, or
Horizontal sand mill.

This can be done using an attritor, colloid mill, etc.

The ratio by weight of the electron-donating colorless dye to the electron-accepting compound used is preferably between /:IQ and /:l, and particularly preferably between l:j and -2:3. that time,
Nitrogen-containing organic compounds such as fatty acid amides, acetoacetanilide, diphenylamine, penzamide, carbazole, etc. or λ.

J-di-m-tolylbutane, 0-fluorobenzoyldurene, chlorobenzoylmesitylene, ≠.

μ′-dimethylbiphenyl, or carboxylic acid esters such as dimethyl isobutanoate, diphenyl phthalate, dimethyl terephthalate, methacryloxybiphenyl, etc., or polyether compounds such as di-m
-) lyloxyethane, β-phenoxyethoxyanisole, l-phenoxy-2-p-ethylphenoxyethane, bis-β-(p-methoxyphenoxy)ethoxymethane, /-J/-)tylphenoxy-λ“-ethyl Phenoxyethane, /-tolyloxy-2-p-methylphenoxyethane, l,2-diphenoxyethane, /
, lA-diphenoxybutane, bis-β-(p-thiomethoxyphenoxy)ethyl ether, l-phenoxy-
λ-p-chlorophenoxyethane, l-2'-methylphenoxy 2-μ〃-ethyloxyphenoxyethane,
It is preferable to use a compound with a melting point of 71'C-/30'C, such as /-41'-methylphenoxy-2-μ"-fluorophenoxyethane, in combination with a colorless dye or an electron-accepting compound. In particular, it is preferable to disperse it simultaneously with a colorless dye from the viewpoint of preventing fogging.The amount of these is added at a weight ratio of -20% to 300% relative to the electron-accepting compound.
Particularly preferred is 1Ao% or more/jO% 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 the support to constitute the recording material.

Specifically, pigments such as kaolin, calcined kaolin, Merck, zinc oxide diatomaceous earth, calcium carbonate, aluminum hydroxide, magnesium hydroxide, calcined oxide, silica, magnesium carbonate, titanium oxide, alumina, barium carbonate, and sulfuric acid are used as pigments. Barium, mica, microballoon, urea-formalin filler, polyethylene particles, cellulose filler, etc. particle size 0. / or l! Selected from μ. As waxes, paraffin wax,
In addition to carboxy-modified paraffin wax, Kaunaparow wax, microcrystalline wax, polyethylene wax, and higher fatty acid esters, etc.

Examples of the Kinkyuseki Gun include polyvalent metal salts of higher fatty acids, ie, zinc stearate, aluminum stearate, calcium stearate, zinc oleate, and the like.

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, imbutylene-maleic anhydride copolymer, and stele/-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-resisting agents (gelling agents, cross-linking agents) are added, or emulsions of hydrophobic polymers, specifically, stainless-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 in an amount of about λ~/Ol//yys 2.

Furthermore, a YJ layer of approximately 0.2 to 2 μm consisting of a water-soluble or water-dispersible polymer compound such as polyvinyl alcohol, hydroxyethyl starch, or epoxy-modified polyacrylamide and a crosslinking agent is provided on the coating surface layer to improve resistance. You can also do that.

In addition, when used for thermal paper, 0LS2.22tjrI
No. 2tt01ju, Tokuko Shoyu λ-201μ2, etc. Alternatively, operations such as preheating, humidity control, or stretching the coated paper may be performed prior to recording.

Examples of electrically conductive thermal paper include Japanese Patent Application Publication No. 2003-100013, No. 3, and JO.
- Manufactured by the method described in .mu.r. No. 30 and the like.

Generally, a conductive layer is formed by coating a support such as paper with a coating liquid in which a conductive substance, a basic dye mainly composed of a fluoran derivative, and an electron-accepting compound are dispersed together with bagondar, or by coating a conductive substance on the support. And on top of that, a colorless dye;
The electrically conductive thermal paper of the present invention is produced by applying a coating liquid in which an electron-accepting substance and a binder are dispersed.

Note that the sensitivity can also be improved by using the thermofusible substance described above in combination.

For example, the photosensitive and pressure sensitive paper is published in Japanese Patent Application Laid-Open No. 37-1999! It is manufactured by the method described in 36 etc. Generally silver iodobromide, silver bromide, silver behenate, Michler's ketone, benzoin derivatives,
A photopolymerization initiator such as a benzophenone derivative and a crosslinking agent such as a polyfunctional monomer such as a polyallylated compound, poly(meth)acrylate, or poly(meth)acrylamide are used together with a colorless dye and optionally a solvent to produce 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 to be colored.

The electron-accepting compound according to the present invention is synthesized by a known method. For example, it is synthesized by reacting the corresponding eg bisphenol S with an aryloxyalkyl halide or an aryloxyalkyl tosylate in the presence of potassium carbonate.

These methods and reaction conditions are already detailed in our pending specification.

<Synthesis example> Bisphenol S and β-
0.001 mol of phenoxyethyl tosylate, respectively.
0 rmol was weighed out. To this, 1 mole of potassium carbonate Q and 100 ml of dimethylformamide were added and stirred on a hot water bath for 3 hours.

The desired monoether and diether as a by-product were obtained.

Using methanol as a reconsolidation solvent, the target product, ≠-hydroxyphenyl-μ'-β-phenoxyethoxyphenylsulfone, was isolated as white crystals with a melting point of 177 to t0C.

The yield was 37%.

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

Examples/■ Preparation of color former sheet Co-anilino 3-methyl- which is an electron-donating colorless dye
6-Dinithylaminofluorane/, 9-alkylated naphthalene 30. SIK was dissolved. Add this solution to gelatin
g and gum arabic≠l were added to a dissolved water toy with vigorous stirring to emulsify them to form oil droplets with a diameter of lμ to ioμ, and then water 2jO9 was added. Add acetic acid little by little and p
Coacervation was caused by setting H to about μ to create a wall of gelatin and gum arabic around the oil droplets, and after adding formalin, the pH was increased to harden the wall.

The thus obtained microcapsule dispersion was applied to paper and dried to obtain a color former sheet.

■ Preparation of color developer sheet μm hydroxyphenyl-μ′, an electron-accepting compound
-β-phenoxyethoxyphenylsulfone 2079
Dispersed in 2% polyvinyl alcohol aqueous solution 20ogK,
Further, 20% of kaolin (Jossia kaolin) was added (dispersed) to form a coating liquid.The resulting coating liquid was applied to paper and dried to obtain a color developer sheet.

When the thus prepared color former sheet and color developer sheet were brought into contact with each other and pressure or impact was applied, a black printed image was instantaneously obtained. This image had a high # degree and excellent light resistance and heat resistance.

Example 2 In place of the electron-accepting compound in the developer sheet of Example 1, ψ
-Hydroxyphenyl-ψ'-β-p-methoxyphenoxyphenylsulfone 109 and μ-β-p-methoxyphenoxyethoxysalicylic acid zinc salt 109 were used. Using 2% polyvinyl alcohol 2009 as a dispersion medium, the particles were dispersed using a horizontal sand mill until the particle diameters were i and rμ.

A developer sheet was obtained in the same manner as in Example 1. When color was developed in the same manner as in Example 1, a black printed image was obtained.

This image had high density (excellent light resistance and heat resistance) and sufficient chemical resistance (fingerprints, alcohol).

Example 3 λ-anilino-3-chloro-6-dinithylaminofluorane and 2-anilino-3-methyl-6-N-methyl-
Equivalent (heavy t) mixture of N-cyclohexylaminofluorane, Hiro-hydroxyphenyl μl-β-p-methoxyphenoxyethoxyphenylsulfone, l-phenoxyco(μ-ethylphenoxy)ethane, 209 each
was weighed and separately dispersed in a ball mill overnight with 100 g of 3% polyvinyl alcohol (Cran PVA/(7T) aqueous solution to obtain a volume average particle size of 3μ.Meanwhile, calcined kaolin (Anisilex-DeJ) 1011 was dispersed in hexamethalin. It was dispersed using a homogenizer together with itog, an O00% solution of acid soda.

The above dispersions were dispersed for 1 m, and each of the dispersions were prepared as follows: electron-donating colorless dye dispersion No. 9, electron-accepting compound dispersion No. 10y, thermofusible substance dispersion No. 11. A coating liquid was obtained by mixing 229 parts of the calcined kaolin dispersion liquid and further adding Emulsion Hiroshi I of zinc stearate and 2% aqueous solution J9 of sodium (2-ethylhexyl)sulfosuccinate. The basis weight of this coating liquid! Dry on high quality paper of rOji/m2, coating amount is &g/
Apply with a wire bar so that it becomes ffl 2, and ro
The coated paper was dried for 5 minutes in an oc oven and calendered to obtain a coated paper.

Color density is Fujitsu High Speed Fax 1JFF-x000
The color density was measured using a Macbeth RD-271 densitometer. On the other hand, chemical resistance was evaluated by impregnating filter paper with ethanol and castor oil and superimposing it on the colored surface of the recording paper obtained by the above method to evaluate the degree of fogging in the white area and decolorization (discoloration and fading) in the colored area. .

The color density was /,01, and it showed a sufficiently legible level in the ethanol and castor oil contact tests.

It can be seen that it has extremely excellent performance.

Claims (1)

[Claims] A recording material containing an electron-donating colorless dye and an electron-accepting compound, characterized in that the electron-accepting compound contains a hydroxyphenylsulfone derivative having an aryloxyalkyloxy group as a substituent.