JPS6022638B2 - recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording material, and particularly to a recording material using a xanthate metal salt as an electron-accepting substance.

A color reaction between an electron-donating organic compound (hereinafter referred to as a coloring agent) and an electron-accepting substance (hereinafter referred to as a complexion agent), such as pressure-sensitive recording paper, heat-sensitive recording paper, current-carrying recording paper, etc. Systems that utilize the are already well known.

For example, U.S. Pat.
, 456, 2,730, 457, 3, 41 & 25
Pi No. 3,432,327, No. 3,981,821,
No. 3,993,831, No. 3,996,156, 3,9
90 405 and 4,000,087 etc., the materials used, composition, uses, etc. are detailed. As mentioned above,
In recording materials, color developers include acid clay, clay minerals such as bentonite and kaolin, salicylic acid derivatives such as salicylic acid, phenol monomers such as phenylphenol, and phenylformaldehyde polymers. Phenol resins or their metal salts have been used.

However, these head coloring agents tend to cause the coating liquid to settle.
o - Unless the pH is high, there is no sufficient color developing ability, and uniform dispersion is difficult, o - Water resistance is not sufficient, and the cost is high. In order to solve these drawbacks, it has also been proposed to use metal salts of alcohol derivatives such as vorivinyl alcohol, but even with this method, in addition to the drawbacks of point B mentioned above, the complexion ability is not sufficient. There were drawbacks.

The present invention solves these drawbacks of the prior art.

The purpose of the present invention is, firstly, to provide a low-cost head coloring agent, and secondly, to provide a color developer with good water resistance.

The above object of the present invention has been achieved by using a zinc salt, aluminum salt or tin salt of xanthic acid having 50 or less carbon atoms as a color developer.

Xanthogenic acid is a compound derived from carbon disulfide and an aliphatic or aromatic alcohol, and is usually isolated in the form of a salt. The alcohol may be monovalent or polyvalent. Furthermore, it may be linear, have a ring, or be branched. Furthermore, the alcohol may be primary, secondary or tertiary. In addition, in the present invention, it is important that the xanthate acid converter is a xanthate derivative and that it has color developing ability, and it may be derived from alcohol with any substituent as long as it does not interfere with the color developing ability. It can be anything.

That is, it may have one or more substituents selected from a halogen atom, an ester bond, an ether bond, a carboxyl group, a carbonato group, a sulfo group, a sulfonato group, an amide bond, a hydroxyl group, and the like.

Specifically, methanol, ethanol, isobronoenol, butanol, Sec-amyl alcohol, n-hexanol, cyclohexylmethanol, dodecyl alcohol, phenethyl alcohol, cinnamyl alcohol, phenoxyethanol, naphthol, chloro Monohydric alcohols such as butanol, carboxyamyl alcohol, etc., polyhydric alcohols such as ethylene glycol, bentaerythritol, bisphenol A, bis1,4-hydroxyethoxybenzene, trihydroxymethylpropane, dodecylphenylpropanediol, etc. etc. are used as starting materials.

The metal forming the xanthate salt according to the present invention is zinc, aluminum or tin. Among these, zinc is particularly advantageous. The xanthate metal salt is about 0
．． It is especially used from 0.1 evening to about 3 evening/end. As is already well known, xanthate polyvalent metal salts are generally obtained by reacting sodium or potassium xanthate with an inorganic polyvalent metal salt.

These may be used in advance as a metal salt of xanthogenic acid, or may be used after being reacted in the system. Next, commonly used pressure-sensitive copying paper will be described in detail.

Coloring agents are usually used in encapsulated form. A known encapsulation method can be used to encapsulate the color former oil. For example, methods for manufacturing capsules include methods using coacervation as seen in U.S. Patent Nos. 2,800,457 and 2,800,458, British Patent No. 990,443, and U.S. Pat. A method using the interfacial polymerization method found in US Patents 3,41 & 2
50 and 3,660,304, and polymerization of glue actant from inside oil droplets as described in U.S. Pat. No. 3,720,804 and U.S. Pat. No. 3,796,66. Specific examples of color formers include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (crystal violet lactone, hereinafter referred to as CVL), 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (crystal violet lactone, hereinafter referred to as CVL), and , 3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)
Phthalide, 3-(p-dimethylaminophenyl)-3-
(2-methylindo-3-yl)phthalide, 3-(
p-dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalide, 3,3-bis(1,
2-dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3
, 3-bis-(9-ethylcarbazol-3-yl)-5-dimethylamino/phthalide, 3,3-bis-(2-phenylindol-3-yl)-5-dimethylaminophthalide, 3-p-dimethylamino Examples include phenyl-3-(1-methylpyrrol-2-yl)-6-methylaminophthalide.

Examples of diphenylmethane color formers include 4,4'-bis-dimethylaminobenzhydrin benzyl ether, N-halophenylleucoauramine, and N-2,4,5-triclo.

Examples include phenylleucoauramine. Examples of xanthene color formers include rhodamine-B-anilinolactam, rhodamine-(p-nitroanilino)lactam, rhodamine-B(p-chloroanilino)lactam, 3-dimethylamino-6-methoxyfluorane, 3-diethylamino-7
-methoxyfluorane, 3-diethylamino-7-chloro-6-methylfluorane, 3-diethylamino-7-
(acetylmethylamino)fluorane, 3-diethylamino-7-(dibenzylamino)fluorane, 3-diethylamino-7-(methylbenzylamino)fluorane, 3-diethylamino-7-(chloroethylmethylamino)fluorane, 3-diethylamino-7-(dibenzylamino)fluorane Examples include 7-(diethylamino)fluoran.

Examples of thiazine-based color formers include benzylleucomethylene blue and p-nitrobenzylleucomethylene blue.

Examples of spiro-based coloring agents include 3-methyl-spirodinaphthopyran, 3-ethyl-spirodinaphthopyran, 3,
3'-dichlorospyrodinaphthopyran, 3-benzylose spirodinaphthopyran, 3-methylnaphthopyran (
3-methoxy-penzo)-spi.

Examples of solid acids that can be used in combination with the xanthate of the present invention as a complexing agent include activated clay materials such as acid clay, activated clay, attapulgite, bentonite, zeolite, etc. Alternatively, there are organic acid substances such as phenol resins, metal salts of aromatic carboxylic acids such as diQ-methylbenzyl salicylate, and the like.

When used together, they are suitably used in amounts of about 1 weight percent to about 2 pitches. Regarding various additives, binders, antioxidants, anti-smearing agents, surfactants, coating methods, usage methods, etc. used in recording systems, please refer to U.S. Pat. No. 1,232, British Patent No. 7, Mochiseki No. 50-144,012, No. 50-50,112, No. 50-127,718, No. 50-30,615, U.S. Patent No. 3, 836 total 3
No. 3,846, No. 331, etc., are well known.

In addition, the microcapsule layer containing the coloring agent is described in Hakama Sekisho 49.
-37,711.

EXAMPLE A solution of zinc ethylxanthate or zinc butylxanthate in ethyl acetate (1 night/20 cc) was applied to paper at a rate of about 0.4 evening/20 cc.

On top of this, a microcapsule layer containing a coloring agent is layered for 60 minutes.
Pressure was applied to 0k9/ground.

The density of the colored images was approximately 0.8, indicating good color development.

Comparative Example A solution of zinc diethylthiocarbamate in 1 night/20 cc of ethyl acetate was applied to paper at a rate of about 0.4 night/20 cc.

This was pressurized in the same manner as in the examples, but no color developed. As can be seen from this result, even though the partial skeletons are similar, the performance is markedly different.

Claims (1)

[Claims] 1. A recording material characterized in that a zinc salt, aluminum salt or tin salt of xanthic acid having 50 or less carbon atoms is used as a color developer.