JPH03266688A - Recording material - Google Patents

Abstract

PURPOSE:To obtain a recording material imparting developed color density, excellent in the preservability of a recording image and not especially generating the fading of a developed color part and background fog by using at least one kind of a specific salicylic acid derivative or a polyvalent metal salt thereof as a developer. CONSTITUTION:This recording material is formed by providing a recording layer containing a colorless or light-colored basic dye and a developer capable of forming a color upon the contact with the basic dye on a support. As the developer, a salicylic acid derivative represented by general formula [I] or a polyvalent metal salt thereof is used. As the polyvalent metal forming a salt along with the salicylic acid derivative represented by the formula [I], divalent, trivalent or tetravalent metals, for example, zinc, calcium, aluminum, magnesium, tin and iron are pref. and zinc is especially pref. By using the salicylic acid derivative represented by the formula [I] and/or the metal salt thereof, the recording material excellent in color forming properties or raw preservability and especially excellent in the preservability of a recording image is obtained and the characteristics thereof are enhanced still more by further together using a metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a recording material, and particularly to a recording material that is excellent in color development, shelf life, and preservation of recorded images.

"Prior Art" Typical examples of recording materials that utilize a color reaction between a colorless or light-colored basic dye and an organic or inorganic coloring agent include pressure-sensitive recording materials, heat-sensitive recording materials, and current-carrying heat-sensitive recording materials. Various types are known.

These recording materials are required to have performances such as sufficient recording density and recording sensitivity, and excellent preservation of recorded images in external environments such as heat, humidity, light, and chemicals. However, at present, nothing that completely satisfies these requirements has been obtained.

-For example, thermal recording media has been diversified in its application fields and forms, along with recent remarkable advances in thermal recording methods.
It can be used not only as a recording medium for thermal facsimiles and thermal printers, but also as a POS (Point of 5ales).
Its use in new applications such as labels is also rapidly increasing.

However, heat-sensitive recording materials generally have drawbacks such as capri formation due to the influence of solvents and the like, and recorded images changing and fading. In particular, there is a strong demand for improvement, as the recorded image will noticeably discolor when it comes into contact with plastic film, and discoloration or fogging may occur when exposed to alcohol, etc. contained in household oils or hair tonics. The current situation is that

``Problems to be Solved by the Invention'' In view of the current situation, the present inventors have particularly aimed at improving the above-mentioned defects found in recording materials that utilize a color reaction between a basic dye and a coloring agent. We conducted a wide range of studies in the field of color formers.As a result, we found that the following color formers (f
) It has been discovered that by using at least one of the salicylic acid derivatives or its polyvalent metal salts, it is possible to obtain a recording material which is extremely excellent not only in color development and shelf life, but also in the preservation of recorded images. It was completed.

"Means for Solving the Problems" The present invention provides a recording layer containing a colorless or light-colored basic dye and a coloring agent capable of forming a color upon contact with the basic dye, on a support. The present invention is a recording material characterized in that at least one of the salicylic acid derivatives or polyvalent metal salts thereof represented by the following General II (1) is used as a coloring agent.

[In the formula, R is a C1-C2 alkyl group which may have a substituent, or a C1-C2 alkyl group which may have a substituent
,. represents an alkenyl group. Also, X is a hydrogen atom, 01
-C2° alkyl group, C6-C7 cycloalkyl group, 02-C1 alkenyl group, 07-C5° aralkyl group, CI-cry alkoxyl group, Ch'' Cr
t represents an aryl group, a C4 to CI□ aryloxy group, a nitro group, or a halogen atom, and Y represents a hydrogen atom, C
~C2° alkyl group, 02~C1 alkenyl group, C
It represents a 1-C1° aralkyl group, a C6-C1□ aryl group, a nitro group, or a halogen atom. [Function] In the salicylic acid derivative represented by the general formula (1) of the present invention, R is an alkyl group of 01 to C2 which may have a substituent, or a 02 to C2 alkyl group which may have a substituent. -C2° alkenyl group, examples of such substituents include halogen atom, alkoxyl group, alkoxyalkoxyl group, alkenyloxy group, phenyl group, phenoxy group, phenoxyalkoxyl group, phenoxyalkoxyalkoxyl group, phenylthio group, phenylsulfonyl group. group, phenylsulfonylalkoxyl group, etc. are preferable, and furthermore,
The phenyl group contained in these substituents is a halogen atom,
It may have a substituent such as a C2 to C4 lower alkyl group or a CI""" Ca lower alkoxyl group.
In particular, X and Y are a hydrogen atom, a C3 to C1° alkyl group,
Preferred are C1-C1 alkenyl groups, C1-CIO aralkyl groups, phenyl groups, and halogen atoms.

In addition, the substitution position of the diphenylmethyl group having a specific substituent in -JIQ formula (1) is the 3-position of salicylic acid,
The 4th and 5th positions are preferred, and the 5th position is particularly preferred.

Furthermore, the polyvalent metal that forms a salt with the salicylic acid derivative represented by -formation (1) includes divalent, trivalent or tetravalent metals, such as zinc, calcium, aluminum, magnesium, tin, iron, etc. Zinc is preferred, and zinc is particularly preferred.

The recording material using the salicylic acid derivative or its metal salt according to the present invention has sufficient color density and the color image is extremely stable, so it cannot be exposed to sunlight for a long time or stored in a high temperature or high humidity environment. The recorded image will hardly change color even if it is exposed to heat, which is extremely advantageous in terms of long-term preservation of the record. In particular, when applied to heat-sensitive recording media, it eliminates the disadvantages of white paper areas developing color due to solvents, etc., and recorded images discoloring and fading due to oils, fats, chemicals, etc., and exhibits extremely excellent properties as a coloring agent. be.

Specific examples of such salicylic acid derivatives represented by (1) include the following.

5-bis(p-methoxyphenyl)methylsalicylic acid,
5-bis(0-methoxyphenyl)methylsalicylic acid,
5-bis(m-methoxyphenyl)methylsalicylic acid,
5-bis(p-ethoxyphenyl)methylsalicylic acid,
5-bis(0-ethoxyphenyl)methylsalicylic acid,
5-bis(m-ethoxyphenyl)methylsalicylic acid, 5-bis(p-isopropyloxyphenyl)methylsalicylic acid, 5-bis(p-tert-butyloxyphenyl)methylsalicylic acid, 5-bis(p-0-hexyloxy phenyl)methylsalicylic acid, 5-bis(p
-n-dodecyloxyphenyl)methylsalicylic acid, 5
-bis(p-n-octadecyloxyphenyl)methylsalicylic acid, 5-bis(p-vinyloxyphenyl)methylsalicylic acid, 5-bis(p-7lyloxyphenyl)methylsalicylic acid, 5-bis(m-allyloxy phenyl)methylsalicylic acid, 5-bis(p-2-chloroethoxyphenyl)methylsalicylic acid, 5-bis[p-(
3-oxa-n-pentyloxy)phenylcomethylsalicylic acid, 5-bis(p-(3,6-dioxa-n-octyloxy)phenyl)methylsalicylic acid, 5-bis(p-(2-vinyloxyethoxy) Phenylcomethylsalicylic acid, 5-bis[p-(2-allyloxyethoxy)phenylcomethylsalicylic acid, 5-bis(p-hensyloxyphenyl)methylsalicylic acid, 5-bisCp
-(2-Phenethyloxy)phenyl]methylsalidylic acid, 5-bis(p-(p-methylbenzyloxy)phenylcomethylsalicylic acid, 5bis(p-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 5-bis(p-(p-methylbenzyloxy)phenylcomethylsalicylic acid,
0-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 5bis(p-(2-p-)lyluogyethoxy)phenylcomethylsalicylic acid, 5-bis[p-(2-
p-methoxyphenoxyethoxy)phenylcomethylsalicylic acid, 5-bis(p-(2-p-ethoxyphenoxyethoxy)phenylcomethylsalicylic acid, 5-bis(
p-(2-p-isopropyloxyphenoxyethoxy)phenylcomethylsalicylic acid, 5-bis(p-(2-
p-chlorophenoxyethoxy) phenylcomethylsalicylic acid, 5-bis(p-(3-phenoxypropyloxy)phenylcomethylsalicylic acid, 5-bis[p-(4
-phenoxybutyloxy)phenylcomethylsalicylic acid, 5-bis(p-(6-phenoxyhexyloxy)
Phenylcomethylsalicylic acid, 5-bis(p-<5-phenoxy-3-oxa-pentyloxy)phenylcomethylsalicylic acid, 5bis(p-(7-phenoxy-3
, 5-dioxa-hebutyloxy)phenylcomethylsalicylic acid, 5-bis(p-(2-phenylthioethoxy)phenylcomethylsalicylic acid, 5-bis[p-(2-
p-chlorophenylthioethoxy)phenylcomethylsalicylic acid, 5-bis(p-(3-phenylsulfonylpropyloxy)phenylcomethylsalicylic acid, 5-bis[p-(3-p-)lylsulfonylpropyloxy)phenylcomethyl Salicylic acid, 5-bis(p-(3-p-
methoxyphenylsulfonylpropyloxy) phenylcomethylsalicylic acid, 5-bis(p-(3-p-ethoxyphenylsulfonylpropyloxy)phenylcomethylsalicylic acid, 5-bis(p-(3-p-chlorophenylsulfonylpropyloxy)phenyl Comethylsalicylic acid, 5-bis(p-(2-p tolylsulfonylethoxy)phenylcomethylsalicylic acid, 5-bis(p-(
4-p-)lylsulfonylbutyloxy)phenylcomethylsalicylic acid, 5-bis(p-(6-p-)lylsulfonylhexyloxy)phenylcomethylsalicylic acid,
5-bis(p-(5-p-)lyl-3-oxersulfonylpentyloxy)phenylcomethylsalicylic acid, 4
-bis(p-methoxyphenyl)methylsalicylic acid, 4
-bis(p-isopropyloxyphenyl)methylsalicylic acid, 4-bis(pn-octadecyloxyphenyl)methylsalicylic acid, 4-bis(p-allyloxyphenyl)methylsalicylic acid, 4-bis(p-benzyloxyphenyl)methylsalicylic acid , 4-bis(p-(2-
phenoxyethoxy)phenyl)methylsalicylic acid, 4
-bis(p-(2-1)-methoxyphenoxyethoxy)phenylcomethylsalicylic acid, 4-bis(p-(3-
p-Tolylsulfonylpro-oxy)phenylcomethylsalicylic acid, 4bis(m-isopropyloxyphenyl)methylsalicylic acid, 3-bis(p-methoxyphenyl)methylsalicylic acid, 3-bis(p-benzyloxyphenyl)methylsalicylic acid, 3-bis(pn-tetradecyloxyphenyl)methylsalicylic acid, 3-bis(
p-(2-p-methoxyphenoxyethoxy)phenylcomethylsalicylic acid, 3-methyl-5-bis(p-(2
-phenoxyethoxy)phenylcomethylsalicylic acid,
3-tertbutyl-5-bis(p-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 3-phenyl5-bis(p-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 3-chloro-5-bis[ p-(2
-phenoxyethoxy)phenylcomethylsalicylic acid,
3-Cyclohexyl-5-bis(p-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 3-vinyl-
5-bis[p-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 3-α,α-dimethylbenzyl-5
= bis(p-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 4-phenoxy-5-bis[p-(2
-phenoxyethoxy)phenylcomethylsalicylic acid,
3-nitro-5-bis(p-(2-phenoxyethoxy)phenylcomethylsalicylic acid, 4-methoxy-5-bis(p-isopropyloxyphenyl)methylsalicylic acid, 5-bis(3tert-butyl-4-methoxy) phenyl)methylsalicylic acid, 5-bis(3-bromo-4
-methoxyphenyl)methylsalicyl 1,5-bis(4
-Methoxy-3-α-methylbenzylphenyl)methylsalicylic 3-phenyl)phenylcomethylsalicylic acid, 5-bis(4-methoxy-3-nitrophenyl)methylsalicylic acid, 5-bis(4-methoxy-3vinylphenyl)methylsalicylic acid etc. Two or more of these salicylic acid derivatives and/or metal salts thereof can be used in combination, if necessary.

In the present invention, the coloring agent is represented by the general formula (1).
By using lytic acid derivatives and/or metal salts thereof,
Although a recording material with excellent color development and raw storage stability, especially storage stability of recorded images, is obtained, these properties can be further improved by using a metal compound in combination.

Such metal compounds include divalent, trivalent, or tetravalent metals such as zinc, magnesium, barium, calcium, aluminum, tin, titanium, nickel, cobalt,
Metal oxides and hydroxides selected from manganese, iron, etc.
sulfides, halides, carbonates, phosphates, silicates,
Examples include sulfates, nitrates, and halogen complex salts, and among these, zinc compounds are particularly preferred.

Specific examples of metal compounds include zinc oxide, zinc hydroxide, zinc aluminate, zinc sulfide, zinc carbonate, zinc phosphate, zinc silicate, aluminum oxide, magnesium oxide, titanium oxide, aluminum hydroxide, and aluminum silicate. , aluminum phosphate, magnesium aluminate, magnesium hydroxide, magnesium carbonate, magnesium phosphate, and the like. Of course, two or more of these metal compounds can also be used in combination.

Although the amount of the metal compound used is not necessarily limited, it is usually 1 part by weight per 100 parts by weight of the salicylic acid derivative and/or its metal salt represented by the general formula [I].
It is desirable to adjust the amount within a range of about 500 parts by weight, preferably about 5 to 300 parts by weight.

Moreover, it is also possible to use various known coloring agents in combination within a range that does not inhibit the desired effects of the present invention.

Specific examples of such coloring agents include the following.

Inorganic coloring agents such as acid clay, activated clay, attapulgite, bentonite, colloidal silica, calcined kaolin, and talc; aliphatic carboxylic acids such as oxalic acid, maleic acid, tartaric acid, citric acid, succinic acid, and stearic acid; benzoic acid,
4-tert-butylbenzoic acid, 4-chlorobenzoic acid,
4-nitrobenzoic acid, phthalic acid, gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-Ler
t-Butylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3-phenyl-5-(α,α-dimethylbenzyl)salicylic acid, 3,5-di(α-methylbenzyl)salicylic acid, 2-hydroxy-1-hensyl - Aromatic carboxylic acids such as 3-naphthoic acid, 4.4'-isopropylidenediphenol (bisphenol A), 4.4'-
Isopropylidene bis(2-chlorophenol), 4.
4'-isopropylidene bis(2,6-dichlorophenol), 4.4'-isopropylidene bis(2,6-dibromophenol), 4.4'-isopropylidene bis(2-methylphenol), 4.4 '-isopropylidene bis(2,6-dimethylphenol), 4.4'-isopropylidene bis(2ter L-butylphenol), 4.4'-5ec butylidene diphenol, 2.
2-bis(4-hydroxyphenyl)-4-methylpentane, 4゜4'-cyclohexylidene bisphenol,
4.4'-Cyclohexylidenebis(2-methylphenol), 4-terL-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-
Naphthol, β-naphthol, methyl-4-hydroxybenzoate, benzyl-4-hydroxybenzoate, 2,2'-thiobis(4°6-dichlorophenol)
, 4-tert-octylcatechol, 2,2'-methylenebis(4-chlorophenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'dihydroxybiphenyl, methyl-bis (4-hydroxyphenyl)acetate, ethyl-bis(
4-hydroxyphenyl)acetate, benzyl-bis(4-hydroxyphenyl)acetate, 4.4'-(
p-phenylene diisopropylidene) diphenol, 4
．． 4'-(m-phenylene diisopropylidene) diphenol, 4-hydroxydiphenylsulfone, 4.4'
-dihydroxydiphenylsulfone, 4-hydroxy-
4'-methyldiphenylsulfone, 4-hydroxy-4
'isopropoxydiphenyl sulfone, 4-hydroxy-3', 4'25 tramethylene diphenyl sulfone, 3
, 3'-diallyl-4,4'-dihydroxydiphenylsulfone; organic coloring agents such as phenolic resins such as p-phenylphenol-formalin resin and p-butylphenol-acetylene resin; Salts of agents with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, and nickel; metal complex compounds such as antipyrine complexes of zinc thiocyanate; and the like.

In the recording material of the present invention, various colorless or light-colored basic dyes are known to be used in combination with the above-mentioned specific salicylic acid derivatives or metal salts thereof, and examples thereof include the following.

3.3-bis(p-dimethylaminophenyl)6-dimethylaminophthalide, 3.3-bis(p-dimethylaminophenyl)phthalide, 3-(4-dimethylaminophenyl)-3-(4-diethylamino- 2-methylphenyl)-6-(dimethylamino)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylamidiphenyl)-3 -(2-methylindol-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)-6-dimethylaminophthalide,
3゜3-bis(2-phenylindol-3-yl)-
6-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylvirol-3-yl)-6
-Triarylmethane dyes such as dimethylaminophthalide, 4,4'-bis(dimethylamino)benzhydrylbenzyl ether, N-halophenyl-leucoauramine, N-2,4゜5-trichlorophenylleucoauramine Diphenylmethane dyes such as 3.3-17s (1,
1-bis(4-pyrrolidinophenyl)ethylene-2yl)-4,5,6,7-tetraflomophthalide, 3.3-
Bis(1-(4-methoxyphenyl)-1-(4-dimethylaminophenyl)ethylene-2-yl)-4,5,
6,7-tetrachlorophthalide, 3,3-bis[1-(
Divinylphthalide dyes such as 4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene-2-yl)-4,5,6,7-tetrachlorophthalide, benzoylleucomethylene blue, p-nitrobenzoylleuco Thiazine dyes such as methylene blue, 3-methyl-spiro-
Dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3-methyl-naphtho(
6'-methoxybenzo)spiropyran, 3-propyl-
Spiro dyes such as spiro-dibenzobilane, lactam dyes such as rhodamine-B-anilinolactam, rhodamine (p-nitroanilino) lactam, rhodamine (0-ri00anilino) lactam, 3-dimethylamino-7-
Methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, 3-diethylamino-7-chlorofluoran,
3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6,7-dimethylfluorane, 3-(N-ethyl-p-1luidino)-7-methylfluorane, 3-diethylamino- 7-(N-acetyl-N-methylamino)fluorane, 3-diethylamino-7-N-methylaminofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-(N-methyl- N-benzylamino)fluoran, 3-diethylamine-7-(N-chloroethyl-
N-methylamino)fluoran, 3-diethylamino-
7-diethylaminofluorane, 4-benzylamino-
8-diethylaminolbenzo[a) fluorane, 3-
(4-(4-dimethylaminoanilino)anilino)-7
-chloro-6-medylfluorane, 8- (4-(4-
dimethylamineanilino)anilino]-benzo(a)fluoran, 3-(N-ethyl-p-toluidino)-6-
Methyl-7-phenylaminofluoran, 3-(N-ethyl-p-)luidino)-6-methyl-7-(p-toluidino)fluoran, 3-diethylamino-6-methyl-7-phenylaminofluoran, 3 dibutylamino-
6-Methyl-7-phenylaminofluorane, 3-diethylamino-7-(2carbome[·xy-phenylamino)fluoran, 3-(N-ethyl-N-isoamylamino)-6methyl-7-phenylaminofluoran Oran, 3
(N-cyclohexyl-N-methylamino)-6methyl-7-phenylaminofluorane, 3-pyrrolidino-6-
Methyl-7-phenylaminofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane, 3-
Diethylamino 6-methyl-7-quizylidinofluorane, 3-diethylamine-7-(o-chlorophenylamino)fluorane, 3-dibutylamino-7-(o-chlorophenylamino)fluorane, 3-(N-ethyl-N
-tetrahydrofurfurylamino)-6=methyl-7-
Phenylaminofluorane, 3-(N-methyl-N-n
-propylamino)-6-methyl-7-phenylaminofluorane, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-phenylaminofluorane, 3-
(N-methyl-N-n-hexylamino)-6-methyltophenylaminofluorane, 3-dibentylamino-
6-Methyl-7-phenylaminofluorane, 3-(N
-(3-ethoxypropyl)-N-methylaminocou6
-Methyl-phenylaminofluorane, 3-[N-
Ethyl-N-(3ethoxypropyl)aminoco-6-methyl-phenylaminofluorane, 3-diethylamino-7-[m-(trifluoromethyl)phenylaminofluorane, 3-diethylamino-7-(0-fluorophenyl) Aminoffluorane, 3-dibutylamino-7-
(o-fluorophenylamino)fluorane, 3-diethylamino-6-chloro-7-phenylaminofluorane, 3-(N-ethyl-N-n-hexylamino)-6
-Methyl-7-phenylaminofluorane, 3-(N-ethyl-N-cyclopentylamino)-6-methyl-7-
Fluoran dyes such as phenylaminofluorane, 3.
6-bis(dimethylamino)fluorene-9-spiro-
3'-(6'-dimethylamino)phthalide, 3-diethylamino-6-(N-allyl-N-methylamino)fluorene-9-spiro-3'-(6'-dimethylamino)
Phthalide, 3,6-bis(dimethylamino)-spiro [
Fluorene-9,6'-6'H-chromeno (4゜3-
b) indole), 3,6-bis(dimethylamine)-
3'-Methyl-spiro[fluorene-9,6'-6'H
-chromeno (4,3-b)indole), 3,6-bis(diethylamino)-3'-methyl-spiro[fluorene-9,6'-6'11-chromeno (4,3-b)
Indole] and other fluorene dyes. Of course, the dyes are not limited to these dyes, and two or more types of dyes can be used in combination.

Further, for example, in the case of a heat-sensitive recording medium, various thermofusible substances can be used as a recording sensitivity improving agent in order to obtain high-speed recording performance. Such thermofusible substances include:
For example, caproic acid amide, capric acid amide, valmitic acid amide, stearic acid amide, oleic acid amide,
erucic acid amide, linoleic acid amide], lylinic acid amide, N-methyl stearic acid amide, stearic acid anilide, N-methyl oleic acid amide, benzanilide, linoleic acid anilide, N-ethyl capric acid amide, N-
Butyllauric acid amide, N-octadecyl acetamide, N-oleicacetamide, N-oleylbenzamide, N-stearylcyclohexylamide, polyethylene glycol, 1-benzyloxynaphthalene, 2-
Benzyloxynaphthalene, 1-hydroxynaphthoic acid phenyl ester, ■, 2-diphenoxyethane, 1.
4-diphenoxybutane, ■, 2-bis(3methylphenoxy)ethane, 1,2-bis(4methoxyphenoxy)ethane, 1-phenoxy-2-(4-chlorophenoxy)ethane, 1-phenoxy-2- (4-Methoxyphenoxy)ethane, dibenzyl terephthalate, dibenzyl oxalate, di-p-methylbenzyl oxalate, benzyl p-benzyloxybenzoate, p~benzylbiphenyl, 1゜5-bis(p −
methoxyphenoxy)-3-oxabencune, 1.4-
One or more examples include bis(2-vinyloxyethoxy)benzene and the like.

Below, various typical recording materials using the salicyl M derivative represented by the -format [1] or its metal salt and the above-mentioned basic dyes will be specifically explained.

Pressure-sensitive recording bodies are disclosed, for example, in U.S. Pat. No. 2,505,470;
No. 2,505,471, No. 2,505,489, No. 2,548,366, No. 2,712,507, No. 2
, No. 730,456, No. 2,730゜457, No. 3,
No. 418,250, No. 3,924,027, No. 4゜0
As described in No. 10.038, there are various types of pressure-sensitive recording bodies, and the present invention can be applied to these various types of pressure-sensitive recording bodies.

-a, at least one of the salicylic acid derivatives or metal salts thereof of the present invention is dispersed in various binders such as styrene-butadiene copolymer latex and polyvinyl alcohol together with other coloring agents and pigments as necessary. A coloring agent sheet (so-called bottom sheet) is produced by applying the coloring agent coating liquid onto a suitable support such as paper, plastic sheet, resin-coated paper, or the like.

On the other hand, the color former sheet (so-called top sheet) used in combination with the above color former sheet is a synthetic oil such as basic dye, alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl; Oil, vegetable oil such as castor oil; animal oil: mineral oil; or a dispersion prepared by dispersing this in a binder. It is produced by containing it in microcapsules by various encapsulation methods such as the 1n-situ method, and coating the dispersion liquid dispersed in a binder on a suitable support such as paper, plastic sheet, resin-coated paper, etc.

Of course, there is a so-called middle sheet in which one side of the support is coated with the coloring agent coating liquid and the other side is coated with a dye dispersion or dye capsule dispersion, and furthermore, dye capsules and coloring agent are coated on the same side of the support. Various types of so-called stand-alone copying sheets, etc., in which dye capsules and coloring agent coexist on the same surface, are produced by applying a coating liquid containing a mixture of dye capsules and coloring agent, or by applying a coloring agent coating liquid on top of a dye capsule dispersion. As mentioned above, this includes the following forms.

In addition, the usage ratio of basic dye and coloring agent depends on the desired coating amount,
Since it varies depending on various conditions such as the form of the pressure-sensitive recording medium, the encapsulation method, the composition of the coating liquid including various auxiliary agents, and the coating method, it may be selected appropriately according to the conditions.

For example, heat-sensitive recording materials are disclosed in Japanese Patent Publication Nos. 44-3680 and 442.
No. 7880, No. 45-14039, No. 48-4383
No. 0, No. 49-69, No. 49-70, No. 52-20
142, etc., and the salicylic acid derivative or its metal salt of the present invention can be applied to these various types of heat-sensitive recording materials.

- For boat fishing, a coating liquid obtained by dispersing the salicylic acid derivative of the present invention or its metal salt and fine particles of a basic dye in a medium in which a binder is dissolved or dispersed is applied to paper, plastic film, synthetic paper, and even woven fabric sheets. The heat-sensitive recording material of the present invention is produced by coating it on a suitable support such as a molded product. The ratio of basic dye and coloring agent used in the recording layer is not particularly limited, but generally the basic dye is 100%
50 to 5000 parts by weight, preferably 10 parts by weight
Color formers ranging from 0 to 500 parts by weight are used.

In addition, for the purpose of improving coloring ability, matting the surface of the recording layer, improving writing properties, etc., inorganic pigments are generally added in an amount of 0.91 to 10 parts by weight, preferably 0.5 to 3 parts by weight, per 1 part by weight of the coloring agent. For example, dispersants, ultraviolet absorbers, thermofusible substances (recording sensitivity improvers as described above),
Various auxiliary agents such as antifoaming agents, fluorescent dyes, and colored dyes can be used in combination as necessary.

As mentioned above, the heat-sensitive recording material of the present invention is generally manufactured by coating a support with a coating liquid in which fine particles of a basic dye and a coloring agent are dispersed. The support may be overcoated with two types of coating liquids dispersed in the same material, or may be produced by impregnation or rolling.

There are no particular restrictions on the preparation method or application method of the coating liquid, and the amount applied is generally 2 to 1 on dry weight.
Approximately 2g/m is applied. Furthermore, for the purpose of protecting the recording layer and improving writability, a dry MO of 12 to 10 g/m', preferably 0.5 to 5 g is added to the recording layer.
It is of course possible to provide a Dt-barco-1 layer or an undercoat layer on the support, and various known techniques in the field of heat-sensitive recording material manufacturing can be added as appropriate.

Examples of the binder include starches, cellulose, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride copolymer salt, acetic acid bee-maleic anhydride copolymer salt, polyacrylate, and styrene-butadiene copolymer. Polymer emulsions and the like are appropriately selected and used.

The electrically conductive heat-sensitive recording material is manufactured, for example, by the method described in JP-A-49-11344 and JP-A-50-48930. Generally, a coating liquid containing a conductive substance, a basic dye, and a coloring agent dispersed together with a binder is applied to a suitable support such as paper, or a conductive substance is applied to the support to form a conductive layer. It is manufactured by applying a coating liquid containing a dye, a coloring agent, and a binder dispersed thereon. In addition, both the dye and the coloring agent are 70%
If it does not melt in the preferred temperature range of ~120°C, sensitivity to Joule heat can be adjusted by using an appropriate thermofusible substance.

Thus, the recording material obtained by the present invention has excellent color development, and even when exposed to high temperature or high humidity environments or in contact with chemicals, the white paper area does not develop color or the recorded image does not change color. It has extremely well-balanced properties in terms of quality.

"Example" The present invention will be described in more detail with reference to Examples below, but the present invention is of course not limited to these.

Further, unless otherwise specified, parts and percentages in the examples indicate parts by weight and percentages by weight, respectively.

Example 1 6 parts of 3-(N-ethyl-N-isoamylamino)-6-methyl-7-phenylamitofluorane was dissolved in 100 parts of isopropylated naphthalene, and 25 parts of big skin gelatin with an isoelectric point of 8 was dissolved. 35 by dissolving 25 parts of gum arabic
It was added to 0 parts of warm water (50°C) and emulsified and dispersed. Add 1000 parts of warm water to this emulsion, adjust the pH to 4 with acetic acid, cool it to 10°C, and add 25 parts of geltaraldehyde.
% aqueous solution was added to harden the capsules.

This capsule-containing coating liquid was coated on one side of a 45 g/cd base paper so that the dry weight was 5 g/rd to obtain a color former sheet.

Meanwhile, in 200 parts of water, 20 parts of zinc salt of 5-bis(p-n-dodecyloxyphenyl)methylsalicylic acid, 80 parts of kaolin, and a styrene-butadiene copolymer emulsion (
A coloring agent coating liquid containing 30 parts (solid content: 50%) of
A coloring agent sheet was obtained by coating a dry weight of 5 g/rd on a base paper of g/rrr.

When the thus prepared coloring agent sheet and coloring agent sheet were stacked and pressed so that the capsule-coated surface and the coloring agent-coated surface were in contact with each other, a black image was instantly obtained. This image had high density and excellent light resistance.

Examples 2 to 4 In the coloring agent coating liquid of Example 1, zinc salt of 5-bis(p-〇-dodecyloxyphenyl)methylsalicylic acid 20
Example 1 except that the following coloring agent was used instead of
A coloring agent sheet was obtained in the same manner as above.

'1lfE Example 2: 20 parts zinc salt of 5-bis(p-(2-phenoxyethoxy)phenyl)methylsalicylic acid JIi Example 3: Zinc salt of 5-bis(p-(3-phenylsulfonylpropyloxy)phenylcomethylsalicylic acid) Zinc salt 20 parts JI Example 4: 3. Zinc salt of 5-bis(α-methylbenzyl)salicylic acid 10 parts Zinc salt of 5-bis(p-n-dodecyloxyphenyl)methylsalicylic acid 10 parts Evaluation was also carried out in the same manner as in Example 1, and a coloring agent sheet with high print density and excellent light resistance was obtained.

Example 5 ■ Preparation of liquid A 3-(N-ethyl-N-isoamylamino)6-methyl-7-phenylaminofluorane 10 parts 1.2-bis(3-methylphenoxy)ethane 20 parts Methylcellulose 5% aqueous solution 20 Department water
110 parts of this composition was ground in a sand mill until the average particle size was 3 μm.

■ Preparation of B solution Zinc salt of 5-bis(p-n-octadecyloxyphenyl)methylsalicylic acid 30 parts Methylcellulose 5% aqueous solution 60 parts water
110 parts of this composition was ground in a sand mill until the average particle size was 3 μm.

■ Formation of recording layer 160 parts of liquid A, 200 parts of liquid B, silicon oxide pigment (oil absorption 1
80 m1/100 g), 150 parts of a 20% oxidized starch aqueous solution, and 210 parts of water were mixed and stirred to prepare a recording layer coating liquid. The obtained coating liquid was applied to a 50 g/rrr base paper so that the dry weight was 6.0 g/rd, and dried to obtain a thermosensitive recording paper.

Examples 6 to 7 In the preparation of Solution B of Example 5, 2 Various types of thermal recording paper were obtained.

Example 6: Zinc salt of 5-bis[p-2-phenoxyethoxy)phenylcomethylsalicylic acid Example 7: Zinc salt of 5-bis(p-(3-phenylsulfonylpropyloxy)phenylcomethylsalicylic acid) 8 In the preparation of Solution B of Example 5, zinc salt of 5-bis(pn-octadecyloxyphenyl)methylsalicylic acid 30
A thermosensitive recording paper was obtained in the same manner as in Example 5, except that 30 parts of 5-bis(p-n-octadecyloxyphenyl)methylsalicylic acid, 30 parts of zinc oxide, and 80 parts of water were used instead of 210 parts of water. Ta.

Examples 9-10 Two types of thermal recording paper were prepared in the same manner as in Example 8, except that the following compound was used instead of 5-bis(pn-octadecyloxyphenyl)methylsalicylic acid in the preparation of Solution B in Example 8. I got it.

Example 9: 5-bis(p-(2-p-methoxyphenoxyethoxy)phenylcomethylsalicylic acid) Example 10: 5-bis(p-<3-p-tolylsulfonylpropyloxyphenyl)methylsalicylic acid Example 11 Practice In preparing Solution A of Example 10, 3-(N-ethyl-N
A thermosensitive recording paper was obtained in the same manner as in Example IO, except that 3-dibdelamino-6-methyl-7-phenylaminofluorane was used instead of -isoamylamino)-6-methyl-7phenylaminofluorane. Ta.

Comparative Examples 1 to 2 In the preparation of Solution B of Example 5, the same procedure as in Example 5 was used except that the following compound was used instead of the zinc salt of 5-bis(p-n-octadecyloxyphenyl)methylsalicylic acid. Two types of thermal recording paper were obtained.

Comparative Example 1: 4,4'-isopropylidenediphenol Comparative Example 2: Zinc salt of 3,5-bis(α-methylbenzyl)salicylic acid Mold 1 (manufactured by Hitachi) was used for mold (manufactured by Hitachi), and its color density was measured using a Macbeth densitometer (RD~91).
The results are shown in Table 1.

In addition, after leaving the thermal recording paper after the above recording under a high temperature drying condition of 60°C for 20 hours, and after leaving it under a high humidity condition of 40°C and 90% R, 11, for 20 hours, the color density of the recorded image was determined. The heat resistance and moisture resistance of the recorded image were evaluated by measurement using a Maches densitometer, and the results are shown in Table 1. Furthermore, in order to evaluate chemical resistance, a vinyl chloride film was layered on the colored side of the recording paper and left at room temperature for 20 hours (plasticizer resistance), and when ethanol was applied to the colored side (ethanol resistance). ) and the case where cottonseed oil was applied to the coloring surface (oil resistance), the degree of fogging in the blank area and fading of the recorded image was evaluated, and the results are shown in Table 2.

"Effects" As is clear from the results in Tables 1 and 2, the recording material according to the present invention has a high color density and has excellent storage stability of recorded images, in particular, no fading of the colored part due to chemicals and no background fogging. It was a recording material.

Claims (4)

[Claims] (1) In a recording material in which a recording layer containing a colorless or light-colored basic dye and a coloring agent capable of forming a color when it comes into contact with the dye is provided on a support, the coloring agent is expressed by the following general formula: [
A recording material characterized by using at least one salicylic acid derivative or its polyvalent metal salt represented by [I]]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R is C_1 to C_2 which may have a substituent
_0 alkyl group or C_ which may have a substituent
It represents an alkenyl group of 2 to C_2_0. In addition, X is a hydrogen atom, an alkyl group of C_1 to C_2_0, and C_5 to C_
7 cycloalkyl group, C_2 to C_7 alkenyl group, C_7 to C_1_0 aralkyl group, C_1 to C_1
_0 alkoxyl group, C_6-C_1_2 aryl group, C_6-C_1_2 aryloxy group, nitro group, or halogen atom, Y is a hydrogen atom, C_1-
Alkyl group of C_2_0, alkenyl group of C_2 to C_7, aralkyl group of C_7 to C_1_0, C_6 to C_
1_2 represents an aryl group, nitro group, or halogen atom. ] (2) The recording material according to claim (1), in which at least one salicylic acid derivative represented by the general formula [I] or a polyvalent metal salt thereof and a metal compound are used together as a coloring agent. (3) Claim (1) or (
2) Recording materials described. (4) Claim (1) or (
2) Recording materials described.