JPS60120090A - Recording material - Google Patents

Abstract

PURPOSE:To enhance developed color density and fastness after color development, by a method wherein an aromatic compound having a sulfamoyl group or an aryloxysulfonyl group and two or more hydroxyl groups as substituent groups is used as an electron-acceptive compound. CONSTITUTION:An electron-acceptive compound consisting of an aromatic compound having a subst. or unsubst. sulfamoyl or aryloxysulfonyl group and two or more hydroxyl groups as substituent groups, an electron-donative colorless dye and, optionally, a heat-fusible substance are pulverized and mixed with each other, and the resultant mixture is added to a liquid obtained by dissolving or dispersing a binder in a solvent or a dispersant, thereby preparing a coating liquid. The coating liquid is applied to a base such as a paper, a plastic sheet and a resin-coated paper, followed by drying to obtain a thermal recording material. The electron-donative colorless dye may be a triarylmethane compound, a diphenylmethane compound or the like.

Description

[Detailed description of the invention] <Field of application of the invention> The present invention relates to recording materials.

The recording material according to the present invention utilizes a color-forming reaction between an electron-donating colorless dye and an electron-accepting compound, and particularly contains a substituted or unsubstituted sulfamoyl group or aryloxysulfonyl group and one or more electron-accepting compounds. The present invention relates to a recording material using an aromatic compound having a hydroxy group as a substituent. The electron-accepting compound according to the present invention is particularly useful as an electron-accepting compound for pressure-sensitive recording materials and heat-sensitive recording materials. sheet, electron beam recording sheet,
It is a compound that can be applied to electrostatic recording sheets, photosensitive printing plate materials, stamping materials, type ribbons, ballpoint pen inks, crayons, etc.

<Prior Art> The use of various phenolic compounds as electron-accepting compounds in pressure-sensitive recording materials or heat-sensitive recording materials is disclosed in Japanese Patent Publication No. Sho San〇-ta 3o, No. 032 of Tokko Sho μj-no. -2? Although disclosed in IJO and the like, these phenolic compounds cannot necessarily be said to be satisfactory electron-accepting compounds. That is, when used in combination with an electron-donating colorless dye, the am1 degree of color development is not sufficient, and the fastness of the color former to light, moisture, etc. after color development is insufficient.

- Regarding conventionally known sulfone compounds, bisphenol S has high water solubility, so it is prone to fogging on the background (coloring of areas that are not printed) and moisture. Furthermore, the hydroxydiphenylsulfone compounds disclosed in JP-A No. 17-2101rt also cause large fogging due to water solubility and have low coloring density, so none of them are satisfactory electron-accepting compounds.

<Objective of the Invention> Accordingly, an object of the present invention is to provide a recording material which, when used in combination with an electron-donating colorless dye, has sufficient color density and sufficient fastness of the colored body after coloring.

<Structure of the Invention> The object of the present invention is to use an electron-donating colorless dye, a substituted or unsubstituted sulfamoyl group or an aryloxysulfonyl group as an electron-accepting compound, and an aromatic compound having a hydroxyl group as a t-tit substituent. This is accomplished by recording materials characterized by the use of traps.

Preferred examples of the electron-accepting compounds according to the present invention are represented by the following general formulas [I] to (■).

! In the above general formulas (I) to (M), R1 and R2 may be the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group, and these substituents further include an alkyl group, a halogen R represents an aryl group, and Y represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or an electron-withdrawing group.

-CN, (R', R'' and R# represent a hydrogen atom, an alkyl group, an aralkyl group or an aryl group), etc., nVi or 3;

Among the substituents represented by R in the above general formulas (I) to (n[), a hydrogen atom and an alkyl group having a carbon atom number of /-4 are preferred, particularly a hydrogen atom and a carbon atom number /-4.
44 alkyl groups are preferred.

Among the substituents represented by R2, hydrogen atom, carbon atom number 1
-Ql alkyl groups, aralkyl groups having 7 to 1-2 carbon atoms, and aryl groups having 6 to 1λ carbon atoms are preferred, particularly hydrogen atoms, alkyl groups having 1 to 1 carbon atoms, and 7 to io carbon atoms. An aralkyl group, an aryl group having 6 to 10 carbon atoms, a halogen-substituted aryl group, an alkoxy-substituted aryl group, and a human-oxygen-substituted aryl group are preferred.

Among the substituents represented by R, aryl groups having t-20 carbon atoms are preferred, particularly phenyl groups having 4-4 carbon atoms, naphthyl groups, halogen-substituted phenyl groups, alkyl-substituted phenyl groups, alkoxy-substituted phenyl groups, and acyl groups. Substituted phenyl groups are preferred.

Among the substituents represented by Y, a hydrogen atom and a carbon atom number of 1.
an alkyl group of I, an aralkyl group having 7 to 2 carbon atoms,
Preferably, an aryl group having a carbon atom number of A-/λ, a chlorine atom, a bromine atom, and an electron-withdrawing group having a carbon atom number/I or less,
Particularly hydrogen atoms, alkyl groups with β-hiro carbon atoms, aralkyl groups with 7 to 2 carbon atoms, aryl groups with t to 2 carbon atoms, chlorine atoms, acyl groups with /-f carbon atoms, and carbon atoms. A substituted carbamoyl group having 2 to 3 carbon atoms, a sulfonyl group having 1 to 1 carbon atoms, and a substituted sulfamoyl group having 1 to 5 carbon atoms are preferred.

In the electron-accepting compound according to the present invention, the sulfamoyl group may be N-monosubstituted, N-disubstituted, or unsubstituted, but N-monosubstituted sulfamoyl group is particularly preferred.

When the electron-accepting compound according to the present invention is used as an electron-accepting compound for a heat-sensitive recording material, it is preferable to use one having a melting point of JO@C or more, and particularly one having a melting point of 70°C-oo'c. preferable.

The characteristics of the electron-accepting compound according to the present invention include the following.

(By combining with 11 electron-donating colorless dye, it gives a high-density colored image.

(2) The color image is stable, and there is little fading due to aging, humidity, light, etc.

(3) Low water solubility.

(4) Stable without sublimation.

(5) Synthesis is easy and easy, and products of high purity can be obtained in high yield. The raw materials are also cheap.

Next, specific examples of the electron-accepting compound of the present invention will be shown, but the present invention is not limited thereto.

(i) N-phenyl-, j-dihydroxybenzenesulfonamide (ii) N-ethyl-N-phenyl-λ, j-dihydroxybenzenesulfonamide Ni+) N-hekydylu-, j-dihydroxybenzenesulfonamide (iV) N-octyl-λl! l Diedroxybenzenesulfonamide (V) N-benzyl-2,! l dihydroxybenzenesulfonamide (yi) phenyl-J,, t-dihydroxybenzenesulfonate (V++) β-su7 thi-, j-dihydroxybenzenesulfonate (viii) p-chloroU phenyl-co,! -dihydroxybenzenesulfonate (+X) p-)zyl-2,! -dihydroxybenzenesulfonate (X) p-isopropylphenyl-J, z-dihydroxybenzenesulfonate (Xi) N-hexyl-2,3-dihydroxy-6-
Naphthalenesulfonamide (Xii) N-octyl-2,3-dihydride
-Naphthalenesulfonamide (Xiii) N-benzyl-2,3-dihydroxy-
t-Naphthalenesulfonamide (XiV) N-r-octyloxypropyl-2゜3-
Dihydroxy-6-naphthalenesulfonamide (XV) N-β-phenylethyl-λ, 3-dihydroxy-6-naphthalenesulfonamide (xvi) N-phenylruco, 3-dihydroxy-4
-Naphthalenesulfonamide (XVti) N-o-butyl-2,
J-dihydroxy-t-naphthalenesulfonamide (XViit) N-p-tbutyl7 x=nyl-
, J-dihydroxy-6-naphthalenesulfonamide (XiX) N-ethyl-N-phenyl-,3-dihydroxy-t-naphthalenesulfonamide (XX) N-butyl-N-phenyl-2,3-dihydroxy-6- Naphthalenesulfonic acid amide (XXi) Phenylluco, 3-dihydroxy-6-
Naphthalenesulfonate (XXii) p-isoprobylphenyl-co, 3-dihydroxy-6-naphthalenesulfonate rxxiii > p-chlorophenyl-λ, 3-dihydroxy-6-naphthalenesulfonate CxX Is7thyruco, 3-dihydroxy-6-naphthalenesulfonate etc. These may be used alone or in combination with other electron-accepting compounds (for example, bisphenol A 1 μm hydroxybenzoic acid benzyl ester, etc.).

The electron-accepting compound according to the present invention is synthesized by a conventionally known method. For example, it can be obtained by reacting a compound represented by the following general formula (V) with a compound represented by the following general formula (Vl) or (■) in a non-aqueous medium in the presence of a base.

(In the above formula, R' represents a hydrogen atom, an acyl group or a lower alkyl group, and X represents a halogen atom. n represents co or 3.) R-OH (■) (In the above formula, R1, R2, RF (same as above) These are published, for example, on Beilstein EI, /J, page 3μ.

Examples of the electron-donating colorless dye used in the present invention include triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, and spiropyran compounds.

To give some examples of these, triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-4-dimethylaminophthalide C (crystal violet lactone), 3゜3-bis(p- dimethylaminophenyl)methane)', J-(p-dimethylaminophenyl)-3-(/, J-dimethylindol-3-yl)phthalide, '(P-dimethylaminophenyl)-3
-(Cotatilindol-3-yl)phthalide, etc., and diphenylmethane compounds include Hiroshi, 4A'-
Bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoolamine, N-,2,μ
, j-trichlorophenylleucoauramine, etc.
Examples of xanthine compounds include rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, codibenzylamino-t-jethylaminofluorone,
-anilino-6-diethylaminofluorane, -anilino-3-methyl-4-diethylaminofluorane,
co-anilino-3-methyl-4-cyclohexylmethylaminofluorane, co-6-rio o-anilino-t-diethylaminofluorane, 'm-chloroanilino-t
-diethylaminofluorane, λ-(3,4t-dichloroanilino)-t-diethylaminofluorane, co-octylamino-6-diethylaminofluorane, colahexylamino-6-diethylaminofluorane, λ-
m-) dichloromethylanilino-6-diethylaminofluorane, coptylamino-J-rio-4-
Diethylaminofluorane, λ-ethoxyethylamino-3-chloro-6-diethylaminofluorane, -1anilino-3-rio-1,-diethylaminofluorane, -2-diphenylamino-t-diethylaminofluorane, -1 AniJ/-J-methyl-6-diphenyl-minofluorane, co-anilino 3-methyl-yo-koo-6y ethylaminofluoran, λ-anilino 3-methyl-t-diethylamino-7-methylfluoran, -1-anilino 3-Methoxy6-cyptylaminofluorane, λ-o-chloroanilino-t-dibutylaminofluorane, λ-p-chloroanilino-3-ethoxy-6-ethylaminofluorane, cophenyl-6
-diethylaminofluorane, etc. Thiadidine compounds include benzoylleucomethylene blue, p-nitrobenzylleucomethylene blue, etc. Spiro compounds include 3-methyl-spiro-cinasitopyran, 3-ethyl-spiro- Dinaphthopyran, 3,3'-cyclorosespiro-dinaphthopyran, 3-benzylspiro-dinaphthopyran, 3-methyl-naphtho-(3-methoxy-benzo)-spiropyran, 3-propyl-spiro-
Examples include dibenzobilane. These may be used alone or in combination.

Next, a specific method for manufacturing the recording material of the present invention will be described.

The pressure-sensitive copying paper according to the present invention is disclosed in US Pat. ! 0j,
No. 41-70, same λ, ! Ojt, No. 71, same.

gos, at, same, j4Lf, 344, same λ
, 712. ! No. 07, No. 730, No. μ56, No. 730, No. 4I77, No. 3. It can take various forms as described in prior patents such as Reference No. 110 and the like. Most commonly, it will consist of at least one pair of sheets separately containing an electron-donating colorless dye and an electron-accepting compound according to the invention. That is, electron-donating colorless dyes may be used alone or in combination with solvents (synthetic oils such as alkylated naphthalene, algylated diphenyl, alkylated diphenylmethane, and alkylated terphenyl; vegetable oils such as cotton oil and castor oil; animal oils; mineral oils; A color former sheet can be prepared by dissolving it in a mixture of these materials, dispersing it in a binder, or containing it in microcapsules, and then applying it to a support such as paper, plastic sheet, resin-coated paper, etc. Alternatively, an electron-accepting compound may be dispersed alone or in combination with other electron-accepting compounds in a binder such as styrene-butadiene latex or polyvinyl alcohol, and applied to a support such as paper, plastic sheet, or resin-coated paper. A developer sheet is obtained by coating.

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.

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

100, $77, a method using coacervation of a hydrophilic colloid sol as described in J, too, art, British Patent No. 147,797, JrO,
444CJ issue, same? JP, No. 2A4', same l.

There are interfacial polymerization methods described in 076, etc.

The heat-sensitive recording material is produced by sufficiently finely pulverizing and mixing an electron-donating colorless dye, an electron-accepting compound according to the present invention, and, if necessary, a thermofusible substance, in a liquid in which a binder is dissolved or dispersed in a solvent or dispersion medium. Furthermore, inorganic pigments such as kaolin, talc, and calcium carbonate are added to form a coating liquid. Add paraffin wax emulsion, latex binder, sensitivity enhancer, metal soap, etc. as necessary.
Antioxidants, ultraviolet absorbers, etc. can be added.

The coating solution is applied to a support such as paper, plastic sheet, or resin-coated paper and dried. When preparing a coating liquid, all the components may be mixed and pulverized at the same time from the beginning, or they may be combined in appropriate combinations, pulverized and dispersed separately, and then mixed.

Further, the coating liquid may be poured into the support.

The components constituting the heat-sensitive recording material are 1-2 parts by weight of an electron-donating colorless dye, 7-6 parts by weight of an electron-accepting compound, 0-30 parts by weight of a thermofusible substance, and 0-16 parts by weight of a pigment. , binder 1, 11 heavy background part and dispersion medium (solvent) 20-300
Parts by weight.

゛ Electron-donating colorless dyes may be used alone or in combination. Water is most desirable as the dispersion medium (solvent).

Examples of binders used in the present invention include styrene-butadiene copolymers, alkyd resins, acrylamide copolymers, vinyl chloride-vinyl acetate copolymers, styrene-maleic anhydride copolymers, synthetic rubbers, gum arabic, polyvinyl alcohol, hydroxy Examples include ethyl cellulose.

In particular, water-soluble binders such as gum arabic, polyvinyl alcohol, hydroxymethyl cellulose, and carboxymethyl cellulose are desirable in relation to the dispersion medium (solvent).

Thermofusible substances include erucic acid, stearic acid, behenic acid, palmitic acid, stearamide,
Behenic acid amide, stearic acid anilide, stearic acid toluiside, N-myristoyl-p-anisidine, N-
Myristoyl-p-phenetidine, l-methoxycarbonyl-ter-N-stearylcarbamoylbenzene, N-
Octadecyl urea, N-hexadecyl urea, N, N
'-shi) "y" silurea, phenylcarbamoyloxydodecane, p-t-butylphenolphenoxyacetate, p-phenylphenol-p-chlorophenoxyacetate, 4c, $'-isopropyritine bismethoxybenzene, β-phenylethyl-p -phenyl phenyl ether, 2-p-chlorobenzyloxynaphthalene, copenzyloxynaphthalene, l-benzyloxynaphthalene, cophenoxyacetyloxynaphthalene, phthalic acid diphenyl ester, l-hydroxy-1-naphthoic acid phenyl ester, λ -benzoyloxynaphthalene, p-benzyloxybenzoic acid hensyl ester, hydroquinone acetate, etc. are used.

These substances are colorless solids at room temperature and are heated at temperatures suitable for copying heating, i.e. 70°C. It is a substance that has a sharp melting point around /1.00C.

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

Example 1 (1) Preparation of color former sheet Co-anilino 3-methyl-6-dinithylaminofluoran//f alkylated naphthalene JOf, which is an electron-donating colorless dye, was dissolved. This solution was added to water j02 in which gelatin 61 and gum arabic 4At had been dissolved, with vigorous stirring, and emulsified to form oil droplets with a diameter of lμ to lOμ, and then water 2jtOf was added thereto. Acetic acid was added little by little to bring the pH to approximately μg to cause coacervation, creating a wall of gelatin and gum arabic around the oil droplets, and formalin was added and 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 Disperse electron-accepting compound phenylco, 3-dihydroxy-6-naphthalene sulfonate (201 ft) in 5% polyvinyl alcohol aqueous solution -001, and further add kaolin (Jossia kaolin) λoy to disperse well. This was used as a coating liquid. The resulting coating solution is applied to paper and dried to obtain a developer sheet.

When the thus prepared color forming agent sheet and color developing agent sheet were brought into contact with each other and subjected to pressure or impact, a black image was instantaneously obtained. This image had high density and excellent light resistance and heat resistance.

Example 2 λ-7 Nilino 3-Mefk, an electron-donating colorless dye
-4-N-Methyl-N-cyclohexylaminofluorane jf was added to 6% polyvinyl alcohol (Ken Measurement Tatachi,
The mixture was dispersed in a ball mill with an aqueous SO2 solution overnight. On the other hand, similarly, N-hexyl-2,3-dihydroxy-t-naphthalenesulfonamide lO1, which is an electron-accepting compound, was dispersed in a ball mill overnight with lOoy of a 5% polyvinyl alcohol aqueous solution, and these two dispersions were mixed. After that, add kaolin (Jossia kaolin) and disperse well, and then paraffin wax emulsion 5ocs dispersion (Middle East oil and fat Cellosol s4Aλ♂)! v was added to prepare a coating liquid.

It was coated onto a base paper having a basis weight of 20 m2 to a solid content of 697 m2, and dried at to''c for 1 minute to obtain a coated paper.

Coated paper is heated by facsimile with energy of 10 mJ/
When heated and colored with crn2, a black printed image was obtained.

Moreover, the obtained color image had excellent light resistance and heat resistance.

Example 3 λ-0-chloroanilino-diethylaminofluoran jl/ was used as the electron-donating colorless dye in place of the electron-donating colorless dye in Example 2, and an electron-accepting compound was used in place of the electron-accepting compound. N-phenyl-2,
3-dihydroxybenzenesulfonamide and 2.2-
A coated paper was obtained in the same manner as in Example 2 using bis-(μm hydroxyphenyl)propane 17.

When coated paper is colored by facsimile, a black impression is obtained.

Example 4 Electron-donating colorless dye 1-a-sono-3-chloro-6-diethylaminofluorane/,j? and electron-accepting compound phenyl-λ,3-dihydroxybenzenesulfonate (0.19 g) and gold acetate (10 ml), and the solid content was applied onto base paper*/, 0? /m. When the color density was measured, the color density was 0.
It was 73.

Example 5 An experiment similar to Example 3 was conducted using the electron-accepting compound /, 31 of Example 3. Color density is l.

It was Oθ.

Comparative Example 1 An experiment similar to Example 13 was conducted using 0.52 of λ and cocose (4t-hydroxyphenyl)propane as an electron-accepting compound instead of the electron-accepting compound of Example 3. The color density was 0.31.

Comparative Example 2 Comparative Example 1 using the electron-accepting compound /, jf of Comparative Example 1
A similar experiment was conducted. The color density was 0°26.

Comparative Example 3 31! as an electron-accepting compound instead of the electron-accepting compound of Example 3! -bis-(α-methylbenzyl)zinc salicylate 0. An experiment similar to Example 3 was conducted using If. The color density was 0.50.

Comparing Example f114.5 with Comparative Examples 1 and 2.3, it is clear that the electron-accepting compound of the present invention has extremely high coloring properties.

Claims (1)

[Claims] In a recording material using an electron-donating colorless dye and an electron-accepting compound, the substituted or unsubstituted sulfamoyl group tyc in the electron-accepting compound is an aryloxysulfonyl group and an aromatic substance having λ or more hydroxy groups as substituents. A recording material characterized by being a group compound.