JP3220511B2 - Novel ether compound and thermosensitive recording material containing it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel ether compound, and more particularly to an ether compound useful as a sensitizer for thermal recording.

[0002]

2. Description of the Related Art Heat-sensitive recording materials utilizing a color reaction between an electron-donating color-forming compound and an electron-accepting compound (a color developer) are well known (for example, Japanese Patent Publication No. Sho 43-4).
No. 160, JP-B-45-14039). Phenolic compounds are widely used as electron-accepting compounds. Among them, 2,2-bis (4′-hydroxyphenyl) propane (also called bisphenol A) is widely used because it is easily available at low cost. Although used, heat-sensitive recording materials using bisphenol A as the electron-accepting compound have the problem of low color sensitivity.
Further, in addition to the electron-donating color-forming compound and the electron-accepting compound, a heat-sensitive recording material containing a heat-fusible compound (sensitizer) and having improved color-forming sensitivity has been widely used. As a heat-fusible compound, for example, 2,2-bis (4'-benzyloxyphenyl) propane has been proposed (Japanese Patent Publication No. 2-59785). However, the thermosensitive recording material containing the compound also has not so high coloring sensitivity,
Further improvements are desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel ether compound useful as a material for thermal recording (sensitizer), and a thermal recording material containing the ether compound. It is to provide.

[0004]

Means for Solving the Problems The inventors of the present invention have synthesized many compounds in order to solve the above-mentioned problems, and as a result of intensive studies, have reached the present invention. That is, the present invention provides an ether compound represented by the general formula ( 1 ′) ( Formula 4) ,

[0005]

Embedded image (Wherein, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R represents a lower alkyl group).
A linear or branched alkylene group, R is related to ether compounds represented by the ether compound and the general formula is a methyl group (2) (Formula 5).

[0006]

Embedded image Further, in a thermosensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound, the following general formula (1)
The present invention relates to a heat-sensitive recording material containing at least one ether compound represented by the formula (6) .

Embedded image (Wherein X is a linear or branched alkylene having 1 to 6 carbon atoms)
R represents a lower alkyl group. However, both ends
The substitution positions of the substituent R on the phenyl group are the same. )

In the compounds represented by the general formulas (1) and (1 ') of the present invention, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, for example, a methylene group, 1,1-
Ethylene group, 1,2-ethylene group, 1,3-propylene group, 2,2-propylene group, 1,1-butylene group, 1,
Examples thereof include a 4-butylene group, a 2,2-butylene group, a 1,5-pentane group, a 1,6-hexylene group, a 2,2-isohexylene group, and more preferably a methylene group, 1,1- Ethylene group, 2,2-propylene group, 1,
It is a 1-butylene group or a 2,2-isohexylene group, and particularly preferably a 2,2-propylene group.

In the compounds represented by the general formulas (1) and (1 ') of the present invention, R represents a lower alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl. Group, isobutyl group, sec-butyl group,
A tert-butyl group and the like can be mentioned, and a methyl group is particularly preferred. In the general formula (1), the substitution position of the substituent R is an ortho position, a meta position or a para position with respect to the ether bond, and is particularly preferably a para position. However
And the substitution positions of the substituents R on both terminal phenyl groups are the same.
is there. Among the compounds represented by formula (1 ′) of the present invention, particularly preferred compounds include compounds represented by formula (2) .

Preferred examples of the compound represented by the general formula (1) of the present invention include the following compounds. -Exemplified compound No.Compound 1.1,1-bis [4 '-(4 "-methylphenyl) oxyphenyl] methane 2.1,1-bis [4'-(3" -methylphenyl) oxyphenyl] methane 3 .1,1-bis [4 '-(2 "-methylphenyl) oxyphenyl] methane 4.1,1-bis [4'-(4" -methylphenyl) oxyphenyl] ethane 5.1,2-bis [4 '-(4 "-methylphenyl) oxyphenyl] ethane 6.1,3-bis [4'-(4" -methylphenyl) oxyphenyl] propane 7.2,2-bis [4 '-(4 "-Methylphenyl) oxyphenyl] propane 8.2,2-bis [4 '-(3" -methylphenyl) oxyphenyl] propane 9.2,2-bis [4'-(2 "-methylphenyl) oxy Phenyl] propane 10.1 , 1-bis [4 ′-(4 ″ -methylphenyl) oxyphenyl] butane

11.2,2-Bis [4 ′-(4 ″ -methylphenyl) oxyphenyl] butane 12.1,5-Bis [4 ′-(2 ″ -methylphenyl) oxyphenyl] pentane 13.1 , 6-bis [4 '-(3 "-methylphenyl) oxyphenyl] hexane 14.2,2-bis [4'-(4" -methylphenyl) oxyphenyl] isohexane 15.2,2-bis [4 '-(3 "-methylphenyl) oxyphenyl] isohexane 16.1,1-bis [4'-(4" -ethylphenyl) oxyphenyl] methane 17.2,2-bis [4 '-(4 "- Ethylphenyl) oxyphenyl] propane 18.2,2-bis [4 '-(4 "-ethylphenyl) oxyphenyl] butane 19.2,2-bis [4'-(3" -ethylphenyl) Oxyphenyl] butane 20.1,1-bis [4 '-(4 "-n-propylphenyl) oxyphenyl] methane 21.1,1-bis [4'-(3" -n-propylphenyl) oxyphenyl ] Ethane 22.2,2-bis [4 '-(4 "-n-propylphenyl) oxyphenyl] propane 23.2,2-bis [4'-(4" -n-propylphenyl) oxyphenyl] butane 24.2,2-Bis [4 '-(4 "-n-propylphenyl) oxyphenyl] isohexane 25.2,2-Bis [4'-(4" -isopropylphenyl) oxyphenyl] propane

26.2,2-bis [4 ′-(3 ″ -isopropylphenyl) oxyphenyl] propane 27.2,2-bis [4 ′-(4 ″ -isopropylphenyl) oxyphenyl] isohexane 28.2 , 2-Bis [4 '-(3 "-n-butylphenyl) oxyphenyl] propane 29.1,4-bis [4'-(4" -n-butylphenyl) oxyphenyl] butane 30.2,2 -Bis [4 '-(4 "-isobutylphenyl) oxyphenyl] propane 31.2,2-bis [4'-(4" -isobutylphenyl) oxyphenyl] butane 32.2,2-bis [4'- (4 "-isobutylphenyl) oxyphenyl] isohexane 33.2,2-bis [4 '-(4" -sec-butylphenyl) oxyphenyl] propane 34.2 -Bis [4 '-(4 "-sec-butylphenyl) oxyphenyl] isohexane 35.1,1-bis [4'-(4" -tert-butylphenyl) oxyphenyl] methane 36.2,2-bis [4 '-(4 "-tert-butylphenyl) oxyphenyl] propane

The ether compounds represented by the general formulas (1) and (1 ') of the present invention can be suitably produced by a per se known etherification method. For example, a base (eg, potassium carbonate, sodium hydroxide, potassium hydroxide) and a copper catalyst (eg, copper powder, chloride 1) are added to 1 mol of the diphenol compound represented by the general formula (3) (formula 7) . In the presence of copper, cuprous bromide, cuprous oxide, copper carbonate, 8-oxyquinoline copper complex, acetylacetone copper complex), about 2-3 mol of a lower alkyl-substituted phenyl halide (for example, lower alkyl-substituted phenyl chloride) ,
Lower alkyl-substituted phenyl bromide).

[0013]

Embedded image (Wherein, X has the same meaning as in formula (1))

In this reaction, a suitable solvent, for example,
Use a polar solvent such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide, 1,3-dimethylpropyleneurea, or a mixed solvent thereof. Is preferred. The reaction temperature is usually 1
The reaction is carried out at a temperature of from 00 to 250 ° C, more preferably from 150 to 230 ° C, and the reaction time depends on the reaction temperature.
It takes several tens of hours. The target substance can be purified by a known purification method (recrystallization, column chromatography, etc.) as necessary to increase the purity.

In the thermosensitive recording material of the present invention, usually,
The electron-accepting compound is used in an amount of 50 to 700 parts by weight, preferably 100 to 5 parts by weight, per 100 parts by weight of the electron-donating color-forming compound.
It is desirable to use 00 parts by weight, 10 to 500 parts by weight, preferably 20 to 400 parts by weight of the ether compound of the present invention.

The electron-donating color-forming compound used in the present invention is a colorless or pale-colored compound, and may be a triarylmethane compound, a diarylmethane compound, a rhodamine-lactam compound, a fluoran compound, or an indolylphthalide compound. , Pyridine compounds, spiro compounds, fluorene compounds and the like. Some specific examples of these compounds include 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide [crystal violet lactone] and 3,3-bis (4-dimethylaminophenyl) -based compound. Bis (4-dimethylaminophenyl) phthalide, 3- (4-dimethylaminophenyl) -3- (1,3-dimethylindol-3-yl)
Phthalide, 3- (4-dimethylaminophenyl) -3-
(2-methylindol-3-yl) phthalide, 3,3
-Bis (9-ethylcarbazol-3-yl) -6-dimethylaminophthalide, 3- (4-dimethylaminophenyl) -3- (1-methylpyrrol-3-yl) -6
Dimethylaminophthalide, 3,3-bis [2,2-bis (4-dimethylaminophenyl) ethenyl] -4,5
6,7-tetrachlorophthalide and the like.

Examples of the diarylmethane compound include 4,
4-bis-dimethylaminobenzhydrin benzyl ether, N-halophenyl-leuco auramine, N-2,
4,5-trichlorophenylleuco auramine and the like. Examples of rhodamine-lactam compounds include rhodamine-B-anilinolactam, rhodamine- (4-nitroanilino) lactam, and rhodamine-B- (4-chloroanilino) lactam.

Examples of the fluoran compounds include 3,6-dimethoxyfluoran, 3-dimethylamino-7-methoxyfluoran, 3-diethylamino-6-methoxyfluoran, 3-diethylamino-7-methoxyfluoran, Diethylamino-7-chlorofluoran, 3-
Diethylamino-6-methyl-7-chlorofluoran,
3-diethylamino-6,7-dimethylfluoran, 3
-N-cyclohexyl-NN-butylamino-7-methylfluoran, 3-diethylamino-7-dibenzylaminofluoran, 3-diethylamino-7-octylaminofluoran, 3-diethylamino-7-di-n −
Hexylaminofluoran, 3-diethylamino-7-
Anilinofluoran, 3-diethylamino-7- (2-
Chloroanilino) fluoran, 3-diethylamino-7
-(3-chloroanilino) fluoran, 3-diethylamino-7- (2,3-dichloroanilino) fluoran,
3-diethylamino-7- (3-trifluoromethylanilino) fluoran, 3-di-n-butylamino-7-
(2-chloroanilino) fluoran, 3-diethylamino-6-chloro-7-anilinofluoran,

3-Di-n-butylamino-6-chloro-
7-anilinofluoran, 3-diethylamino-6-methoxy-7-anilinofluoran, 3-di-n-butylamino-6-ethoxy-7-anilinofluoran, 3-
Pyrrolidino-6-methyl-7-anilinofluoran, 3
-Morpholino-6-methyl-7-anilinofluoran,
3-dimethylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3-di-n-butylamino-6-methyl-
7-anilinofluoran, 3-di-n-pentylamino-6-methyl-7-anilinofluoran, 3-di-n-
Octylamino-6-methyl-7-anilinofluoran, 3-N-ethyl-N-methylamino-6-methyl-
7-anilinofluoran, 3-Nn-propyl-N-
Methylamino-6-methyl-7-anilinofluoran,
3-N-n-propyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isopropyl-N
-Methylamino-6-methyl-7-anilinofluoran, 3-NN-butyl-N-methylamino-6-methyl-7-anilinofluoran, 3-NN-butyl-N
-Ethylamino-6-methyl-7-anilinofluoran,

3-Nn-butyl-NNn-propylamino-6-methyl-7-anilinofluoran, 3-N-
Isobutyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-isobutyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-isopentyl-N-ethylamino -6-methyl-7-anilinofluoran, 3-NN-hexyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-
n-octyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-N-methylamino-6-methyl-7-anilinofluoran, 3-
N-cyclohexyl-NN-propylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-NNn-butylamino-6-methyl-7-anilinofluoran, 3-N- Cyclohexyl-Nn-pentylamino-6-methyl-7-anilinofluoran, 3-
N-cyclohexyl-NN-hexylamino-6-methyl-7-anilinofluoran, 3-N-cyclohexyl-Nn-heptylamino-6-methyl-7-anilinofluoran, 3-N- Cyclohexyl-Nn-octylamino-6-methyl-7-anilinofluoran, 3
-N-cyclohexyl-NN-decylamino-6-methyl-7-anilinofluoran,

3-N-2'-methoxyethyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N
-2'-methoxyethyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-2'-ethoxyethyl-N-methylamino-6-methyl-7-anilinofluoran, 3 -N-2'-ethoxyethyl-N-ethylamino-6-methyl-7-anilinofluoran, 3-N-3 '
-Methoxypropyl-N-methylamino-6-methyl-
7-anilinofluoran, 3-N-3'-ethoxypropyl-N-methylamino-6-methyl-7-anilinofluoran, 3-N-2'-methoxyethyl-N-isobutylamino-6 Methyl-7-anilinofluoran, 3-N
-2'-tetrahydrofurfuryl-N-ethylamino-6
-Methyl-7-anilinofluoran, 3-N- (4'-methylphenyl) -N-ethylamino-6-methyl-7-
Anilinofluoran, 3-diethylamino-6-ethyl-7-anilinofluoran, 3-di-ethylamino-6
-Methyl-7- (2 ', 6'-dimethylphenylamino) fluoran, 3-di-n-butylamino-6-methyl-7
-(2 ', 6'-dimethylphenylamino) fluoran, 3-di-n-butylamino-7- (2', 6'-dimethylphenylamino) fluoran, 2,2-bis [4 '-(3- N-cyclohexyl-N-methylamino-6-methylfluoran) -7-ylaminophenyl
And propane.

As the indolylphthalide compound,
3,3-bis (1-ethyl-2-methylindole-3
-Yl) phthalide, 3,3-bis (1-octyl-2-
Methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3
-(2-ethoxy-4-dibutylaminophenyl) -3
-(1-Ethyl-2-methylindol-3-yl) phthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-octyl-2-methylindole-
3-yl) phthalide and the like.

Examples of the pyridine compound include 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-octyl-2-methylindol-3-yl) -4 or 7-azaphthalide, Ethoxy-4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3-
(2-hexyloxy-4-diethylaminophenyl)
-3- (1-Ethyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-ethyl-
2-phenylindol-3-yl) -4 or 7-azaphthalide, 3- (2-butoxy-4-diethylaminophenyl) -3- (1-ethyl-2-phenylindol-3-yl) -4 or 7- Azaphthalide and the like.

Examples of the spiro compounds include 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran,
Benzyl-spiro-dinaphthopyran, 3-methyl-naphtho- (3-methoxybenzo) spiropyran, 3-propyl-spiro-dibenzopyran and the like.

As the fluorene compound, 3 ′, 6 ′
-Bisdiethylamino-5-diethylaminospiro (isobenzofuran-1,9'-fluoren) -3-one,
3 ', 6'-bisdiethylamino-7-diethylamino-2
-Methylspiro (1,3-benzoxazine-4,9 ′
-Fluorene). These electron-donating color-forming compounds may be used alone or as a mixture of two or more kinds for the purpose of adjusting the color tone of a color-formed image or obtaining a multicolor heat-sensitive recording material.

The electron accepting compound used in the present invention includes organic electron accepting compounds such as phenol derivatives, organic acids or metal salts and complexes thereof, urea derivatives, and inorganic electron accepting compounds such as acidic clay. . Some examples of these compounds include 4-tert-butylphenol, 4-tert-octylphenol,
Phenylphenol, 1-naphthol, 2-naphthol, hydroquinone, resorcinol, 4-tert-octylcatechol, 2,2′-dihydroxydiphenyl,
2,2-bis (4′-hydroxyphenyl) propane [also known as bisphenol A], 1,1-bis (4′-hydroxyphenyl) cyclohexane, 2,2-bis (4′-hydroxy-3′-methylphenyl) ) Propane, 2,2-bis (4′-hydroxyphenyl) acetic acid ethyl ester, 4,4- (4′-hydroxyphenyl)
Pentanoic acid-n-butyl ester, 4-hydroxybenzoic acid benzyl ester, 4-hydroxybenzoic acid phenethyl ester, 2,4-dihydroxybenzoic acid phenoxyethyl ester, 4-hydroxyphthalic acid dimethyl ester, phthalic acid monobenzyl ester, phthalate Acid monophenyl ester,

Hydroquinone monobenzyl ether, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (2-methyl-4-hydroxyphenyl) sulfide, bis (3-phenyl-4-hydroxyphenyl) sulfide, bis (3 -Cyclohexyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone, 4-hydroxy-4'-n- Propoxydiphenylsulfone, 4-hydroxy-4'-
Isopropoxydiphenylsulfone, 4-hydroxy-4′-n-butoxydiphenylsulfone, 3,4-
Dihydroxy-4'-methyldiphenylsulfone, bis (2-hydroxy-4-tert-butylphenyl) sulfone, bis (2-hydroxy-4-chlorophenyl)
Sulfone, 4-hydroxybenzophenone, 2,4-
Dihydroxybenzophenone, 1,7-di (4-hydroxyphenylthio) -3,5 dioxaheptane, 1,5
Phenol derivatives such as -di (4-hydroxyphenylthio) -3oxapentane,

Salicylic acid, 3-isopropylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-te
rt-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 3-methyl-5-α-methylbenzylsalicylic acid, 5- [2 ′-(4-methoxyphenyloxy) ethyloxy] salicylic acid, 2-hydroxy- 3-
Organic acids such as naphthoic acid, 2-hydroxy-6-naphthoic acid, monobenzyl phthalate and monophenyl phthalate, and metal salts thereof (for example, metal salts such as nickel, zinc, aluminum and calcium);
Complexes such as zinc thiocyanate antipyrine complex and acetylacetone molybdate complex, phenylthiourea, di (3-trifluoromethylphenyl) thiourea, 1,4
Organic electron-accepting compounds such as urea derivatives such as -di (3'-chlorophenyl) -3-thiosemicarbazide, acid clay, attapulgite, activated clay, aluminum chloride,
Preferred compounds include inorganic electron-accepting compounds such as zinc chloride and zinc bromide. These electron accepting compounds may be used alone or in combination of two or more. In particular, phenol derivatives are used as preferred electron accepting compounds.

The heat-sensitive recording material of the present invention is a heat-sensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound, and further contains at least one ether compound of the present invention. In response to the,
A heat-fusible compound (compound having a melting point of about 60 to 150 ° C.) as a sensitizer may be further added to the heat-sensitive recording material of the present invention. In this case, usually, the electron-accepting compound is added in an amount of 50 to 700 parts by weight with respect to 100 parts by weight of the electron-donating color-forming compound.
Preferably 100 to 500 parts by weight, 10 to 500 parts by weight, preferably 20 to 400 parts by weight of the ether compound of the present invention, and 10 to 500 parts by weight, preferably 20 to 400 parts by weight of the heat-fusible compound. Is desirable.

Specific examples of such a heat-fusible compound include:
For example, nitrogen-containing compounds such as stearic acid amide, palmitic acid amide, stearyl urea, N-ethylcarbazole, 4-methoxydiphenylamine, benzyl 4-benzyloxybenzoate, phenyl 2-naphthoate, 1-hydroxy-2- Naphthoic acid phenyl ester, oxalic acid dibenzyl ester, oxalic acid di (4-methylbenzyl) ester, oxalic acid di (4-chlorobenzyl) ester, glutaric acid diphenacyl ester, di (4-methylphenyl) carbonate, terephthalic acid Ester compounds such as acid dibenzyl ester;
Benzylbiphenyl, m-terphenyl, fluorene,
Hydrocarbon compounds such as fluoranthene, 2-benzyloxynaphthalene, 2- (4'-methylbenzyloxy)
Naphthalene, 1,4-diethoxynaphthalene, 1,2-
Bis (3′-methylphenoxy) ethane, 1-phenoxy-2- (4-ethylphenoxy) ethane, 4- (4 ′
-Methylphenoxy) biphenyl, 1,4-bis (2 ′
-Chlorobenzyloxy) benzene, 4,4'-di-n
-Butoxydiphenylsulfone, 1,2-diphenoxybenzene, 1,4-bis (3'-methylphenyloxymethyl) benzene, 4-chlorobenzyloxy-
And ether compounds such as (4'-ethoxybenzene). These heat-fusible compounds may be used alone or in combination of two or more.

The heat-sensitive recording material of the present invention can be manufactured by a known method without a special method. In general, the electron-donating color-forming compound, the electron-accepting compound and the ether compound of the present invention are each usually 3 μm or less, preferably 1.5 μm, in a water-soluble binder by means of a ball mill, a sand mill or the like. The coating liquid can be prepared by pulverizing and dispersing the particles to the following particle diameters and mixing them. Specific examples of such a water-soluble binder include, for example, polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, isobutylene-anhydride. Examples include maleic acid copolymer, polyacrylic acid, polyacrylamide, methylol-modified polyacrylamide, starch derivatives, casein, gelatin, methylcellulose, carboxymethylcellulose, gum arabic, and carboxyl-modified polyvinyl alcohol.

If necessary, the recording layer of the heat-sensitive recording material of the present invention may contain a pigment, a water-insoluble binder, a metal soap, a wax, a surfactant, an ultraviolet absorber, a hindered phenol, an antifoaming agent, and the like. Added. As pigments, zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, titanium oxide, talc, laurite, kaolin, diatomaceous earth, aluminum hydroxide, magnesium hydroxide, alumina, silica, amorphous Silica, urea-formalin filler, polyethylene particles, cellulose filler and the like are used. As the water-insoluble binder, synthetic rubber latex or synthetic resin emulsion is generally used, and styrene-butadiene rubber latex, acrylonitrile-butadiene latex,
Methyl acrylate-butadiene rubber latex, vinyl acetate emulsion and the like are used.

As the metal soap, higher fatty acid metal salts are used, and zinc stearate, calcium stearate,
Aluminum stearate or the like is used. Examples of the wax include paraffin wax, microcrystalline wax, carboxy-modified paraffin wax, carnauba wax, polyethylene wax, polystyrene wax, and higher fatty acid esters. Examples of the surfactant include a sulfosuccinic acid-based alkali metal salt, a fluorine-containing surfactant, and the like. Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, and benzotriazolylphenol derivatives.

The hindered phenol is preferably a phenol derivative in which at least one of the ortho positions of the phenolic hydroxyl group is substituted with a branched alkyl group.
3-tris (2-methyl-4-hydroxy-5-tert-
Butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl)
Butane, 1,1,3-tris (2-ethyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3
-Tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (2-methyl-
4-hydroxy-5-tert-butylphenyl) propane, 2,2′-methylene-bis (6-tert-butyl-4)
-Methylphenol), 2,2′-methylene-bis (6
-Tert-butyl-4-ethylphenol), 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-tert
-Butyl-4-hydroxybenzyl) benzene, 1,
3,5-tris (4-tert-butyl-3-hydroxy-
2,6-dimethylbenzyl) isocyanuric acid, 1,3
5-tris (4-tert-butyl-3-hydroxy-2-
Methyl-6-ethylbenzyl) isocyanuric acid, bis (2-methyl-4-hydroxy-5-tert-butylphenyl) sulfide and the like.

In the heat-sensitive recording material of the present invention, the method for forming the recording layer is not particularly limited, and it can be formed according to a conventionally known technique. For example, a coating solution for a heat-sensitive recording layer is coated on a support with an appropriate coating device such as an air knife coater, a blade coater, a bar coater, a gravure coater, a curtain coater, a wire bar, and dried to form a recording layer. can do. The amount of the coating solution is not particularly limited, and is generally 1.5 to 12 g / dry weight.
m ² , preferably in the range of 2.5 to 10 g / m ² . Paper, plastic sheet, synthetic paper, etc. are used as the support. If necessary, a protective layer may be provided on the front and / or back surface of the heat-sensitive recording layer, and an undercoat layer may be provided between the support and the heat-sensitive recording layer. Various known techniques in a method for manufacturing a recording material can be provided.

[0036]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 Preparation of Compound of Exemplified Compound No. 7 In 150 g of toluene and 30 g of methanol, 2,2-bis (4′-hydroxy) was prepared from 23 g of 2,2-bis (4′-hydroxyphenyl) propane and 8 g of sodium hydroxide. 27 g of anhydrous phenyl) propane disodium salt were prepared. To this, 43 g of 4-bromotoluene, 0.2 g of cuprous chloride and 100 g of N-methyl-2-pyrrolidone
Was added and stirred at 170 ° C. for 10 hours. After discharging the reaction mixture into water, the resulting solid was collected by filtration and recrystallized from isopropanol to give the target compound 2,2-
30 g of bis [4 ′-(4 ″ -methylphenyl) oxyphenyl] propane was obtained, yield 73%, melting point 75-7.
6 ° C. ¹ H-NMR (CDCl ₃ ) δ: 1.59 (s, 6H), 2.37 (s, 6H), 6.8 to 7.0 (m, 8H), 7.1 to 7.5 (M, 8
H)

Example 2 100 g of solution A, 250 g of solution B, and C prepared by the following method
250 g of each dispersion and 30% paraffin wax 23
g, mixed with a high-quality paper, and the dry coating amount was 5.0 ±
The coating was dried at 0.5 g / m ² and dried to prepare a thermosensitive recording paper. With respect to the obtained heat-sensitive recording paper, the coloring characteristics with respect to temperature were measured by the following method, and the results are shown in Table 1 (Table 1). (Coloring performance test for temperature) 5 sheets of heat-sensitive recording paper were placed on a metal block heated to each surface temperature.
For 2 seconds, and the density of the color image is measured using a Macbeth densitometer (T
R-524). The larger the value, the deeper the color.

[Method for Preparing Dispersion for Thermosensitive Recording Layer] (Solution A) Electron-donating color-forming compound 10 g Polyvinyl alcohol (Kuraray-117) 10% aqueous solution 10 g Water 80 g Total 100 g (Solution B) Electron acceptor Hydrophobic compound (bisphenol A) 20 g Light calcium carbonate (Okutama Kogyo, TP-123) 40 g Polyvinyl alcohol (Kuraray-117) 10% aqueous solution 60 g Water 130 g Total 250 g (Composition of liquid C) Compound of general formula (1) 20 g Polyvinyl Alcohol (Kuraray-117) 10% aqueous solution 10 g Water 220 g Total 250 g The above solution A, solution B and solution C were each dispersed by a sand grinding mill so that the average particle diameter became 1.5 μ or less, to prepare a dispersion. The electron-donating color-forming compound in the solution A used in Example 2 was 3-di-n-butylamino-6-methyl-7-anilinofluoran,
The compound of the general formula (1) in the liquid is 2,2-bis [4 ′-(4 ″ -methylphenyloxy) phenyl] propane produced in Example 1.

COMPARATIVE EXAMPLE 1 A dispersion of 100 g of Liquid A and 250 g of Liquid B and 23 g of 30% paraffin wax were mixed without using Liquid C, and the resulting mixture was coated on a high quality paper with a dry coating amount of 5.0 ± 0.5. It was applied to 5 g and dried to prepare a thermal recording paper. Evaluation was performed in the same manner as in Example 2, and the results are shown in Table 1. The electron-donating color-forming compound used was 3-di-n-butylamino-6.
-Methyl-7-anilinofluoran.

Comparative Example 2 As the electron-donating color-forming compound in Solution A, 3-di-n-
Using butylamino-6-methyl-7-anilinofluoran, instead of 2,2-bis [4 ′-(4 ″ -methylphenyloxy) phenyl] propane in solution C,
A thermosensitive recording paper was prepared in the same manner as in Example 2, except that 2-bis (4′-benzyloxyphenyl) propane was used. Evaluation was performed in the same manner as in Example 2, and the results are shown in Table 1.

[0041]

[Table 1] As is clear from Table 1, the heat-sensitive recording material of the present invention
Compared to conventional heat-sensitive recording materials comprising an electron-donating color-forming compound and an electron-accepting compound and heat-sensitive recording materials containing 2,2-bis (4'-benzyloxyphenyl) propane as a sensitizer, It can be said that it is a high-sensitivity heat-sensitive recording material that rapidly develops color at low temperatures and is suitable for high-speed recording.

[0042]

According to the present invention, color is rapidly formed at a low temperature,
It has become possible to provide a heat-sensitive recording material having good color-forming sensitivity.

Claims (4)

(57) [Claims] 1. An ether compound represented by the general formula (1 ′) : Embedded image (Wherein, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R represents a lower alkyl group) 2. The ether compound according to claim 1, wherein X is a straight or branched alkylene group having 3 carbon atoms, and R is a methyl group. 3. An ether compound represented by the general formula (2). Embedded image 4. A heat-sensitive recording material containing an electron-donating chromogenic compound and an electron-accepting compound represented by the following general formula
(1) A thermosensitive recording material comprising at least one ether compound represented by the formula (3) . Embedded image (Wherein X is a linear or branched alkylene having 1 to 6 carbon atoms)
R represents a lower alkyl group. However, both ends
The substitution positions of the substituent R on the phenyl group are the same. )