JPH0315587A - Recording material - Google Patents

Abstract

PURPOSE:To improve the color forming property and preservative property of a recording material and the preservative property of a recording image by using a derivative of salicylic acid expressed by a specific formula or metal lic salt thereof as a color reaction agent capable of forming color through contact with a colorless or light basic dye. CONSTITUTION:For a color reaction agent which forms color through contact with a colorless or dim basic dye, a derivative of salicylic acid expressed by a formula [I] or its metallic salt is used. In the formula [I], R represents an alykyl group which may have a substitution group or an aryl group which may have a substitution group, and X represents a hydrogen atom, alkyl group, cycloalkyl group, alkenile group, an aralkyl group, aryl group, alkoxyl group, aryloxy group, nitro group or halogen atom. In order to manufacture a thermal recording body, the derivative of salicylic acid or its metallic salt and basic dyes and fine particles are dispersed in a medium wherein binders are dissolved or dispersed, whereby an application liquid is obtained. By applying this liquid onto a paper, plastic film, a synthetic paper, a woven sheet or a support body of moldings, etc., the thermal recording body is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" 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 require that the recording material itself be white, that the recording density and recording sensitivity are sufficient, and that the preservation of the recorded image under external environments such as heat, humidity, and chemicals, and the retention of whiteness in the blank area. Performance such as excellent properties are required, but there is currently no material that completely satisfies these requirements.

For example, thermal recording materials are relatively inexpensive, and along with the remarkable progress in thermal recording methods, their fields of use and forms are diversifying.They are not only used as recording media for thermal facsimiles and thermal printers, OS (Point
of Sales) Its use in new applications such as labels is also rapidly increasing.

However, heat-sensitive recording materials generally have drawbacks such as fogging due to the influence of solvents and the like, and recorded images changing and discoloring. In particular, if it comes into contact with plastic film, the recorded image will fade significantly, or if it is stored in contact with diazo copy paper, especially diazo copy paper immediately after copying, it may have defects such as fogging which is extremely likely to occur. Currently, there is a strong need for improvement.

``Problems to be Solved by the Invention'' In view of the current situation, the present inventors aimed to improve the above-mentioned defects observed in recording materials that utilize the color reaction between basic dyes and coloring agents, and in particular, The field of coloring agents was extensively studied. As a result, as a coloring agent, the following general 2 (1)
It has been discovered that by using at least one salidylic acid derivative represented by the formula or its metal salt, a recording material which is extremely excellent not only in color development and raw storage stability but also in recording image storage stability has been completed, and the present invention has been completed. I ended up doing it.

“A thousand steps to solving the problem” The present invention provides a recording material that utilizes a color reaction between a colorless or light-colored basic dye and a coloring agent that can change color when it comes into contact with the dye. This is a recording material characterized in that at least one salicylic acid derivative represented by the following general formula [I] or a metal salt thereof is used as a coloring agent.

[Wherein, R represents an alkyl group that may have a substituent or an aryl group that may have a substituent, and X represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, It represents an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group, a nitro group, or a halogen atom. [Function] In the salicylic acid derivative represented by the general formula [I] of the present invention, substituents for the alkyl group represented by R include a halogen atom, an alkoxyl group, an alkoxyalkoxyl group, an alkenyloxy group, a phenyl group, and a naphthyl group. A phenyloxy group, a phenoxyalkoxyl group, a phenoxyalkoxyalkoxyl group, a naphthyloxy group, a phenylthio group, a naphthylthio group, etc. are preferable, and the aromatic ring contained in these substituents further includes a halogen atom, a lower alkyl group, a lower alkoxyl group, It may have a substituent such as a phenyl group, a phenyloxy group, or a lower alkoxycarbonyl group.

Further, as the aryl group represented by R, phenyl group,
A naphthyl group or a heteroaromatic group is preferable, and substituents for these aryl groups include a halogen atom, a nitro group,
Preferred are an alkyl group, an alkoxyl group, an alkylthio group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, and the like.

Further, as the metal atom forming a salt with a salicylic acid derivative, a divalent, trivalent or tetravalent metal atom is preferable, and zinc, calcium, alkium, magnesium, tin, and iron are particularly preferable.

The salicylic acid derivative represented by the above general formula (1) can be obtained, for example, by alkylating or arylating the corresponding mercaptosalidylic acid derivative, or by carboxylating the corresponding (alkylthio)phenol derivative or hydroxydiaryl sulfide derivative. The test can be performed by a known method such as the above method.

The recording material using the salicylic acid derivative or its metal salt according to the present invention has sufficient color density and the developed pigment 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 hardly changes color even when exposed to heat, which is extremely advantageous from the viewpoint of long-term preservation of the record. In particular, when applied to heat-sensitive recording materials, it eliminates the disadvantages of white paper areas becoming colored 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 the salicylic acid derivative represented by the general formula (1) include the following.

5-(ethylthio)salicylic acid, 5-(hexylthio)
salicylic acid, 5-(cyclohexylthio)salicylic acid,
5-(octylthio)salicylic acid, 5-(decylthio)
Salicylic acid, 5-(dodecylthio)salicylic acid, 5-(
Tetradecylthio)salicylic acid, 5-(pentadecylthio)salicylic acid, 5-(hexadecylthio)salicylic acid, 5-(octadecylthio)salicylic acid, 5-(eicosylthio)salicylic acid, 5-(6-chlorohexylthio)salicylic acid, 5- (8-chlorooctylthio)salicylic acid, 5-(10-chlorodecylthio)salicylic acid, 5
-(12-chlorododecylthio)salicylic acid, 5-(2
-Methoxyethylthio)salicylic acid, 5-(2-ethoxyethyldio)salicylic acid, 5-(2-propoquinethylthio)salicylic acid, 5-(2-butoxyethylthio)
Salicylic acid, 5-(1-(2-ethoxyethoxy)ethylthio)salicylic acid, 5-C3-(3-methoxy)
・xypropoxy)probylthio]salicylic acid, 5-[
2(2-butoxyethoxy)ethylthio]salicylic acid,
5-(2-(2-hexyloxyethoxy)ethylthio]salicylic acid, 5-(pendylthio)salicylic acid,
5-(phenethylthio)salicylic acid, 5-(α-methylbenzylthio)salicylic acid, 5(p-chloropenzylthio)salicylic acid, 5(p-methylbenzylthio)salicylic acid, 5-(p-methoxybenzylthio)salicylic acid,
5-(0-chloropendylthio)salicylic acid, 5-(o
Methylbenzylthio)salicylic acid, 5-(αnaphthylmethylthio)salicylic acid, 5-(2-phenoxyethylthio)salicylic acid, 5-(3-phenoxypropylthio)
Salicylic acid, 5-(4phenoxybutylthio)salicylic acid, 5-[27 8 (p-methylphenoxy)ethylthio]salicylic acid, 5
- C3 - (p-methylphenoxy)propylthio]salicylic acid, 5-(4-(p-methylphenoxy)
Butylthio]salicylic acid, 5-[2(0-methylphenoxy)ethylthio]salicylic acid, 5-(2-(m-methylphenoxy)ethylthio)salicylic acid, 5-(2-(
p-chlorophenoxy)ethylthio]salicylic acid, 5-
(3-(p-chlorophenoxy)propylthio]salicylic acid, 5-(4-(p-chlorophenoxy)butylthio)salicylic acid, 5-(2-(p-methoxyphenoxy)ethylthio)salicylic acid, 5-[3(p-
Methoxyphenoxy)propylthio]salicylic acid, 5-
(4-(p-methoxyphenoxy)butylthio]salicylic acid, 5-[2-(o-methoxyphenoxy)ethylthio]salicylic acid, 5[3-(o-methoxyphenoxy)probylthio]salicylic acid, 5-(4-( o-Methoxyphenoxy)butylthio]salicylic acid, 5-(2-
(m-methoxyphenoxy)ethylthio]salicylic acid, 5
-(3-(m-methoxyphenoxy)propylthio]salicylic acid, 5-[4-(m-methoxyphenoxy)butylthio]salicylic acid, 5-[2(p-ethylphenoxy)ethylthio]salicylic acid, 5-(2- (p-isopropylphenoxy)ethylthio]salicylic acid, 5-
(2-(p-tertbutylphenoxy)ethylthio]salicylic acid, 5-(2-(p-cyclohexylphenoxy)ethylthio)salicylic acid, 5-(2-(
p-Phenylphenoxy)ethylthio]salicylic acid, 5
-[2-(p-phenoxyphenoxy)ethylthio]salicylic acid, 5-(2-α-naphthyloxyethylthio)
Salicylic acid, 5-(2-β-naphthyloxyethylthio)salicylic acid, 5-(3-α-naphthyloxypropylthio)salicylic acid, 5-(3-β-naphthyloxypropylthio)salicylic acid, 5-(4 -α-naphthyloxybutylthio)salicylic acid, 5-(4-β-naphthyloxybutylthio)salicylic acid, 5-(5-phenoxy-3
oxapentylthio) salicylic acid, 5-[59 10 (p-methylphenoxy)-3-oxapentylthio]
1.1 tylic acid, 5-(5-(p-chlorophenoxy)
~3-oxapentylthio]salicylic acid, 5-(5
- (p-methoxyphenoxy)-3-oxapentylthio]salicylic acid, 5-(8-phenoxy-3.6-
Dioxaoctylthio)salicylic acid, 5-CB-(p-
methoxyphenoxy)3,6-dioxaoctylthio]
Salicylic acid, 5(2-vinyloxyethylthio)salicylic acid, 5-(2-allyloxyethylthio)salicylic acid, 4-(hexylthio)salicylic acid, 4-(octylthio)salicylic acid, 4-(tetradecylthio)salicylic acid, 4- (hexadecylthio)salicylic acid, 4-(octadecylthio)salicylic acid, 4(2-ethoxyethylthio)salicylic acid, 4-(2-butoxyethylthio)salicylic acid, 4-[2(2-ethoxyethoxy)ethylthio]
Salicylic acid, 4- (2- (2-butoxyethoxy)
ethylthio]salicylic acid, 4-(pendylthio)salicylic acid, 4-(phenethylthio)salicylic acid, 4(α-methylbenzylthio)salicylic acid, 4(p~chloropenzylthio)salicylic acid, 4-(2-phenoxyethylthio)salicylic acid , 4-(3-phenoxypropylthio)salicylic acid, 4(4-phenoxybutylthio)salicylic acid, 4(2-(p-methoxyphenolic)ethylthio]salicylic acid, 4-(3-(p-methoxyphenoxy)propylthio) ] Salicylic acid, 4-[4-(p-methoxyphenoxy)butylthio]salicylic acid, 4-(
2-(m-methoxyphenoxy)ethylthio]salicylic acid, 4-(2-(0-methoxyphenoxy)
Ethylthio]salicylic acid, 4-(2-(p-chlorophenoxy)ethylthio)salicylic acid, 4-(2
- (p-phenylphenoxy)ethylthio]salicylic acid, 4 - [2 - (p-phenoxyphenoxy)
ethylthio]salicylic acid, 4-(5phenoxy-3-oxabentylthio)salicylic acid, 4-(5-(
p~methylphenoxy)-3oxapentylthio]salicylic acid, 4-[5~(p-chlorophenoxy)-3-oxapentylthio]salicylic acid, 4-(5-(p-methoxyphenoxy)- 3-oxapentylthio]salicylic acid, 4
-(8-phenoxy-3,6-dioxaoctylthio)
Salicylic acid, 4-CB-(p-methoxyphenoxy)-3,6-dioxaoctylthio]salicylic acid,
3-chloro5-(2-phenoxyethylthio)salicylic acid, 3-methyl-5-(2phenoxyethylthio)salicylic acid, 3-methoxy5-(2-phenoxyethylthio)salicylic acid, 3-aryl-5- (2-phenoxycetylthio)salicylic acid, 3-chloro-5-(2-(p
methoxyphenoxy)ethylthio]salicylic acid, 3-methyl-5-(2-(p-methoxyphenoxy)ethylthio)salicylic acid, 3-methoxy~5(2-(p-methoxyphenoxy)ethylthio)salicylic acid, 3-aryl-5-( 2-(p-methoxyphenoxy)ethylthio]salicylic acid, 4(phenylthio)salicylic acid, 5-(phenylthio)salicylic acid, 4-(p-methoxyphenylthio)salicylic acid, 5-(p-methoxyphenylthio)salicylic acid, 4-( p-Ethoxyphenyldio)salicylic acid, 5-(p-ethoxyphenylthio)salicylic acid, 4
-(p-butoxyphenylthio)salicylic acid, 5-(p
-butoxyphenylthio)salicylic acid, 4-(p-hexyloxyphenylthio)salicylic acid, 5-(p-hexyloxyphenylthio)salicylic acid, 4-(p-octyloxyphenylthio)salicylic acid, 5-(p-hexyloxyphenylthio)salicylic acid, octyloxyphenylthio)salicylic acid, 4(p-henzyloxyphenylthio)salicylic acid, 5-(p-phenethyloxyphenylthio)salicylic acid, and the like.

The above salicylic acid derivatives and/or metal salts thereof are
Two or more types can be used in combination if necessary.

In the present invention, the amount of the salicylic acid derivative and/or its metal salt to be used is not particularly limited, but is generally in the range of 50 to 5000 parts by weight, preferably 100 to 500 parts by weight, based on 100 parts by weight of the basic dye. It is preferable to adjust with

l3 14 In the present invention, by using a salicylic acid derivative represented by the general formula (1) and/or its metal salt as a coloring agent, a recording material with excellent color development and raw storage stability, especially storage stability of recorded images, can be obtained. However, these characteristics 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, cohardt,
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 alkunate, zinc sulfide, zinc carbonate, zinc phosphate, zinc silicate, aluminum oxide, magnesium oxide, titanium oxide, aluminum hydroxide, and silicate. Examples include aluminum acid, aluminum 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, akpalgyol, bentonite, colloidal silicate, 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, 15 16 phthalic acid, gallic acid, salicylic acid, 3-isoprobylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid , 3,5-di-tertbutylsalicylic acid,
3-Methyl-5-pendylsalicylic acid, 3-phenyl-5-(α,α-dimethylbenzyl)salicylic acid, 3.
5-'; mono(α-methylbenzyl)salicylic acid,
Aromatic carboxylic acids such as 2-hydroxy-1henjiru-3-naphthoic acid; 4,4'-isopropylidene diphenol (bisphenol A), 4.4'-isopropylidene bis(2-chlorophenol), 4.4' -isopropylidene bis(2,6-dichlorophenol), 4.
4'-isopropylidene bis(2.6 dibromophenol L 4,4'-isopropylidene bis(2-methylphenol), 4.4'isopropylidene bis(2.6-
dimethylphenol), 4.4'-isopropylidene bis(2ter t-butylphenol), 4. 4'
-sec butylidene diphenol, 2,2-bis(4
-hydroxydiphenyl)-4-methylpentane, 4,4
'-Cyclohexylidene bisphenol, 4,4'-cyclohexylidene bis(2-methylphenol), 4
-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α-naphthol,
β-Naphthol, Methinole 4-Hydroxybenzoate, Benzyl-4-Hydroxybenzoate, 2.2'-
Thiobis(4,6-dichlorophenol), 4-t
ert-octylcatechol, 2,2'-methylenebis(4-chlorophenol L 2,2'-methylenebis(
4-methyl-6-tert-butylphenol L 2,2
'dihydroxybiphenyl, methyl-bis(4-hydroxyphenyl) acetate, ethyl-bis(4-hydroxyphenyl) acetate, hengerubis(4-hydroxyphenyl) acetate, 4.4'-(p-phenylenediisobropylidene) di Phenol, 4.4'-(m
-phenylene diisopropylidene) diphenol, 4-
Hydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfone, 4-hydroxy-4' monomethy1
7 18 Diphenylsulfone, 4-hydroxy-4'isopropoxydiphenylsulfone, 4-hydroxy-3'
4'-tetramethylene diphenyl sulfone, 3,3'-
Phenolic compounds such as diallyl-4,4'-dihydroxydiphenylsulfone; organic coloring agents such as phenolic resins such as p-phenylphenol-formalin resin and p-butylphenol-acetylene resin; For example, salts with polyvalent metals such as zinc, magnesium, aluminum, calcium, titanium, manganese, tin, nickel, etc.; metal complex compounds such as antipyrine complex of zinc thiocyanate; hydrogen chloride, hydrogen bromide, hydrogen iodide, etc. Hydrohalic acids such as: boric acid, silicic acid, phosphoric acid, sulfuric acid, nitric acid, perchloric acid, aluminum, zinc, nickel, tin,
Halides such as titanium and boron; carbon tetrabromide, α, α
．． α-tribromoacetophenone, hexachloroethane,
Organic halogen compounds such as iodoform, 2-tribromomethylpyridine, trichloromethylsulfonylbenzene; 0-quinonediazide compounds; phenolic esters of carboxylic or sulfonic acids that cause photo-Fries transfer; 4-diazo-1-morpholino- 2. Diazo compounds that convert into phenol when exposed to light, such as 5-dibutoxyhensentetraphenylboron salt.

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 the following are exemplified.

3.3-bis(p-dimethylaminophenyl)6-dimethylaminophthalide, 3,3-bis(p-dimethylandanophenyl)phthalide, 3-(4dimethylaminophenyl)-1-(4-dimethylaminophthalide) 2-methylphenyl)-6-(dimethylano)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylindol-3-yl)phthalide, 3-(p-dimethylanophenyl)- 3-('2-methylindol-3yl)
Phthalide, 3,3-bis(1,2-dime19 20 tylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindole-3
-yl)-6-dimethylaminophtha IJt', 3.3-
Bis(9-ethylrubazol-3-yl)-6-dimethylaminophthalide, 3.3-bis(2-phenylindol-3-yl)6-dimethylaminophthalide, 3-p
-Triallylmethane dyes such as dimethylaminophenyl-3-(1-methylvirol-3-yl)-6-dimethylagonophthalide, 4,4'-bis-dimethylaminobenzhydrylbenzyl ether, N-halophenyl leucoaura 3. Diphenylmethane dyes such as 5-ton, N-2.4.5-trichlorophenylleucoauramine;
3-bis[1,1bis(4-pyrrolidinophenyl)ethylene-2yl)-4.5.6.7-tetrabromophthalide, 3 3-bis(1-(4-methoxyphenyl)1-
(4-dimethylaminophenyl)ethylene 2-yl)-
4.5,6.7-tetrac-orophthalide, 3.3-bis(1-(4-methoxyphenyl)-1-(4-pyrrolidinophenyl)ethylene 2-yl)-4.5,6. Divinyl phthalide dyes such as 7-tetrachlorophthalide, thiazine dyes such as penzoyl leucomethylene blue, p-nitrobenzoyl icomethylene blue, 3-methyl-spirodinaphthopyran, 3-ethyl-spirodinaphthopyran, 3 -Phenylsupidinaphtoviran, 3-
Spiro dyes such as penzyl-spirodinaphthopyran, 3-methyl-naphtho(6'-methoxybenzo)spiropyran, 3-propyl-sbyrodibenzopyran, rhodamine B-anilinolactam, rhodamine (p-nitroanilino)lactam, rhodamine [Lactam dyes such as (0-chloroanilino)lactam, 3-dimethylacuno-7-
Methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamino-7-chlorofluorane,
3-diethyl fluorane 6-methyl-7-chlorofluorane, 3-diethyl fluorane 6.7-dimethylfluorane 2
1 22 , 3-(N-ethyl-p-}luidino)-7methylfluorane, 3-diethylamino-7-(N-acetyl-N-methylamino)fluorane, 3-diethylamino-7-N-methylacunofluorane, 3-diethyl-7-dibenzylaminofluorane, 3-diethyl-7-(N-methyl-N-pendylamino)fluorane, 3-diethyl-7-(N-chloroethyl-N-methyl-5)fluorane, 3-diethyl-7-(N-methyl-N-pendylamino)fluorane 7-diethylaminofluorane, 4-benzyl 8-diethylaminobenzo(a) fluorane, 3-(4- (
4-dimethylaminoanilino)anilino]-7-chloro6-methylfluorane, 8-(4-(4-dimethylaminoanilino)anilino)-benzo[a]fluorane, 3(N-ethyl-P-1 luidino)-6-methyl 7
-phenylagonofluorane, 3-(N-ethyl-p-
1-Luidino)-6-methyl-7-(p-toluidino)fluorane, 3-diethyl-6-methyl-7-phenylaminofluorane, 3-dibutyl-6-methyl-
7-phenylaminofluorane, 3-diethylamino ξ-
7-(2-carpomethoxyphenylamino)fluorane, 3-(N-ethyl-N-isoamyl-amino)-6methyl-7-phenylaminofluorane, 3(N-cyclohexyl-N-methylamino)-6 1-methyl-7-phenylachofluorane, 3-pyrrolidino-6-methyl-7-
Phenylanofluorane, 3-piperidino-6-methyl-7-phenylaminofluorane, 3-diethylamino6-methyl-7-xylidinofluorane, 3-diethylamino7-(o-chlorophenylamino)fluorane, 3- Dibutylamino-7-(o-chlorophenylamino)fluorane, 3-(N-ethyl-N-tetrahydrofurfurylagono)-6-methyl-7-phenylaminofluorane, 3(N-methyl-N-n-propylamino) -6methyl-7-phenylaminofluorane, 3-(
N-ethyl-N-isobutylagono)-6-methyl-7
-phenylaminofluorane, 3-(N23 2 4-methyl-Nn-hexylamino)-6-methyl 7-phenylaminofluorane, 3-dipentylaminofluorane 6-
Methyl-7-phenylachofluorane, 3- (N-
(3-ethoxypipill)-1N-methylamino]-6
-Methyl-7-phenylaminofluorane, 3-[N-ethyl-N=(3ethoxypropyl)amino]-6-methyl-7-phenylaminofluorane, 3-diethylamino-7-(m-(}ly) Fluoromethyl)phenylamino]fluoran, 3-diethylamino-7(0-fluorophenylamino)fluoran, 3-dibutylamino7-
(o-fluorophenylamino)fluorane, 3-diethylamino-6chloro-7-phenylaminofluorane, 3-(N-ethylN-hexylamino)-6-
Fluoran dyes such as methyl-7-phenylaminofluorane, 3-(N-ethyl-N-cyclopentylamino)-6-methyl-7-phenylaminofluorane, 3,6
-bis(dimethylano)fluorene-9-subilo 3
'-(6'-dimethylamino)phthalide, 3-diethylamino-6-(N-aryl-N-methylamino)
Fluorene-9spiro-3'-(6'-dimethylamino)phthalide, 3,6-bis(dimethylamino)-subiro[fluorene-9.6'-6'H-chromeno
(43-b) indole), 3,6-bis(dimethylamino)-3'-methyl-spiro[fluorene-9.6'
-6' H-chromeno (4.3-b) indole L
3,6-bis(diethylamino)-3'methyl-spi[fluorene-9.6'-6'H-chromeno(4,3
-b) Fluorene dyes such as indole]. 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, palcinic acid amide, stearic acid amide, oleic acid amide,
Erucic acid amide, linoleic acid amide, linolenic acid amide, N-methyl stearic acid amide, stearic acid anilide, N-methyl oleic acid amide, penzanilide, linoleic acid anilide, N-ethyl puric acid amide , N-butyllauric acid amide, N-octadecyl acetate, N-oleic acid acetate, N-oleyl benzene, N-stearyl hexylamide, polyethylene glycol, l-penzyloxynaphthalene, 2-penzyloxynaphculene, l-hydroxynaphthoic acid phenyl ester, 1,2-diphenoxyethane, 1,4-diphenoxybutane, 1,2-bis(3methylphenoxy)ethane, 1,2-bis (4methoxyphenoxy)ethane, 1
-phenoxy 2-(4-chlorophenoxy)ethane, 1
-phenoxy-2-(4-methoxyphenoxy)ethane, terephthalic acid dihenzyl ester, dibenzyl oxalate, p-penzyloxybenzoic acid benzyl ester, p
-Pendylbiphenyl, 1,5bis(p-methoxyphenoxy)-3-oxapentane, and 1,4-bis(2-vinyloxyel-1-xy)benzene.

Below, various representative recording materials using the salicylic acid derivative represented by the general formula [I] 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. 2.730457, No. 3, 4
No. 18,250, No. 3,924,027, No. 4,01
As described in No. 0,038, there are various types of pressure-sensitive recording media, and the present invention can be applied to these various types of pressure-sensitive recording bodies.

Generally, at least one of the salicylic acid derivatives or metal salts thereof of the present invention is dispersed in various binders such as styrene-bookdiene copolymer latex and polyvinyl alcohol, along with other coloring agents and pigments as necessary. A color former sheet 1- (27 28 so-called bottom sheet) is produced by coating the color former coating liquid on 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 made of basic dyes such as alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated terphenyl, etc.; cotton; A dispersion obtained by dissolving this in a suitable solvent such as oil, vegetable oil such as castor oil; animal oil; mineral oil or a mixture thereof, or the like, and dispersing it in a binder, or the above solution can be processed by coacervation method, interfacial polymerization method, It is manufactured by containing it in microcapsules by various encapsulation methods such as in-situ method, and coating the dispersion liquid dispersed in a binder on a suitable support such as paper, plastic sheet, resin-coated paper, etc. Ru.

Of course, there are so-called intermediate sheets 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 made 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 media are disclosed in Japanese Patent Publication No. 44-3680 and No. 4.
No. 427880, No. 45-14039, No. 48-43
No. 830, No. 49-69, No. 49-70,
As described in No. 52-20142, there are various types of salicylic acid derivatives, 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.

Generally, a coating liquid obtained by dissolving or dispersing a binder and dispersing the salicylic acid derivative of the present invention or its metal salt and fine particles of a basic dye in a medium is applied to paper, plastic film, laminated paper, and even textiles. The heat-sensitive recording material of the present invention is produced by coating it on a suitable support such as a cloth sheet or an ornament. The ratio of basic dye and coloring agent used in the recording layer is not particularly limited, but is generally 1 part by weight of dye.
About 50 parts by weight, preferably 1 to 10 parts by weight of the coloring agent is 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 0.1 to 10 parts by weight, preferably 0.5 to 3 parts by weight, per 1 part by weight of the coloring agent. They can be used together in parts by weight, and various auxiliaries such as dispersants, ultraviolet absorbers, thermofusible substances (recording sensitivity improvers), antifoaming agents, fluorescent dyes, and coloring dyes can be added as necessary. Can be used together as appropriate.

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/n'f is applied. Furthermore, it is of course possible to provide an overcoat layer on the recording layer 2 for the purpose of protecting the recording layer, or to provide an undercoat layer on the support, and various known techniques in the heat-sensitive recording material manufacturing field can be used as appropriate. ” can be added.

Examples of binders include starches, celluloses, proteins, gum arabic, polyvinyl alcohol, styrene-maleic anhydride Ml combined salt, acetic acid bee-maleic anhydride copolymer salt, polyacrylate, and styrene-butadiene copolymer emulsion. etc. are selected and used as appropriate.

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 in which a conductive substance, a basic dye, and a coloring agent are 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, if both the dye and the coloring agent do not melt in the preferred temperature range of 70 to 120°C, the sensitivity to Joule heat can be adjusted by using an appropriate thermofusible substance in combination. .

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 high quality characteristics.

"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-phenylatonofluorane were dissolved in 100 parts of isoprobylated naphthalene, and 25 parts of big skin gelatin with an isoelectric point of 8 and Arabica were dissolved. 350 with 25 parts of rubber dissolved
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 remove the glutaraldehyde.
The capsules were cured by adding 10 parts of a 5% aqueous solution.

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

On the other hand, add 5-(2-phenoxyedylthio) to 200 parts of water.
20 parts of zinc salt of salicylic acid, 80 parts of kaolin, styrene-butadiene copolymer emulsion (solid content = 50%)
A coloring agent coating liquid in which 30 parts of the coloring agent was dispersed was applied to a base paper weighing 45 g/rd so that the dry weight was 5 g/rd to obtain a coloring agent sheet.

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 production of the coloring agent sheet of Example 1, the following examples were used except that the following coloring agent was used instead of 20 parts of zinc salt of 5(2-phenoxyethylthio)salicylic acid. Three types of coloring agent sheets were obtained in the same manner as in Example 1.

Example 2: 20 parts zinc salt of 5-(2-(P-methoxyphenoxy)ethylthio)salicylic acid Example 3
: Zinc salt of 5-(4-phenoxybutylthio)salicylic acid 20 parts Example 4 : Zinc salt of 5-(2-phenoxyethylthio)salicylic acid 10 parts 3.5-bis(α-methylbenzyl) When 10 parts of the zinc salt of salicylic acid and the three types of color formers obtained were used to develop color in the same manner as in Example 1, a black image was instantly obtained in all cases. These images had high density and excellent light resistance.

Example 5 ■ Preparation of liquid A 3-(N-ethyl-N-isoamyl-fluorane)-6-methyl-7-phenylafluorane 10 parts 1.2-bis(3-methylphenoxy)ethane 20 parts Methyl cellulose 5% aqueous solution 15 parts water
120 parts of this assembly was ground in a sand mill until the average particle size was 3 μm.

■ Preparation of Solution B 5-(2-phenoxyethylthio)zinc salt of salicylic acid 30 parts Methylcellulose 5% aqueous solution 30 parts water
70 parts of this composition was ground with a sander until the average particle size was 3 μm.

■ Form of recording layer: 165 parts of liquid A, 130 parts of liquid B, silicon oxide pigment (oil absorption 1
80ml/100g) 30 parts, 150 parts of a 20% oxidized starch aqueous solution, and 155 parts of water were mixed and stirred to prepare a recording layer coating liquid. The resulting coating liquid was applied to base paper of 50 g/nf so that the dry weight was 6.0 g/rrf and dried to obtain a heat-sensitive recording paper.

Examples 6 to 16 35 36 B of Example 5? Eleven types of thermal recording paper were obtained in the same manner as in Example 5, except that the following compound was used instead of the zinc salt of 5-(2-phenoxyethylthio)salicylic acid in the preparation.

Example 6: Zinc salt of 5-(5-phenoxy-3-oxabentylthio)salicylic acidExample 7: Zinc salt of 5-(hexadecylthio)salicylic acidExample 8: Zinc salt of 4-Ctetradecylthio)salicylic acid Implementation Example 9: Zinc salt of 5-(2-(2-ethoxyethoxy)ethylthio)salicylic acidExample 10: Zinc salt of 5-(4-phenoxybutylthio)salicylic acidExample 11: 5-(2-(m Zinc salt of 5-(2-(P-methoxyphenoxy)ethylthio)salicylic acid Example 13: 4-(2-(P-methoxyphenoxy)ethylthio) ] Zinc salt of salicylic acid Example 14: 5-(P-butoxyphenylthio)salicylic acid Example 15: 5-(2-phenoxyethylthio)salicylic acid Example 16: 5-(occudecylthio)salicylic acid Example 17 Implementation A thermal paper was obtained in the same manner as in Example 5 except that 30 parts of zinc oxide and 40 parts of water were used instead of 70 parts of water in the BitPJ product.

Examples 18-28 In the preparation of Solution B of Example 17, 11 kinds of A thermosensitive recording paper was obtained.

Example 18: Zinc salt of 5-(5-phenoxy-3-oxapentylthio)salicylic acid Example 19: Zinc salt of 5-(hexadecylthio)salicyl 37 38 acid Example 20: Zinc salt of 4-(tetradecylthio)salicylic acid Zinc salt Example 21: 5-(2-phenokyethylthio)salicylic acid Example 22: 5-C4-phenoxybutylthio)salicylic acid Example 23: 5-(2-(m-methylphenoxy)ethylthio)salicylic acid Example 24: 5-(2-Cp-Methoxyphenoxy)ethylthio]salicylic acid Example 25: 4-(2-(P-methoxyphenoxy)ethylthio)salicylic acid Example 2675-(P-Butoxyphenylthio)salicylic acid Example 21: 5-C?/- (2-ethoxyethoxy)ethylthio]salicylic acid Example 28: 5-(octadecylthio)salicylic acid Examples 29 to 31 In the preparation of solution B of Example 17, the following compound was used instead of zinc oxide. Three types of thermal recording paper were obtained in the same manner as in Example 17 except that .

Example 29: Zinc carbonate Example 30 Magnesium dioxide Example 31: Aluminum hydroxide Comparative Examples 1 to 5 In the preparation of Solution B of Example 5, instead of the zinc salt of 5-(2-phenoxyethylthio)salicylic acid Five types of thermal recording papers were obtained in the same manner as in Example 5, except that the following compounds were used.

Comparative example 1: 4,4'-isopropylidene diphenol Comparative example 2: 4,4'-cyclohexylidene bisphenol Comparative example 3: Dimethyl 4-hydroxy-O-phthalate Comparative example 4: 3,5-bis(α -Methylbenzyl) salicylic acid zinc salt Comparative example 5: p-chlorobenzoic acid zinc salt 39 40 The 32 types of thermal recording paper thus obtained were subjected to thermal facsimile (Hitachi HI FAX-700 model, Hitachi Co., Ltd.) made)
The color density was recorded using a Macbeth densitometer (R
The results are shown in Table 1.

After the above-mentioned recording, the thermal recording paper was left for 20 hours under high temperature drying conditions at 60°C, and then dried at 40°C and 90% R. l{.
After being left for 20 hours under high humidity conditions, the color density of the recorded image was measured using a Macbeth densitometer, and the heat resistance and moisture resistance of the recorded image were evaluated. 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 1 hour (plasticizer resistance), and when ethanol was applied to the colored side (ethanol resistance). ), when cottonseed oil is applied to the coloring surface (
The degree of fog in the blank area and the degree of fading of the recorded image was evaluated for each of the oil resistance), and the results are shown in Table 1.

"Effect" As is clear from the results in Table 1, the recording material according to the present invention has a high color density and is an excellent recording material with excellent storage stability of recorded images, especially without fading of the colored area due to chemicals and without blurring of the background. there were.

4l 42

Claims (4)

[Claims] (1) In a recording material that utilizes a coloring reaction between a colorless or light-colored basic dye and a coloring agent that can change color when it comes into contact with the dye, the coloring agent is expressed by the following general formula [I]. A recording material characterized by using at least one salicylic acid derivative or a metal salt thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R represents an alkyl group that may have a substituent or an aryl group that may have a substituent, and X is a hydrogen atom. , an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkoxyl group, an aryloxy group, a nitro group, or a 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 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.