JPS63153182A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a pressure-sensitive or thermal recording material having favorable color forming properties, raw preservability and stability of developed color images, by using a derivative of hydroxybenzenesulfonic acid (or sulfinic acid) as an electron-acceptivie compound, in a recording material comprising an electron-donative colorless dye and the electron-acceptive compound. CONSTITUTION:As an electron-acceptive compound, a compound expressed in general formula (I) is used, wherein R1 is an slkyl, alkoxyl, alkenyl, halogen, hyroxyl or hydrogen, R2 is a 1-10C divalent group, X is a divelent group containing S or O, Ar is an aromatic ring, and n is 1 or 2. The electronacceptive compound, when being combined with an electrondonative colorless dye, gives a developed color image with high density, the image being extremely high in stability. The electron-donative colorless dye may be a triarylmethane compound, a diphenylmethane compound, a xanthene compound, a thiazine compound, a spiropyran compound or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention provides a recording material that conveniently uses an electron-donating colorless dye and an electron-accepting compound, which has improved color development and storage stability. Regarding.

(Prior Art) Recording materials using colorless electron-donating dyes and electron-accepting compounds are already widely available 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/≠Q Hiro≠, US patent≠≠1
0012, rotation tIJ49λ01 special public Sho Otsu 0-23, ri 2λ, JP 17-17-/7-ri, t36, same tO-/23
, j to 6, same 60-/ko 3. ! ! I am familiar with 7 etc.

The performance that the recording material should have is (I1 color development 7 degrees and color development sensitivity are sufficient, (2) no fogging occurs, (31 color development body has sufficient fastness after color development, (
4) Appropriate color hue and compatible with copying machines, (5)
The S/N ratio must be controlled, and 16) the color former must have sufficient chemical resistance, but at present no product has been obtained that completely satisfies these requirements.

(Object of the invention) Therefore, the object of the present invention is to improve color development, shelf life, and color development surface 1.
To provide a recording material l+ using a mental material that has good stability for elephants and satisfies the conditions that the pond should have.

(Structure of the Invention) The object of the present invention has been achieved by a recording material characterized in that a compound represented by the following general formula (I) is used as an electron-donating colorless dye and an electron-accepting compound.

il However, here R1 is an alkyl group, an alkoxy group, an alkenyl group, a halogen atom, a hydroxy group or a hydrogen atom,
R2 represents a divalent group having 1 to 10 carbon atoms, a divalent group containing XViS or O, Ar represents an aromatic ring, and n represents an integer of l or co.

More specifically, R1 is less than or equal to the number of carbon atoms/j, preferably μ
It represents the following alkyl group, alkoxy group, alkenyl group, halogen atom, hydroxy group, or hydrogen atom. Specific examples include methyl group, ethyl group, propyl group, inpropyl group, methoxy group, ethoxy group, allyl group, chlorine atom, fluorine atom, and hydrogen atom.

R2 is a divalent group having 7 to 10 carbon atoms, and particularly preferably linear or branched alkylene, oxaalkylene, thiaalkylene, or alkenylene. Among these, straight-chain fullkylene, oxaalkylene, polyoxaalkylene, thiaalkylene, etc. having a6 or less carbon atoms are excellent in terms of ease of synthesis and ease of producing the product from a tree.

X is a divalent group containing S or 0, preferably S, -O-
This is the case for C-O-1CO.

n represents/or an integer, and the case where n=2 is particularly preferable.

Ar represents a substituted or unsubstituted J-membered or T-membered aromatic ring consisting of a monocyclic ring or a condensed ring. It may contain oxygen atoms, nitrogen atoms, sulfur atoms, etc. in addition to carbon atoms.

From the viewpoint of raw material availability and handling, benzene buoy and naphthalene ring are the most advantageous.

Yang groups having substituents include cyan group, alkylthio group,
Acyl group, alkyl group, aryloxy group, alkoxy group, acylamino group, halo)J atom, alkyloxycarbonyl group, aralkyl group or aralkyloxycarbonyl group, alkenyl group, cycloalkenyl group, oxy group, alkanesulfonyl group, Examples include one or more of carbonato groups, sulfo groups, sulfonato groups, and aryl groups.

Among these, carbon atom Kei/! The following groups preferably have excellent performance.

For example, methyl group, ethyl group, isopropyl group, methquine group, ethoxy group, allyl group, chlorine atom, fluorine atom,
Acetyl group, propionyl group, 7 groups, oxy group,
Examples include methylthio group, methoxycarbonyl group, and chloromethyl group.

Further, in the general formula (I), the -8On- group is preferably located at the para position with respect to the OH group.

When the electron-accepting compound according to the present invention is used as an electron-accepting compound for heat-sensitive recording materials, t.

Those having a melting point of 0C or higher are preferable, and the melting point is preferably 7s 0
Those having a melting point of C~/jO0C are preferred.

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

When combined with an electron-donating colorless dye, it gives a four-density colored image. Furthermore, it has the characteristic that the resulting colored image has extremely high stability.

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

/)/-(≠-hydroquinobenzenesulfonyl)-3-
Benzenethioprononξnλ)/-(<=-Hydroxybenzenesulfonyl)-3
-(≠-methylbenzenethio)propane J)/ -(Hiro-hydroxybenzenesulfonyl)-X
-(≠-hydroxybenzenethio)ethane 4)/, 3-his(≠-hydroxybenzenesulfinyl)propanej)/-(44-hydroxybenzenesulfonyl)-dibenzenesulfonyl-hexane 4)/-(cohydroxybenzenesulfonyl) )-6-
Benzenesulfonyl-hexane7)/,6-bis(Hiro-hydroxybenzenesulfonyl)hexaner)2.2'-bis(μmhydroxybenzenesulfonyl)ethyl ether)/-(4cmhydroxybenzenesulfonyl)-1-72 Noxyethane 10)/-(μm hydroxybenzenesulfonyl)-7
-7 dinoxyethane//)/-(μm hydroxybenzenesulfonyl)-3
-7 dinoxypropane/J)/-(4C-hydroxybenzenesulfonyl)-
2-Phenoxyprono-13) λ-(4!-Hydroxybenzenesulfonyl)-
Examples include 2'-7 dinoxy diethyl ether, 4A-hydroxybenzoic acid (4t-hydroxybenzenesulfonylmethyl) ester, and the like.

These may be used singly or in combination with other electron-accepting compounds (e.g., biphenol A, H-hydroxybenzoic acid benzyl ester, co-, φ-dihydroxybenzoic acid-
β-Hiro-methoxyphenoxyethyl ester and the like are used.

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

Particularly preferred are black xanthine-based compounds, including rhodamine-B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine B (p-chloroanilino)lactam, colabenzylamino-4-diethylaminofluoran, -1 Anilino 6-diethylaminofluorane, co-anilino J-methyl-6-dinithylaminofluorane, co-anilino 3-methyl-4-
N-cyclohexyl-N-methylaminofluorane, -
1-anilino 3-methyl-4-N-ethyl-N-amylaminofluorane, λ-〇-chloroanilino-
Di-diethylaminofluorane-m-chloroanilino-
Bu-diethylaminofluorane, λ-(3,Hiro-dichloroanilino)-4-diethylaminofluorane, λ-octylamino-4-diethylaminofluorane, -1-dihexylamino-6-ethylaminofluorane, ---
m-) dichloromethylanilino-6-diethylaminofluorane, -1butylamino-3-chloro-6-diethylaminofluorane, -1ethoxyethylamino-3-
Chloro-t-diethylaminofluorane, λ-anilino-3-chlorog-diethylaminofluorane, 2-
Diphenylamino-6-diethylaminofluorane, Koani 177-3-methyl-t-diphenylaminofluorane, λ-anilino-3-methyl-j-chloro-6-
Diethylaminofluorane, co-anili/-j-,
+1 thyl-6-dinithylamino-7-methylfluorane, -1 anilino 3-methoxy-6-cyptylaminofluorane, λ-0-chloroanilino-6-cyptylaminofluorane, λ-p-chloroanilino 3- Ethoxy-6-ethylaminofur.

Examples include orane, cophenylated 6-diethylaminofluorane, and the like. These may be used alone or in combination.

When mixing, it is preferable that at least one component accounts for 4 wt% or more.

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

The pressure-sensitive copying paper according to the present invention is disclosed in US Pat. No. 2,10! , Hiro 7
No. 0, same, 101, ≠ No. 77, same.

303, Datori issue, same co,! ≠♂, 3t6, same co,
7/ Ko,! No. 07, same, 730, ≠ j6, same No. 2
, 730.1137, 3.1iar, 2jO, and other prior patents. Pressure-sensitive copying paper can be produced by applying the techniques disclosed in these documents to the electron-accepting compound of the present invention.

The heat-sensitive recording material is produced by sufficiently finely pulverizing 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 a dispersion medium. Further, oil-absorbing pigments such as kaolin, calcined kaolin, talc, waxite, limestone, calcium carbonate, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, titanium oxide, barium carbonate, urea-formalin filler, cellulose filler, etc. To this, add paraffin wax emulsion, latex binder, sensitizer, metal soap, antioxidant, ultraviolet absorber, image preservation improver, etc. as necessary. be able to.

The coating liquid is applied to a support such as paper, plastic sheet, high-quality paper, or neutral high-quality 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.

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

The amounts of each component constituting the heat-sensitive recording material are: ~2 parts by weight of an electron donating colorless dye, 7 to 6 parts by weight of an electron accepting compound, 0 to 30 parts by weight of a thermofusible substance, and 0 to 75 parts by weight of a pigment. , binder/-/3 parts by weight and dispersion medium (solvent)
The amount is N parts.

Electron-donating colorless dyes may be used singly 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-hinyl acetate copolymers, styrene-maleic anhydride copolymers, constituent rubbers, gum arabic, polyvinyl alcohol, and hydroxyethyl cellulose. etc. can be mentioned.

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

As the thermofusible substance, erucic acid, stearamide, methylene bisstearamide, stearic acid-p-anisidide, stearic acid anilide, stearic acid toluide, N-myristoyl-p-anisidine, N-myristoyl- p-7 enethidine, /-methoxysulfonyl-μ-N-stearylcarbamoylbenzene, N-octadecylurea, N-hexadecylurea, N, N/-didodecylurea, phenylcarbamoyloxide dodeca7, p-t-methylphenol Phenoxy acetate, p-phenylphenol-p-chlorophenoxy acetate, Hiro, Hiro'-isobropylidene hismethkinbenzene, β-phenylethyl-p-phenyl phenyl ether, λ-p-chlorobenzyl oxy/naphthalene, λ-benzyloxynaphthalene, l-benzyloxynaphthalene, 2-phenoxyacetyloxynaphthalene, phthalic acid diphenyl ester, /-hydroxy-λ-naphthoic acid phenyl ester, cobenzoyloxynaphthalene, p-benzyloxybenzoic acid benzyl ester, hydroquinone Acetate, or Japanese Patent Publication No. 6l-j7ri♂ri, No. j♂-170 free, or Japanese Patent Publication No. 6l-j7ri/-! There are aromatic ether compounds and aromatic thioether compounds disclosed in No. 7r. For example, l-phenoxy-λ-p-methosyphenoxyethane, β-phenoxyethyl biphenyl, benzyloxynaphthalene, 2,2'-bis-p, p'-methoxyphenoxyethane, /-7 di/-2- Examples include p-methylphenoxyethane.

An ether compound having at least λ aromatic rings with a melting point of ro
A compound having a temperature of 0C to /300C has the advantage of having a high first temperature at which color development starts and a good color density when used in combination with the electron-accepting compound of the present invention.

In that case, it is preferable to use the ether compound in an amount of about 10 to ≠00%, particularly about 10 to -jO%, based on the weight of the nucleo-receptive compound.

Examples of storage improvers include phenol or its derivatives in which at least one or more of the co- or 6-positions is replaced with an alkyl group, and among these, at least 7 or more of the co- or 6-positions are substituted with tert-butyl. A phenol or a derivative thereof is preferred. Moreover, those having a plurality of phenol groups in the molecule are preferable, and those having co- to three heptene groups are particularly preferable. Specific examples of these monsters include bis-[3,3-bis-(Hiro'-hydroxy-3'-
tert-butylphenyl)-phtanoic acid] glycol ester, bis-[3,3-bis-(3'-hydroxy-3'),
μ′-di-tert-butylphenyl)butanoic acidocoglycol ester, bis-[3,3-bis-(2
'-Methyl-μ'-hydroxy-j'-tert-butylphenyl)-butanoic acidocoglycol ester, /, /,! -tris(2-methyl-der-hydroxy-r
-tert-butylphenyl)phthane, Hiroshi, μ'-thiobis(3-methyl-a-tert-butylphenol)
, ≠, Hiro'-thiobis(λ-methyl-4-tert-butylphenol), 2, λ'-methylenebis(Hiro-ethyl-t-tert-
butylphenol), Hiroshi, 3'-butylidenebis(3-methyl-ot-tert)
-butylphenol), Hiroshi, μ'-methylenebis(-16-di-tert-butylphenol), coat-tert-butyl-≠-tert-butoxyphenol, λ, λ-dimethyl-≠-isopropyl-7-tert-
Butyl-6-chromanol, co,--cymethyl-t-t
-7' Chill-! -benzofuranol, ≠ [[μ,6-bis(tertbutylthio)-s-triazine-choyl]amino), 2. j-tert-
Butylphenol etc.

The fecal dosage of these compounds is j-200 weight percent, preferably λo-1oo weight percent, relative to the adult-receptive compound.

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

Further, a fluorescent whitening agent, an oil-soluble fluorescent whitening agent, a conductive agent, a coating aid, an antioxidant, etc. are added to prepare a coated coat.

The coating solution obtained in this way is then coated with A, by coating, blade coating, curtain coating, gravure coating, etc. to a coating solution of 3 to 0. / 7FL 2, and is calendered in some cases.

(Example of the invention) Preparation of dispersion fi+ Electron-donating colorless dye dispersion-/co-anilino 3-methyl-J-N-methyl-N-isoamylaminofluorane-, rff was dispersed overnight with 3% polyvinyl alcohol aqueous solution JOrnl.

(2) Electron-donating colorless dye dispersion-2 Coanilino-3-chloro-4-diethylaminofluorane λ,j1 in 3% polyvinyl alcohol aqueous solution-jm
They dispersed all day and night together with L.

(3) Electron-donating colorless dye dispersion-3 Co-anilino-3-methyl-A-N-methyl-N-cyclohexylaminofluorane! Disperse with 11% polyvinyl alcohol aqueous solution j Ornt in a ball mill all day and night.

(4) Electron-accepting compound dispersion-Hiroshi/-(e-hydroxybenzenesulfonyl)-2-phenoxypropane IO? ,/-7 dinoxy 2-p-methoxyphenoxyethane If/f was mixed and dispersed in a boiler mill for one day with 100 ml of a 1% polyvinyl alcohol aqueous solution.

(5) Shoshiuke G performance compound dispersion-Yo/, A-His (Hiro-Hydroxybenzenesulfonyl)-Hexane 1
0? , 1. -bis-m-methylphenoxyethane rt
was dispersed in a ball mill overnight with an aqueous solution of jqb polyvinyl alcohol at 10θd.

(6) Electron-accepting compound dispersion-6 21λ'-His (Hiro-hydroxybenzenesulfonyl)
-ethyl ether 101!1/ , / , j -tris-j-t-butyluda-hydroxy-4-methylphenylbutane 0.3? , 11-phenoxy-2-p-ethylphenoxyethane 102 was dispersed overnight with j% polyvinyl alcohol aqueous solution.

Coating liquid-l Joshia Kaolin/j1, Thyroid! f was well mixed with the dispersion of (5), and then the dispersion of (I1, (2)) and paraffin wax emulsion zo% dispersion (Cellosol Hiro λr manufactured by Nakasume Yushi Co., Ltd.) If were added.

Coating Solution-2 After thoroughly mixing with the dispersion of Joesia kaolin/It, zinc oxide, 21, and aluminum hydroxide J 9 ft (4), the dispersions of (2) and (3) were added.

Coating liquid-3 Joshia kaolin/jf, minor calcium carbonate!
? Add the emulsion of and coating liquid to the dispersion of (6) and mix well. Next, add the dispersions of (I) and (3) and mix well.

Coating liquid-≠ The same procedure was carried out except that in coating liquid-3, a t/- mixture of the dispersion liquid of (6) and the dispersion liquid of (5) was used instead of the dispersion liquid of (6).

In this way, various coating liquids are obtained.

Example/-μ The above-mentioned coating solution l-≠ was applied to neutral high-quality paper so that the coating radius was 4PK. The coated paper was then dried at 0c for 7 minutes to obtain a coated paper.

Coated paper is heated by facsimile with energy≠omJ/
When heated and colored at a temperature of 1.5 cm, a black printed image was obtained, and the color density of each image was greater than o and Pθ.

The color image obtained in this way shows almost no decrease in color density (not showing any decrease in color density) over a period of 3 months.

Comparative Example An electron-accepting adduct dispersion v4 was prepared using 1 oyft of benzyl p-hydroxybenzoate by the method of dispersion-≠. This liquid was replaced with the dispersion liquid in (5) of Coating liquid -/, and then Coating liquid v4 was prepared in the same manner as above, and applied on high-quality paper.
It was coated and dried to a thickness of m2. A black image was obtained by heat color development, and then the color faded over the course of λ weeks.

Claims (1)

[Scope of Claims] A recording material containing an electron-donating colorless dye and an electron-accepting compound, characterized in that a compound represented by the following general formula (I) is used as the electron-accepting compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, here, R_1 is an alkyl group, alkoxy group, alkenyl group, halogen atom, hydroxy group, or hydrogen atom, and R_2 is a divalent group having 1 to 10 carbon atoms. group, X is a divalent group containing S or O, Ar is an aromatic ring, n is 1 or 2
represents an integer.