JPH05310629A - New ether compound and heat-resistant recording material containing the same - Google Patents

Abstract

PURPOSE:To provide the novel ether compound useful as a photosensitizer for heat-resistant recording materials rapidly coloring at low temperatures and good in the coloring sensitivity. CONSTITUTION:An ether compound of formula I (X is 1-6C linear or branched alkylene; R is lover alkyl) (especially preferably an ether compound of formula II), e.g. 2,2-bis[4'-methylphenyl)oxyphenyl]propane. The compound of formula I is obtained e.g. by reacting a diphenol compound with a lower alkyl-substituted phenyl halide in the presence of a base and a copper catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel ether compound, and more particularly to an ether compound useful as a sensitizer for heat-sensitive recording.

[0002]

2. Description of the Related Art Conventionally, a heat-sensitive recording material utilizing a color reaction between an electron-donating color-forming compound and an electron-accepting compound (developing agent) has been well known (for example, JP-B-43-4).
No. 160, Japanese Patent Publication No. 45-14039). Phenolic compounds are widely used as electron-accepting compounds. Among them, 2,2-bis (4'-hydroxyphenyl) propane [also known as bisphenol A] is widely used because it is inexpensive and easily available. Although used, the heat-sensitive recording material using bisphenol A as an electron-accepting compound has a problem of low color developing 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 is also widely used. For example, 2,2-bis (4'-benzyloxyphenyl) propane has been proposed as a heat-fusible compound (Japanese Patent Publication No. 2-59785). However, the heat-sensitive recording material containing the compound also has not so high color-developing sensitivity,
Further improvements are desired.

[0003]

An object of the present invention is to provide a novel ether compound useful as a material (sensitizer) for heat-sensitive recording, and further a heat-sensitive recording material containing the ether compound. Is to provide.

[0004]

The present inventors have arrived at the present invention as a result of synthesizing many compounds and intensively studying them in order to solve the above-mentioned problems. That is, the present invention provides an ether compound represented by the general formula (1) (formula 3),

[0005]

[Chemical 3] (In the formula, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, and R represents a lower alkyl group.) X represents 3 carbon atoms.
Of a linear or branched alkylene group, wherein R is a methyl group, and an ether compound represented by the general formula (2) (formula 4).

[0006]

[Chemical 4] Further, the present invention relates to a heat-sensitive recording material containing an electron-donating color forming compound and an electron-accepting compound, and further to a heat-sensitive recording material containing at least one ether compound of any of these.

In the compound represented by the general formula (1) of the present invention, X represents a linear or branched alkylene group having 1 to 6 carbon atoms, such as methylene group, 1,1-ethylene group,
1,2-ethylene group, 1,3-propylene group, 2,2-
Propylene group, 1,1-butylene group, 1,4-butylene group, 2,2-butylene group, 1,5-pentane group, 1,6
-Hexylene group, 2,2-isohexylene group and the like can be mentioned, and more preferably, methylene group, 1,1-ethylene group, 2,2-propylene group, 1,1-butylene group, 2,2-isohexylene group. A group, and particularly preferably a 2,2-propylene group.

In the compound represented by the general formula (1) of the present invention, R represents a lower alkyl group, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-
A butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and the like can be mentioned, and a methyl group is particularly preferable. 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 particularly preferably a para position. In the compound represented by the general formula (1) of the present invention, a particularly preferred compound is the general formula (2)
The compound represented by can be mentioned. General formula (2)
In the compound represented by, the substitution position of the methyl group on the phenyl group is the ortho position, the meta position or the para position with respect to the ether bond, and the para position is particularly preferable.

Among the compounds represented by the general formula (1) of the present invention, preferred specific examples include the following compounds. -Exemplified compound number 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 compound represented by the general formula (1) of the present invention can be suitably produced by a method of etherification known per se. For example, a base (eg, potassium carbonate, sodium hydroxide, potassium hydroxide) and a copper catalyst (eg, copper powder, first chloride) are used for 1 mol of the diphenol compound represented by the general formula (3) (formula 5). Copper, cuprous bromide, cuprous oxide, copper carbonate, 8-oxyquinoline copper complex, acetylacetone copper complex) in the presence of about 2 to 3
It can be produced by reacting with a mole of a lower alkyl-substituted phenyl halide (eg, lower alkyl-substituted phenyl chloride, lower alkyl-substituted phenyl bromide, etc.).

[0013]

[Chemical 5] (In the formula, X has the same meaning as in the case of the formula (1))

During the 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. Preferably. The reaction temperature is usually 1
It is carried out at 00 to 250 ° C, more preferably 150 to 230 ° C, and the reaction time depends on the reaction temperature, but is usually several hours to
It takes dozens of hours. If desired, the desired product can be purified by a known purification method (recrystallization, column chromatography, etc.) to improve the purity.

In the heat-sensitive recording material of the present invention, usually,
50 to 700 parts by weight, preferably 100 to 5 parts by weight of the electron-accepting compound relative to 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 light-colored compound, and is a triarylmethane compound, a diarylmethane compound, a rhodamine-lactam compound, a fluorane compound, an indolylphthalide compound. , Pyridine compounds, spiro compounds, fluorene compounds and the like. Some specific examples of these compounds include, as triarylmethane compounds, 3,3-bis (4-dimethylaminophenyl) -6-dimethylaminophthalide [crystal violet lactone] and 3,3- 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.

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

Examples of the fluorane compound include 3,6-dimethoxyfluorane, 3-dimethylamino-7-methoxyfluorane, 3-diethylamino-6-methoxyfluorane, 3-diethylamino-7-methoxyfluorane, and 3-diethylamino-7-methoxyfluorane. Diethylamino-7-chlorofluorane, 3-
Diethylamino-6-methyl-7-chlorofluorane,
3-diethylamino-6,7-dimethylfluorane, 3
-N-cyclohexyl-N-n-butylamino-7-methylfluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-di-n −
Hexylaminofluorane, 3-diethylamino-7-
Anilinofluorane, 3-diethylamino-7- (2-
Chloroanilino) fluorane, 3-diethylamino-7
-(3-chloroanilino) fluorane, 3-diethylamino-7- (2,3-dichloroanilino) fluorane,
3-diethylamino-7- (3-trifluoromethylanilino) fluorane, 3-di-n-butylamino-7-
(2-chloroanilino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane,

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

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

3-N-2'-methoxyethyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N
-2'-methoxyethyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-2'-ethoxyethyl-N-methylamino-6-methyl-7-anilinofluorane, 3 -N-2'-ethoxyethyl-N-ethylamino-6-methyl-7-anilinofluorane, 3-N-3 '
-Methoxypropyl-N-methylamino-6-methyl-
7-anilinofluorane, 3-N-3'-ethoxypropyl-N-methylamino-6-methyl-7-anilinofluorane, 3-N-2'-methoxyethyl-N-isobutylamino-6- Methyl-7-anilinofluorane, 3-N
-2'-tetrahydrofurfuryl-N-ethylamino-6
-Methyl-7-anilinofluorane, 3-N- (4'-methylphenyl) -N-ethylamino-6-methyl-7-
Anilinofluorane, 3-diethylamino-6-ethyl-7-anilinofluorane, 3-di-ethylamino-6
-Methyl-7- (2 ', 6'-dimethylphenylamino) fluorane, 3-di-n-butylamino-6-methyl-7
-(2 ', 6'-Dimethylphenylamino) fluorane, 3-di-n-butylamino-7- (2', 6'-dimethylphenylamino) fluorane, 2,2-bis [4 '-(3- N-cyclohexyl-N-methylamino-6-methylfluorane) -7-ylaminophenyl]
There is propane etc.

The indolyl phthalide compound is
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.

As the pyridine compound, 3- (2-ethoxy-4-diethylaminophenyl) -3- (1-octyl-2-methylindol-3-yl) -4 or 7-azaphthalide, 3- (2- 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- There is azaphthalide.

As the spiro compounds, 3-methyl-spiro-dinaphthopyran, 3-ethyl-spiro-dinaphthopyran, 3-phenyl-spiro-dinaphthopyran, 3-
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'-fluorene) -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 in admixture of two or more for the purpose of adjusting the color tone of a color image and obtaining a multicolor heat-sensitive recording material.

Examples of the electron-accepting compound used in the present invention include organic electron-accepting compounds such as phenol derivatives, organic acids or metal salts or complexes thereof, urea derivatives, and inorganic electron-accepting compounds such as acid clay. .. Some examples of these compounds are 4-tert-butylphenol, 4-tert-octylphenol, 4-tert-butylphenol,
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- Propoxydiphenyl sulfone, 4-hydroxy-4'-
Isopropoxydiphenyl sulfone, 4-hydroxy-4′-n-butoxydiphenyl sulfone, 3,4-
Dihydroxy-4'-methyldiphenyl sulfone, 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, phthalic acid monobenzyl ester and phthalic acid monophenyl ester, or metal salts thereof (for example, metal salts such as nickel, zinc, aluminum and calcium),
Zinc thiocyanate antipyrine complex, complexes such as molybdate acetylacetone 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,
Inorganic electron-accepting compounds such as zinc chloride and zinc bromide can be mentioned as preferable compounds. These electron-accepting compounds may be used alone or in combination of two or more. Particularly, the phenol derivative is used as a preferable electron accepting compound.

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, 50 to 700 parts by weight of the electron-accepting compound is added to 100 parts by weight of the electron-donating color forming compound.
Preferably, 100 to 500 parts by weight, the ether compound of the present invention is used in 10 to 500 parts by weight, preferably 20 to 400 parts by weight, and the heat-fusible compound is used in 10 to 500 parts by weight, preferably 20 to 400 parts by weight. Is desirable.

Specific examples of such a heat-fusible compound include:
For example, stearic acid amide, palmitic acid amide, stearyl urea, N-ethylcarbazole, nitrogen-containing compounds such as 4-methoxydiphenylamine, 4-benzyloxybenzoic acid benzyl ester, 2-naphthoic acid phenyl ester, 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, terephthalate Ester compounds such as acid dibenzyl ester, 4-
Benzyl biphenyl, 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-
Examples thereof include 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 using a special method. Generally, the electron-donating color-forming compound, the electron-accepting compound, the ether compound of the present invention, etc. are each usually in a water-soluble binder by a means such as a ball mill or a sand mill, and usually 3 μm or less, preferably 1.5 μm or less. The coating liquid can be prepared by pulverizing and dispersing to the following particle size and mixing. Specific examples of such a water-soluble binder include polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, epichlorohydrin-modified polyamide, ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and isobutylene-anhydrous. Examples thereof include maleic acid copolymer, polyacrylic acid, polyacrylamide, methylol-modified polyacrylamide, starch derivative, casein, gelatin, methylcellulose, carboxymethylcellulose, gum arabic, and carboxyl group-modified polyvinyl alcohol.

Further, in the recording layer of the heat-sensitive recording material of the present invention, a pigment, a water-insoluble binder, a metal soap, a wax, a surfactant, an ultraviolet absorber, a hindered phenol, an antifoaming agent, etc. may be added, if necessary. Added. As the pigment, zinc oxide, zinc carbonate, calcium carbonate, magnesium carbonate, barium carbonate, barium sulfate, titanium oxide, talc, wax, 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 ester. Examples of the surfactant include sulfosuccinic acid-based alkali metal salts and fluorine-containing surfactants. Examples of the ultraviolet absorber include cinnamic acid derivatives, benzophenone derivatives, and benzotriazolylphenol derivatives.

As the hindered phenol, a phenol derivative in which at least one ortho position of the phenolic hydroxyl group is substituted with a branched alkyl group is preferable, and 1,1,1,
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 can be mentioned.

In the heat-sensitive recording material of the present invention, the method for forming the recording layer is not particularly limited, and the recording layer can be formed according to a conventionally known technique. For example, the coating liquid for the 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, and a wire bar, and dried to form a recording layer. can do. Also, the coating amount of the coating liquid is not particularly limited, and is generally 1.5 to 12 g / dry weight.
It is adjusted in the range of m ² , preferably 2.5 to 10 g / m ² . As the support, paper, plastic sheet, synthetic paper or the like is used. If necessary, a protective layer may be provided on the front surface and / or the back surface of the thermosensitive recording layer, or an undercoat layer may be provided between the support and the thermosensitive recording layer. Various known techniques in the manufacturing method of the recording material can be applied.

[0036]

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 Production of Compound of Exemplified Compound No. 7 In 2,150 g of toluene and 30 g of methanol, 23 g of 2,2-bis (4'-hydroxyphenyl) propane and 8 g of sodium hydroxide were used to prepare 2,2-bis (4'-hydroxy). 27 g of anhydrous phenyl) propane disodium salt was 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 the reaction mixture was discharged into water, the resulting solid was collected by filtration and recrystallized from isopropanol to give 2,2-the desired compound.
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 and mix it onto fine paper with a dry coating amount of 5.0 ±
The heat sensitive recording paper was prepared by coating and drying so as to give 0.5 g / m ² . With respect to the obtained heat-sensitive recording paper, the color forming characteristics with respect to temperature were measured by the following method, and the results are shown in Table 1 (Table 1). (Color development performance test against temperature) A thermal recording paper was brought into contact with a metal block heated to each surface temperature for 5 seconds, and the color image density was measured using a Macbeth densitometer (TR-524 type). The larger the value is, the deeper the color is developed.

[Preparation Method of Dispersion for Thermosensitive Recording Layer] (Composition of Liquid A) Electron-donating color forming compound 10 g Polyvinyl alcohol (Kuraray-117) 10% aqueous solution 10 g Water 80 g Total 100 g (Composition of liquid B) Electron accepting Compound (bisphenol A) 20 g Light calcium carbonate (Okutama industry, TP-123) 40 g Polyvinyl alcohol (Kuraray-117) 10% aqueous solution 60 g Water 130 g Total 250 g (C liquid composition) Compound of general formula (1) 20 g Polyvinyl Alcohol (Kuraray-117) 10% aqueous solution 10 g Water 220 g Total 250 g The above liquids A, B and C were dispersed by a sand grinding mill so that the average particle diameter was 1.5 μm or less to prepare a dispersion liquid. The electron-donating color-forming compound in the liquid A used in Example 2 was 3-di-n-butylamino-6-methyl-7-anilinofluorane, and C
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 Without using the C liquid, a dispersion of 100 g of the A liquid and 250 g of the B liquid was mixed with 23 g of 30% paraffin wax, and this was applied to a fine paper with a dry coating amount of 5.0 ± 0. 5 g was applied 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-anilinofluorane.

Comparative Example 2 3-di-n-as the electron-donating color forming compound in the liquid A
Butylamino-6-methyl-7-anilinofluorane was used, and instead of 2,2-bis [4 '-(4 "-methylphenyloxy) phenyl] propane in solution C, 2,2
A thermal 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 is
Compared with a conventional thermal recording material comprising an electron-donating color forming compound and an electron-accepting compound and a thermal recording material 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 develops color rapidly at low temperatures and is suitable for high-speed recording.

[0042]

According to the present invention, color is rapidly developed at a low temperature,
It has become possible to provide a thermosensitive recording material having good color development sensitivity.

Claims (4)

[Claims] 1. An ether compound represented by the general formula (1) (formula 1). [Chemical 1] (In the formula, 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 linear or branched alkylene group having 3 carbon atoms, and R is a methyl group. 3. An ether compound represented by the general formula (2) (formula 2). [Chemical 2] 4. A heat-sensitive recording material containing an electron-donating color-forming compound and an electron-accepting compound, further containing at least one ether compound of any one of claims 1 to 3.