JPH02233286A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material excellent in color developability by containing an electron donating leuco dye, an electron acceptive compound and a specific benzylthioether derivative. CONSTITUTION:An electron donating leuco dye, an electron acceptive compound and a benzylthioether derivative represented by general formula (I) (wherein Ar1 and Ar2 are an aromatic ring which may have a substituent) are contained. Further, as the benzylthioether derivative, a compound represented by formula (II) (wherein R<1>, R<2>, R<3> and R<4> are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a cyano group or an acyl group) is pref. As the electron donating leuco dye, there are a triphenylmethane phthalide compound and a fluorane compound and, as the electron acceptive compound, a phenol derivative and a metal salt of aromatic carboxylic acid are used.

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. 60-23
9 9 2, JP 57-179836, JP 60-12
3556, 60-123557, etc.

In recent years, research has been conducted to improve properties of recording materials, such as (1) color density and color sensitivity, and (2) fastness of color formers.

The present inventors have investigated the oil solubility, water solubility, partition coefficient, pKa, polarity of substituents, position of substituents, and crystallinity when used in combination for each of the electron-donating colorless dye and 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.

(Object of the Invention) Therefore, the object of the present invention is to provide a recording material using a material that has good coloring properties and also satisfies other requirements (Structure of the Invention) This was achieved using a recording material characterized by containing an electron-donating colorless dye, an electron-accepting compound, and a benzylthioether derivative represented by the following general formula (1). Art SCH2 Ar2
(I) (Ar. and Ar2 represent an aromatic ring which may have a substituent.) Among the benzylthioether derivatives according to the present invention, those represented by the following general formula (II) are preferred.

(In the above formula, R', R', R3 and R4 may be the same or different, and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, a cyano group, an acyl group. )Rl, R2,
The substituents represented by R3 and R4 may further have a substituent.

When Rl, R2, R3 and R4 represent an alkyl group, an alkoxy group, or an alkylthio group, the number of carbon atoms is 1
-6 alkyl groups, alkoxy groups, and alkylthio groups are preferred.

Specifically, Rl, R2, R3 and R4 include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, an ethyl group, an isoprobyl group, a butyl group, a methoxy group,
Ethoxy group, propoxy group, butoxy group, methylthio group, ethylthio group, phenyl group, cyan group, acyl group, propionyl group, etc. are preferable, and especially hydrogen atom, fluorine atom, chlorine atom, methyl group, methoxy group, ethoxy group,
A methylthio group is preferred.

The substitution position of the substituent Rl is preferably the ortho or para position with respect to the pendylthio group, and the substitution position of the substituent R3 is preferably the para position with respect to the phenylthiomethyl group.

Among the benzyl thioether derivatives represented by general formula (II), those (III) in which at least one of R' or R3 is an alkoxy group, or R1R2, R
The melting point of the benzyl thioether derivative according to the present invention, which is particularly preferably one in which neither 3 nor R4 is an alkoxy group (IV), is preferably 40 to 120°C,
Particularly preferred is 60 to 105°C.

Specific examples of benzyl thioether derivatives according to the present invention are shown below, but the present invention is not limited thereto. Specific examples of (III) (4-methylbenzyl)-4-methoxyphenyl thioether, (4-chlorobenzyl)-4-methoxyphenyl thioether, (4-methoxybenzyl)-4-methoxyphenyl thioether, (4 -ethoxybenzyl)
-4-methoxyphenyl thioether, (4-methoxybenzyl)-4-ethoxyphenyl thioether, (4
-ethoxybenzyl)-4-ethoxyphenylthioether, (4-methoxybenzyl)-1phenylthioether, (4-methoxybenzyl)-4-methylphenylthioether, (4-methoxybenzyl)-4-fluoro Phenylthioether, (4methoxybenzyl)-
4-chlorophenylthioether, (4-methoxybenzyl)-4-7enylphenylthioether, (4-methoxybenzyl)-2-chlorophenylthioether,
Examples include 4-ethoxybenzylphenyl thioether and (4-ethoxybenzyl)-4-chlorophenyl thioether.

Specific examples of (IV): (4-1 benzyl)monophenylthioether, (4
-chlorobenzyl)-4-methylphenylthioether, (4-chlorobenzyl)-4-ethylphenylthioether, (4-chlorobenzyl)-4-1 oral phenylthioether, (4-chlorobenzyl)-4 Examples include -promophenylthioether, (4-methylbenzyl)-11-phenylthioether, (4-promobenzyl)monophenylthioether, and (4-promobenzyl)4-chlorophenylthioether.

Electron-donating colorless dyes involved in this development include triphenylmethane phthalide compounds, fluoran compounds, phenothiazine compounds, and indolyl phthalide compounds. Leuco auramine compounds. There are various compounds such as oral lactam compounds, triphenylmethane compounds, triazene compounds, spiropyran compounds, and fluorene compounds. Specific examples of phthalides are given in U.S. Reissue Patent No. 23.024. U.S. Patent No. 3.491.111, U.S. Patent No. 3,491,
112, 3.491.116 and 3.5.
No. 09,174, and specific examples of fluorans are given in U.S. Patent No. 3.
．． 624.107 No. 3,627,787, No. 3
．． No. 641,011, No. 3,462,828, No. 3,681.390. 3.920.510, 3.959,571, specific examples of spirodipyrans are U.S. Pat. No. 3,971,808, 1 pyridine and pyrazine compounds are U.S. Pat. No. 3,775.424,
No. 3,853,869, No. 4,246,318 1 Specific examples of fluorene compounds are given in Japanese Patent Application No. 61-240.
It is described in No. 989, etc. Among these, fluoran compounds are particularly preferred. Specific examples include 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-N-cyclohexyl-N-methylaminofluorane, and 2-p-chloroanilino-3-methyl-6-dibutyl. aminofluorane,
2-anilino 3-methyl-6-dioctylaminofluorane, 2-anilino 3-chloro-6-diethylaminofluorane, 2-anilino 3-methyl-6-diisobutylaminofluorane, 2-anilino 3-methyl-
6-N-ethyl-N-isoamylaminofluorane, 2
-anilino-3-methyl-6-N-ethyl-N-dodecylaminofluorane. 2-anilino 3-methoxy-6
-Dibutylaminofluorane. 2-0 chloroanilino-
6-Dibutylaminofluorane, 2-p-chloroanilino-3-ethyl-6-N-ethyl-N-isoamylaminofluorane. 2-0-chloroanilino-6-p-butylanilinofluorane, 2-anilino-3-pentadecyl-6-diethylaminofluorane. 2 Anilino 3-
Ethyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-o
-}Luidino-3-methyl-6-diisopropylaminofluorane, 2-anilino-3-methyl-fl+-N-
Isobutyl-N-ethylaminofluorane, 2-anilino-3-methyl-6-N-ethyl-N-tetrahydrofurfurylaminofluorane 2-anilino-3-chloro-
6-N-ethyl-N-isoamylaminofluorane, etc. 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
0 9, JP 45-14039, JP 51-1
No. 40483, JP-A-48-51510. Japanese Unexamined Patent Publication No. 1983
No.-210886, Japanese Patent Application Publication No. 1986-8-8 7 0 8 9
No., JP-A-59-11286, JP-A-60-1767
No. 95. In the recording material according to the present invention described in JP-A-61-95988 etc., the electron-accepting compound is
It is preferable to use 50 to 5000% by weight of the electron-donating colorless dye. More preferably, it is 100 to 2000% by weight. The benzyl thioether derivative is preferably used in an amount of 10 to 500% by weight, more preferably 50 to 200% by weight of the electron-accepting compound used. When these are applied to recording materials, they are used in the form of fine dispersions, minute droplets, or films.

When used for thermal paper, JP-A-62-144,989
No. 62-244.883, the specification of Japanese Patent Application No. 62-244.883, etc. Specifically, the electron-donating colorless dye, the electron-accepting compound, and the benzyl thioether derivative are 10 μm or less in the dispersion medium. It is preferably used after being crushed and dispersed to a particle size of 3μ or less. As a dispersion medium, generally 0
．． A water-soluble polymer aqueous solution with a concentration of about 5 to 10% is used and dispersion is carried out using a ball mill. Sand mill, horizontal sand mill,
This is done using an attritor, colloidal mill, etc. Additives are added to the coating liquid thus obtained as necessary to meet various requirements. Examples of additives include dispersing oil-absorbing substances such as inorganic pigments and polyurea fillers in the binder to prevent the recording head from becoming dirty during recording, and also to improve the releasability of the head. Fatty acids, metal soaps, etc. are added to the koma. Therefore, in general. In addition to electron-donating colorless dyes, electron-accepting compounds, and benzyl thioether derivatives that directly contribute to color development, thermofusible substances (such as amide compounds and urea compounds, such as stearic acid amide and palmitic acid amide) Additives such as N-phenyl stearamide, N-stearyl urea, etc.), pigments, waxes, antistatic agents, ultraviolet absorbers, antifoaming agents, conductive agents, fluorescent dyes, and surfactants are coated on the support. If necessary, a protective layer may be provided on the surface of the heat-sensitive recording layer that constitutes the recording material. Two or more protective layers may be laminated as necessary. Also, to correct the curl balance of the support. For the purpose of improving chemical resistance from the back side, a protective layer and an IP coating liquid may be applied to the back side. You can also apply adhesive to the back side and add release paper to form a label. Usually, electron-donating colorless dyes and electron-accepting compounds are. It is dispersed and applied in a binder. Water-soluble binders are generally used, such as polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, and shrimp chlorohydrin-modified polyamide 1.
Examples include ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer polyacrylic acid, polyacrylic acid amide, methylol-modified polyacrylamide, starch derivatives zein, gelatin, etc. A water-resisting agent is added to the binder for the purpose of imparting water resistance, and an emulsion of a hydrophobic polymer is added. Specifically, styrene-book diene rubber latex acrylic resin emulsion, etc. can also be added. The coating liquid is base paper and high quality paper. Synthetic paper, plastic sheet. Electric thermal paper coated on resin-coated paper or neutral paper is produced, for example, by the method described in JP-A-49-11344 and JP-A-50-48930. Photosensitive and pressure sensitive paper is manufactured, for example, by the method described in JP-A-57-179836. (Embodiments of the Invention) Examples are shown below, but the present invention is not limited thereto. Unless otherwise specified in the examples. Not expressed as weight percent. Example-1 2-anilino-3-methyl-6-N-ethyl-N-isoamylaminofluorane bisphenol A, and 4-methoxybenzylphenylthioether 20 each
g to 100g of 5% polyvinyl alcohol (Kuraray PV
A105) Disperse with an aqueous solution in a ball mill overnight,
The volume average particle size was set to 3μ. On the other hand, calcined kaolin (Ani)
silex-93) was dispersed in a homogenizer together with 160 g of a 0.5% solution of sodium hexamecrylate. 10 g of electron-accepting compound dispersion. A coating liquid was obtained by mixing 10 g of a thermofusible substance dispersion and 22 g of a calcined kaolin dispersion, and then adding 4 g of an emulsion of zinc stearate and 5 g of a 2% aqueous solution of (2-ethylhexyl) sodium sulfosuccinate. Ta. Apply this coating liquid to a dry coating amount of 6 g/m2 on high-quality paper with a basis weight of 5 og/m2.
Apply it with a wire bar so that it looks like this. A coated paper was obtained by a tire rendering process. Example-2, 3 (4-methoxybenzyl)-4-chlorophenylthioether (Example-2), (4-methoxybenzyl)-4-methoxyphenylthioether (4-methoxybenzyl)-4-chlorophenylthioether (Example-2) A coated paper was obtained in the same manner as in Example 1 using enyl thioether (Example 3).
), hydroquinone dibenzyl ether (Comparative Example-2)
Coated paper was obtained in the same manner as in the examples except for the following.The performance comparison color density was determined using a thermal printing tester manufactured by Kyocera Corporation.
Example 1' of printing at 0 mmJ/mm2 and measuring the color density using a Macbeth RD-918 densitometer 1.35 Example 2 1.32 Example 3 1.34 Comparative Example 1 1 .22 Comparative Example-2 1.10 Comparison of color density shows that the recording material of the present invention has excellent color development, Patent Applicant: Fuji Photo Film Co., Ltd. 151

Claims (1)

[Scope of Claims] A recording material characterized by containing an electron-donating colorless dye, an electron-accepting compound, and a benzylthioether derivative represented by the following general formula (I). Ar_1SCH_2Ar_2(I) (Ar_1 and Ar_2 represent an aromatic ring that may have a substituent.)