JPH02196687A - Recording material - Google Patents

Abstract

PURPOSE:To enhance color forming properties by containing an electron donating leuco dye, an electron acceptive compound and a compound having at least one aryl group and a dialkylamino group and specific in the total number of carbon atoms and an m.p. CONSTITUTION:An electron donating leuco dye, an electron acceptive compound and a compound having at least one of an aryl group and a dialkylamino group and containing 32 or less carbon atoms in total and having an m.p. of 60-140 deg.C are contained. As this compound 1-m-dimethylaminophenoxy-2-phenoxyethane, 1-p-dimethylaminophenoxy-2-o-ethoxyphenoxyethane and 1-octyloxy-5- diethylaminonaphthalene are designated and said compound is pref. used in an amount of 10-500% by wt. of the electron acceptive compound and used in a form of a microdispersion or film when used for a recording material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a recording material, and particularly to a recording material with improved color development.

(Prior Art) Recording materials using electron-donating colorless dyes and electron-accepting compounds are already well known as pressure-sensitive paper, thermal paper, light-sensitive pressure-sensitive paper, electrically conductive thermal recording paper, thermal transfer paper, and the like. For example, British Patent No. 2140449, U.S. Patent No. 4480052, U.S. Patent No. 4436920, Japanese Patent Publication No. 60-23992, Japanese Unexamined Patent Publication No. 57
-179836, 60-12'3556, 60-1
I am familiar with 23557 etc.

As a recording material, in recent years (1) Color density and color sensitivity
(2) Research is being carried out to improve properties such as the fastness of coloring bodies.

The present inventors have investigated the oil solubility, water solubility, partition coefficient, polarity of the pKa1 substituent, position of the Shin substituent, crystallinity when mixed, for each of the electron-donating colorless dye and the electron-accepting compound. Focusing on characteristics such as changes in solubility, we have pursued the development of good materials for recording materials and recording materials.

(Objective of the Invention) Therefore, an object of the present invention is to provide a recording material using a material that has good color development and satisfies other requirements.

(Structure of the Invention) The object of the present invention is to provide an electron-donating colorless dye, an electron-accepting compound, and a compound having at least one aryl group or dialkylamino group, having a total number of carbon atoms of 32 or less, and a melting point of 60°C to 14
This was achieved by a recording material characterized by containing a compound at 0°C.

Preferred compounds of the present invention are shown in General 2N).

Ar-〇-R(1) A substituent such as a thio group, an arylsulfonyl group, or a phenyl group may be present.

A more preferred compound of the present invention is a compound represented by general formula (I[).

In the above formula, Ar represents an aryl group, R represents an aryl group or an alkyl group, and either Ar or R has a dialkylamino group.

In addition, an alkyl group represents a saturated, unsaturated, or cycloalkyl group, and these are substituents such as an aryl group, an alkoxy group, an aryloxy group, an arylthio group, an acyloxy group, a halogen atom, an acylamino group, an aminocarbonyl group, or a cyano group. It may have.

In addition, the aryl group represents a phenyl group, a naphthyl group, or a heterocyclic group, and these include an alkyl group, an alkoxy group,
Aryloxy group, halogen atom, nitro group, cyano group, substituted carbamoyl group, substituted sulfamoyl group, substituted amino group, substituted oxycarbonyl group, substituted oxysulfonyl group, alkyl Ar1-0R+ -〇-Art
(II) In the above formula, Arc and Ar2 represent an aryl group,
R+ represents a divalent group, and at least one of Arc and Art has a dialkylamino group.

Ar, Ar2 is preferably a phenyl group or a naphthyl group, which may have a substituent, from the viewpoint of raw material cost and synthetic handling.

In detail, the substituents include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, methoxy group,
Ethoxy group, propoxy group, butoxy group, methoxyethyl group, ethoxyethyl group, phenoxy group, benzyloxy group, methoxyphenoxy group, tolyloxy group, chlorine atom, bromine atom, fluorine atom, nitro group, cyano group, acetyl group, benzoyl group, phenylacetyl group, methylsulfonyl group, phenylsulfonyl group, acetylamide 7 group,
Examples include methylthio group, ethylthio group, and phenyl group.

R3 is preferably a divalent group having 18 or less carbon atoms, particularly 12 or less carbon atoms.

R is more preferably an alkylene group or an arylene group,
These are -CO2--5Ch --3O-3OCOOC
O2 -NHCONH--NHCO□--CONH-C) (O
It may be linked by H-.

As R1, Cp Htq (Z Cp Hz-) --C,R
Particularly preferred are those represented by 2,-(Z-C,R2,) and Z-C,Htq.

Here, p, q, x, y are integers from 1 to 18, r is an integer from 0 to 4, and Z is -Co2S.

t S OS O-C0-OCO2--
NHCONH--NHCOl-CONH--CHoH-
1 represents a single bond.

Preferred examples of CP R21C and H2y include -C
H2--(CR2)2-1-(CH2)3-1-(CH
2) 4-1(CH2'6% (CH2)10
.

etc. can be mentioned.

The dialkylamino group is represented by Rz Rs N-, and R2 and Rs are methyl group, ethyl group, n-propyl group, 15O-propyl group, n-butyl group, 1so
-butyl group, n-amyl group, iso-amyl group, n-
Hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-dodecyl group, n-octadecyl group, methoxypropyl group, ethoxypropyl group, phenoxyethyl group, cyclopentyl group, cyclohexyl group, tetrahydrofurfuryl group , benzyl group, phenethyl group, etc.

R2 and Rs may be bonded to each other to form a ring which may contain a 5- to 8-membered heteroatom, such as piperidine, morpholine, piperazine, hexamethyleneimine, pentamethyleneimine, and the like.

Rz Rs N- includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, N-ethyl-N-iso-amylamino group, N-ethyl-N-1so-butylamino group, N-ethyl- N
-hexylamino group, N-methyl-N-propylamino group, N-ethyl-N-tetrahydrofurfurylamino group, N-ethyl-N-cyclopentylamino group, pentamethyleneimino group, N-ethyl-N-methF Preferred are oxypropylamino group, N-ethyl-N-ethoxypropylamino group, and the like.

Next, specific examples related to the present invention will be shown, but the present invention is not limited thereto.

l-m-dimethylaminophenoxy-2-phenoxyethane, l-m-dimethylaminophenoxy-2-p-methoxyphenoxyethane, l-m-dimethylami/phenoxy-2-I)-chlorophenoxyethane, ■-m-
Dimethylaminophenoxy-2-p-methylphenoxyethane, 1-m-diethylaminophenoxy-2-phenoxyethane, l-m-diethylaminophenoxy-2
-p-methoxyphenoxyethane, l-m-diethylaminophenoxy-2-p-methylphenoxyethane, ■
-m-diethylaminophenoxy-2-p-chlorophenoxyethane, t-p-dimethylaminophenoxy-2
-Phenoxyethane, 1-p-dimethylaminophenoxy-2-p-methoxyphenoxyethane, 1-p-dimethylaminophenoxy-2-m-ethylphenoxyethane, 1-p-dimethylaminophenoxy-2-0-ethoxyphenoxy Ethane, 1-p-diethylaminophenoxy-2-phenoxyethane, 1-p-dibutylaminophenoxy-2-phenoxyethane, 1-p-dimethylaminophenoxy-5-p-methoxyphenoxy-3-
Oxapencune, l-m-diethylaminophenoxy-
12-phenoxydodecane, 1 m-diethylaminophenoxy-2-β-naphthyloxyethane, 1-m-N
-Methyl-N-propylaminophenoxy-2-phenoxyethane, 1-m-N-methyl-N-cyclohexylaminophenoxy-2-phenoxyethane, 1.2-bis(m-dimethylaminophenoxy)ethane, 1.2 −
Examples include bis(m-diethylaminophenoxy)ethane, p-methoxybenzyl-m-diethylaminophenyl ether, p-methoxybenzyl-m-dimethylaminophenyl ether, and 1-octyloxy-5-diethylaminonaphthalene.

Electron-donating colorless dyes according to the present invention include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, indolyl phthalide compounds, leucoauramine compounds, rhodamine lactam compounds, and triphenylmethane compounds. , triazene compounds, spiropyran compounds, and fluorene compounds.

Specific examples of phthalides can be found in the US reissued patent specification contribution 23.0
No. 24, U.S. Patent Specification Contribution 3. ．． No. 491゜111, No. 3.491.112, No. 3.491.116 and No. 3.509.174; specific examples of fluorans are given in U.S. Patent Specification No. 3.624.107; 3.6
No. 27.787, No. 3.641.011, No. 3,
No. 462.828, No. 3.681,390, No. 3
．． No. 920.510, No. 3.959.571, and specific examples of spiropyrans can be found in U.S. Patent Specification No. 3.971.8.
No. 08, pyridine-based and pyrazine-based compounds are disclosed in U.S. Patent Specifications No. 3.775.424 and No. 13,853.8.
Specific examples of fluorene compounds are described in Japanese Patent Application No. 61-240989, etc.

Among these, fluoran compounds are particularly preferred. Specific examples include 2-anilino-3-methyl-6-dinithylaminofluorane, 2-anilino-3-methyl-6-N-cyclohexyl-N-methylaminofluorane, 2-p-chloroanilino-3 -methyl-6-sibutylaminofluorane,
2-anilino-3-methyl-6-sioctylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino -3-methyl-
6-N-ethyl-N-ynamylaminofluorane, 2
-anilino-3-methyl-6-N-ethyl-N-dodecylaminofluorane, 2-anilino-3-methoxy-6
-sibutylaminofluorane, 2-o-chloroanilino-6-sibutylaminofluorane, 2-〇-chloroanilino-5-p-butylaminofluorane, 2-anilino-3-pentadecyl-6-diethylaminofluoran Orane, 2-anilino-3-methyl-6-sibutylaminofluorane, 2-0-)cyidino-3-methyl-6-diitubrobylaminofluorane, 2-anilino-3-methyl-6-N -inbutyl-N-ethylaminofluorane,
2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluorane, 2-anilino-
3-chloro-6-N-ethyl-N-isoamylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-methoxypropylaminofluorane, 2-anilino-3-methyl-6- Examples include N-methyl-N-ethoxypropylaminofluorane.

The electron-accepting compound according to the present invention is a phenol derivative,
Metal salts of aromatic carboxylic acids, acid clay, bentonite,
Novolac resins, metal-treated novolac resins, metal complexes, etc. are used. Examples of these are JP-B No. 40-9309, JP-A-45-14039, and JP-A-52-14048.
No. 3, JP-A-48-51510, JP-A-57-210
No. 886, JP-A-58-87089, JP-A-59-1
No. 1286, JP-A-60-116795, JP-A-61
-95988 etc.

In the recording material according to the present invention, the electron-accepting compound is preferably used in an amount of 50 to 5000% by weight, more preferably 100 to 2000% by weight of the electron-donating colorless dye.
It is.

The compounds of the present invention are 10% of the electron-accepting compounds used.
It is preferable to use 500 to 500% by weight, more preferably 50 to 200% by weight.

When these are applied to recording materials, they are used in the form of finely dispersed particles or films.

When used for thermal paper, JP-A-62-144゜989
No. 62-244.883, etc. Specifically, the electron-donating colorless dye, the electron-accepting compound, and the compound of the present invention are used after being 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, an aqueous polymer solution having a concentration of about 0.5 to 10% is generally used, and dispersion is carried out using a ball mill, sand mill, horizontal sand mill, attritor, colloidal mill, or the like.

Additives may be added to the thus obtained coating liquid as necessary 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 reason, fatty acids, metal soaps, etc. are added. Therefore, in addition to electron-donating colorless dyes and electron-accepting compounds that directly contribute to color development, thermofusible substances (such as amide compounds and urea compounds, such as stearic acid amide and palmitic acid amide) are generally used. , N-phenylstearamide, N-stearylurea, etc.), pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, surfactants, and other additives are coated on the support. and the recording material is constructed.

Furthermore, a protective layer may be provided on the surface of the heat-sensitive recording layer, if necessary. □Two or more protective layers may be laminated as necessary. Further, a coating liquid similar to a protective layer may be applied to the back surface in order to correct the curl balance of the support or to improve chemical resistance from the back surface. An adhesive may be applied to the back side and a release paper may be further added 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 polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, and ethylene-
Examples include maleic anhydride copolymer, styrene-maleic anhydride copolymer, inbutylene-maleic anhydride copolymer, polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives, casein, gelatin, etc. . Further, for the purpose of imparting water resistance to these binders, a water resistance agent may be added, or an emulsion of a hydrophobic polymer, specifically, styrene-butadiene rubber latex, acrylic resin emulsion, etc. may be added. The coating liquid is applied onto base paper, wood-free paper, synthetic paper, plastic sheet, resin-coated paper, or neutral paper.

The electrically conductive thermal paper is manufactured, for example, by the method described in JP-A-49-11344 and JP-A-50-48930.

The photosensitive and pressure sensitive paper is manufactured, for example, by the method described in δ8 in Japanese Patent Application Laid-open No. 57-179836.

(Examples of the Invention) Examples are shown below, but the present invention is not limited thereto. In the examples, unless otherwise specified, % represents weight %.

Example-1 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane, bisphenol A, and l-
20 g of each m-diethylaminophenoxy-2-p-methoxyphenoxyethane was dispersed in a ball mill overnight with 100 g of a 5% polyvinyl alcohol (Kuraray PVA105) aqueous solution to give a volume average particle size of 3 μm. On the other hand, 80 g of calcined kaolin (Anisilex-93) was dispersed with 160 g of a 0.5% solution of sodium hexametaphosphate using a homogenizer.

After dispersing as described above, each of the dispersions was mixed in a ratio of 5 g of the electron-donating colorless dye dispersion, 10 g of the electron-accepting compound dispersion, 10 g of the thermofusible substance fraction, and 22 g of the calcined kaolin dispersion, and then A working coating solution was obtained by adding 4 g of an emer resin of zinc stearate and 5 g of a 2% aqueous solution of sodium (2-ethylhexyl)sulfosuccinate. Apply this coating liquid to a dry coating amount of 6 g/m on high-quality paper with a basis weight of 50 g/m *
” It was coated with a wire bar and calendered to obtain coated paper.

Examples-2, 3 ■-m-diethylaminophenoxy-2 of Example-1
-p-methoxyphenoxyethane instead of 1-p-
Dimethylaminophenoxy-2-phenoxyethane (Example 2), 1-m-dimethylaminophenoxy-2-
A coated paper was obtained in the same manner as in Example-1 using p-methylphenoxyethane (Example-3).

Comparative Examples-1, 2 l-m-diethylaminophenoxy-2 of Example-1
-p-methoxyphenoxyethane, 1-p-ethoxyphenoxy-2-〇-chlorophenoxyethane (Comparative Example-1), β-benzyloxynaphthalene (Comparative Example-2)
A coated paper was obtained in the same manner as in the example except that .

Performance comparison color density was determined using a thermal printing tester manufactured by Kyocera Corporation.
Printing was performed at 0 mmJ/mm', and the color density was measured using a Macbeth Co., Ltd. RD-918 type densitometer.

Examples 11 and 31 Examples 21 and 30 Examples 31 and 32 Comparative Examples 11 and 18 Comparative Examples 21 and 11 Comparison of color density shows that the recording material of the present invention has excellent color development. .

Claims (1)

[Claims] It is characterized by containing an electron-donating colorless dye, an electron-accepting compound, and a compound having at least one aryl group or dialkylamino group, having a total number of carbon atoms of 32 or less, and a melting point of 60°C to 140°C. recording material