JPS6054883A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a sufficient developed color density and enhance fastness of a developed color, by blending an electron-donative colorless dye with an electron-acceptive compound which is a naphthylphenylsulfone derivative having a hydroxyl group as a substituent group. CONSTITUTION:One or more of electron-donative colorless dyes used singly or in combination are dissolved in a solvent such as a synthetic oil and a vegetable oil, the resultant solution is dispersed in a binder, and the resultant material is applied to a base such as a paper and a plastic paper to produce a color former sheet. On the other hand, one or more naphthylphenylsulfone derivatives used singly or in combination are dispersed in styrene-butadiene latex or the like, and the resultant material is applied to a base such as a paper to produce a color developer sheet. When the color former sheet and the color developer sheet are brought into contact with each other and a pressure or an impact is exerted thereon, a black image is instantaneously obtained which has a high density and excellent light resistance and heat resistance.

Description

[Detailed description 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 records using a naphthylphenyl sulfone derivative having a hydroxyl group as a substituent as an electron-accepting compound. Regarding materials.

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. It is a compound that can be applied to electron beam recording sheets, electrostatic recording sheets, photosensitive printing plates, stamping materials, type ribbons, ballpoint pen inks, crayons, etc.

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. 4c0-ta-30, No. 4AOJ, No. 4AOJ, No. 4AOJ, No. 4AOJ, etc. However, these phenolic compounds are not necessarily satisfactory electron-accepting compounds. That is, when used in combination with an electron-donating colorless dye, the coloring density is not sufficient, and the coloring material after coloring does not have sufficient fastness to light, moisture, etc.

Regarding conventionally known sulfone compounds, bisphenol S is highly water-soluble and therefore causes a large amount of fogging on the background (coloring of areas not printed) and moisture.

Also, JP-A-57-. The hydroxydiphenyl sulfone compounds disclosed in No. 2IOlrt also have large fog due to their water solubility, so none of them are satisfactory electron-accepting compounds.

Therefore, an object of the present invention is to provide a recording material which has a sufficient color p degree when used in combination with an electron-donating colorless dye and has a sufficient fastness of the colored body after coloring.

The object of the present invention has been achieved by a recording material characterized in that it uses an electron-donating colorless dye and a naphthylphenyl sulfone derivative having a hydroxyl group as a substituent as an electron-accepting compound.

Among the electron-accepting compounds according to the present invention, preferred ones are represented by the following general formula CI) or (If).

The substituent represented by Y represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or an electron-withdrawing group.

The substituent represented by Z represents a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, a hydroxy group, or an electron-withdrawing group.

SO□几, CN, (几, 几', 几" represent a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group), and the like.

In the above general formula (1) or (II), among the substituents represented by Y, a hydrogen atom, an alkyl group having carbon atoms/~g, an aralkyl group having carbon atoms 7 to 1λ, and a carbon atom number 6 to 1 Aryl groups, chlorine atoms, bromine atoms, and electron-withdrawing groups with the following carbon atoms are preferred, particularly hydrogen atoms, alkyl groups with 7 to 2 carbon atoms, aralkyl groups with 7 to 2 carbon atoms, and electron-withdrawing groups with the following carbon atoms: Aryl group with 6 to 1 carbon atoms, chlorine atom, acyl group with 1 carbon atoms, substituted carbamoyl group with 2 to 2 carbon atoms, sulfonyl group with carbon number/-f, and substituted sulfamoyl group with carbon number/-4 Groups are preferred.

Among the groups represented by Z, hydrogen atoms, alkyl groups with carbon atoms / -f, chlorine atoms, bromine atoms, alkoxy groups with carbon atoms / -f, hydroxy groups, and electron-withdrawing groups with carbon atoms less than or equal to Particularly preferred is a hydrogen atom, an alkyl group having 1 carbon atoms, a chlorine atom, an alkoxy group having 1 carbon atoms, a hydroxy group, an acyl group having 1 carbon atoms, and a substitution with λ to 2 carbon atoms. A carbamoyl group, a sulfonyl group having 1/-4 carbon atoms, and a substituted sulfamoyl group having 1/-t carbon atoms are 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 that the electron-accepting compound has a melting point of jO"C or higher, particularly 7o"c-xoo 0c.
It is preferable to have a melting point of .

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

(1) In combination with an electron-donating colorless dye, a high-density colored image is produced.

(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) It is easy to synthesize and can be obtained in high yield and purity. The raw materials are also cheap.

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

/) ≠-α-naphthylsulfonylphenol +2)
3-Methyl-≠-α-naphthylsulfonylphenol 3) 3-ethyl-Hiro-α-naphthylsulfonylphenol 4’) j-Impropyl-gu α-naphthylsulfonylphenol j) 4cmβ-naphthylsulfonylphenol/-L A)
3-Methyl-≠-β-naphthylsulfonylphenol7) 3-ethyl-≠-β-naphthylsulfonylphenolf)j-4soprovir-≠-β-naphthylsulfonylphenol, -ruta) 2-chloro-α-naphthylsulfonylphenol 10) 2-l Rolow β-naphthylsulfonylphenol//) +-[/-Hydroxynaphthalenesulfonyl (
≠)) Phenol/2) a-(2-hydroxynaphthalenesulfonyl (
2)) Phenol 13) Hiro-benzenesulfonyl l-naphthol 80 ≠-(ko, Hiro-dimethylbenzenesulfonyl)-/-
naphthol lj) ≠-(2,j-dimethylbenzenesulfonyl)
-/-Naphthol16) ≠-p, =) Glucosulfonyl-l-naphtho-/
7) 7-penzenesulfonyl-λ-naphthol II)
Examples include t-benzenesulfony-λ-naphthol.

These may be used alone or in combination, or in combination with other electron-accepting compounds (eg, bisphenols, ≠-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 (III) and a compound represented by the following general formula (IV) in a nonaqueous medium in the presence of a catalyst.

In the above formulas (II) and (IV), Y and 2 have the above meanings, and X is a halogen atom, such as a chlorine atom or a bromine atom. Also, as a catalyst, AIQ! 3.F
ecg3, Znα2, Snα5bc15 or BF3
A Lewis acid such as These manufacturing methods include, for example, Be1
llstein, E[+1,,I! 2~rj! stated on the page.

Another method is synthesis by dehydration condensation of an aromatic sulfonic acid compound that may have a hydroxy group and an aromatic compound that may have a hydroxy group.

As the electron-donating colorless dye used in the present invention, triarylmethane compounds, diphenylmethane compounds, xanthine compounds, thiazine compounds, spiropyran compounds, etc. are used.

Some examples of these triarylmethane compounds include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (i.e., crystal violet lactone), 3゜3-bis( p-dimethylami/phenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(/,3-dimethylindol-3-yl)phthalide, 3(1)-dimethylaminophenyl)-
Examples of diphenylmethane compounds include 3-(λ-methylindoτ-3-yl)phthalide, tt, a'
-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leucoauramine, N-2,Hir'l''lichlorophenylleucoauramine, etc., and xanthine compounds include rhodamine-B-anilinolactam. , Rhodamine (p-nitroanilino)lactam, Rhodamine B (p-chloroanilino)lactam,
co-anilino-t-diethylaminofluorane, λ-anilino-t-diethylaminofluorane, co-anilino-3-methyl-6-dinithylamino/fluora/
, noanilino-3-methyl-6-cyclohexylmethylamino/fluoran, 2-0-chloroanilino-6-dinithylaminofluoran, λ-m-chloroanilino t
- Diethylaminofluorane! -(J, Hiro-dichloroanilino)-A-diethylaminofluorane, co-octylamino-t-diethylaminofluorane, colahexylamino-4-diethylaminofluorane, λ-m
-) Dichloromethylanilino-6-diethylaminofluorane, λ-butylamino-3-chloro-t-diethylaminofluorane, λ-ethoxyethylamino-3-chloro-6-diethylaminofluorane, λ-anili/-
3-rioo-1-diethylaminofluorane, co-phenylamino-6-diethylaminofluoran, 2-anilino-3-methyl-t-diphenylami/fluoran, co-anilino-3-methyl-y-chloro-t-diethylaminofluoran, -1-anilino-3-methyl-t-
Diethylamino-7-methylfluorane, co-anili/
-3-methoxy t-dibutylaminofluorane, 2-〇-chloroanilino-t-dibutylaminofluorane, chloroanilino-3-ethoxy-6-diethylaminofluorane, 2-phenyl-6-diethylaminofluorane, etc. Aphthiazine compounds include 3, benzoyl leucomethylene blue, p-nitrobenzyl leucomethylene blue, etc., and spiro compounds include 3-
Methyl-spiro-dinaphthopyran, 3-cyclotyl-spirodinaphthopyran, 3. J/-Cyclolose Spirosina 7 Tobiran, 3-Benzyl Spiro-Dinaphthopyran, 3
-Methyl-naphtho-(3-methoxy-benzo)-spiropyran, 3-propyl-spiro-dibenzopyran, and the like. 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 Patent No. 2 SO! ,4/
No. 70, same, 2,! 0! , #7/issue, same co.

top, qr number, same number, j$f, JJA number, same number 2.7
/2.107, 2,730. 'lfi! No. A, No. +2.730, No. Fj7, No. J, II/I, 1!
It can take various forms as described in prior patents such as No. O. 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, alkylated 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. In addition, electron-accepting compounds, alone or in combination, or together with other electron-accepting compounds, are dispersed in a binder such as styrene-butadiene latex or polyvinyl alcohol.
A developer sheet is obtained by applying the color developer to a support such as paper or resin-coated paper.

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 for manufacturing capsules is described in US Patent λ.

A method utilizing coacervation of a hydrophilic colloid sol described in No. 100.4117, Ibid., I, Too, Use, British Patent No. 1t7,727, Ibid. to,
3rd issue, 1st issue, 2nd issue, 1st issue.

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 amounts of each component constituting the heat-sensitive recording material are 1-2 parts by weight of an electron-donating colorless dye, 1-2 parts by weight of an electron-accepting compound, 0-30 parts by weight of a thermofusible substance, and 0-30 parts by weight of a pigment o-is. , binder/-16 parts by weight and dispersion medium (solvent) -0 to 300
Parts by weight.

One or more electron-donating colorless dyes may be used 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, Bravia rubber, polyvinyl alcohol, and hydroxyethyl cellulose. etc. can be mentioned.

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).

As the thermofusible substance, stearic acid anilide, benzoin, α-su7tol benzoate, β-
Naphthol p-methylbenzoate, halal-phenylphenol p-chlorophenoxyacetate, v, φ'-
Cyclohexylitene diphene/-ludiacetate,! ,l
'-Isoprohyritene dimethoxybenzene, β-phenylethyl-p-phenyl ether, λ-p-chlorobenzyloxynaphculene, λ-benzyloxynaphthalene, l-benzyloxynaphthalene, 2-phenoxyacetyloxynaphthalene, N -Octadecylurea, N-
Hexadecyl urea, N, N/-cytotecylurea, phenylcarbamoyloxydodecane, stearic acid amide, behenic acid amide, behenic acid, stearic acid, erucic acid, palmitic acid, /chlorhydroxybenzoic acid methyl ester, seaphenyl phthalate Nisdel, triphenyl phosphate, para-hydroxydipheniether, co, 2-bis(≠-(β-hydroxyethoxy)phenylene/V)propane, para-bis(β-hydroxyethoxy)be/ze/, hydroquinone diphenylene One or more types of acetate etc. can be used.

These substances are colorless solids at room temperature and have sharp melting points at temperatures suitable for copying heating temperatures, that is, around 70-160°C.

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

Example 1 ■ Preparation of color former sheet Noanilino-3-methyl- which is an electron-donating colorless dye
6-Dinithylaminofluorane/9 was dissolved in alkylated naphthalene 30f. This solution was added to water jOf in which gelatin 6f and gum arabic φq were dissolved with vigorous stirring and emulsified to form oil droplets with a diameter of lμ to 10μ.
Added water. Acetic acid was added little by little to adjust the pH to cause coacervation, forming a wall of gelatin and gum arabic around the oil droplets.Formalin was added, the pH was lowered, and the wall was hardened.

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

0 Preparation of color developer sheet V-α-naphthylsulfonylphenol which is an electron-accepting compound + 2 Off 1% $ ribinyl alcohol aqueous solution 2
The mixture was dispersed in σoy, and 20f of kaolin (Jossia kaolin) was further added and dispersed well to obtain a coating liquid. The obtained 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 high density and excellent light resistance and heat resistance.

Example 2 Coanilino 3-methyl-, an electron-donating colorless dye
A-N-methyl-N-cyclohexylaminofluorane jg! The mixture was dispersed overnight in a ball mill with an aqueous solution of polyvinyl alcohol (polyvinyl alcohol, polymerization degree: 10θθ) in a ball mill. On the other hand, similarly, l is an electron-accepting compound.
10 fl of -α-naphthylsulfonylphenol was dispersed with s% polyvinyl alcohol aqueous solution tL/00 f in a ball mill for a day and night, and after mixing these two types of dispersions, 20 f of kaolin (Jossia kaolin) was added and well dispersed, and then /e Rough-in Wax Emulsion jQ Chi Dispersion (Middle East Oil Cellosol #12r) sy was added to prepare a coating liquid.

The coating liquid was applied onto a base paper having a basis weight of jOf/yn2 so that the solid content coating amount was tyim2, and to 0c
After drying for 1 minute, a coated paper was obtained.

Coated paper is heated by facsimile energy ≠ Om J
/ car 2, a black printed image was obtained.

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

Example 3 Co-9-chloroanilino-6-dinithylaminofluorane jy was used as the electron-donating colorless dye in place of the electron-donating colorless dye in Example 1, and in place of the electron-accepting compound, electron Coated paper was prepared in the same manner as in Example C using q-benzenesulfonyl-l-naphthol ty and co,2-bis-(+-hydroxypheni)prono(nQ,f) as acceptor compounds. Obtained.

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

Example 4 Co-anilino 3-chloro-t-diethylaminofluoran/, jf, which is an electron-donating colorless dye, and l-β-naphthylsulfonylphenol, which is an electron-accepting compound.
jf was dissolved in acetone/00 g and coated on the atom so that the solid content coating amount was 1.017 m2. When the color development me was measured, the color development a degree was 0.77;

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

It was 00.

Comparative Example 1 An experiment similar to Example 3 was conducted using 2,2-bis-(≠-hydroxyphenyl)propane o, zy as an electron-accepting compound instead of the electron-accepting compound of Example 3. The color density was 00SS.

Comparative Example 2 Electron-accepting compound of Comparative Example 1/Comparative Example 1 using IQ
A similar experiment was conducted. The color density was 0.000.

Comparative Example 3 As an electron-accepting compound instead of the electron-accepting compound of Example 3, 3. An experiment similar to Example 3 was conducted using zinc j-bis-(α-methylbenzyl)salicylate o, sy. The color density was 00SO.

Comparing Example ≠, j and Comparative Example 11λ, 3, it is clear that the electron-accepting compound of the present invention has extremely high coloring properties.

Claims (1)

[Claims] A recording material using an electron-donating colorless dye and an electron-accepting compound, wherein the electron-accepting compound is a naphthylphenyl sulfone derivative having a hydroxy group as a substituent.