Phthalide dimer compound and recording material using the same

Abstract

To provide a recording material that is excellent in various performances such as background whiteness, storage stability, and image fastness, and is useful as colored image-making of vivid cyan color.SOLUTION: For example, the phthalide dimer compound of the following formula (2) is shown.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a phthalide dimer compound and a recording material containing the same. More specifically, a coloring compound having an electron-donating property that develops a cyan color, that is, a phthalide dimer compound and an electron-accepting developer react with a photo-thermal conversion agent that generates heat by near-infrared light of a thermal head or a laser, and the present invention relates to a phthalide dimer compound suitable for a recording material capable of recording an image or data.

Background Art

[0002] In recent years, from the viewpoint of global environmental conservation, the development of rewritable recording material technology has been remarkable. As a reversible recording medium capable of reversibly recording and erasing information by heat or light, the popularity of various prepaid cards, point cards, credit cards, IC cards, etc. has been progressing, and further, the use of reversible recording media has been studied even in the field of displays. In parallel, full-colorization has been progressing from the viewpoint of design. Among the three primary colors, a leuco dye that develops a clear cyan color and has excellent durability before and after coloring is required. Patent Document 1 discloses an azaphthalide compound that develops a cyan color, but improvement is required from the viewpoint of clarity. Patent Document 2 discloses a diazaphthalide compound that develops a clear cyan color. However, since the light resistance before and after coloring is low and the color changes, it poses a problem as a full-color thermal recording material, and improvement is required. Patent Document 3 discloses a thermal recording material using a phthalide compound that develops a cyan color. The light resistance before coloring is relatively high, but the light resistance after coloring is low and the coloring image density is also low, so improvement is required.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a full-color reversible heat-sensitive recording material containing a phthalide dimer compound that develops a clear cyan color at a high concentration and has high light resistance with no color change before and after development.

Means for Solving the Problems

[0005] As a result of investigations regarding the above problems, the present inventors have found that this can be solved by including a phthalide dimer compound having a specific structure in the coloring composition, and have thus completed the present invention.

[0006] That is, the present invention is (i) A phthalide dimer compound represented by the general formula (1). TIFF0007697782000001.tif83160

[0007] (In formula (1), R1 to R4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group,

[0008] R5 to R7 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an unsubstituted or substituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, A substituted or unsubstituted arylthio group, A substituted or unsubstituted amino group, A substituted or unsubstituted alkylcarbonyl group, Represents a substituted or unsubstituted arylcarbonyl group.

[0009] X1 and X2 represent a carbon atom or a nitrogen atom, provided that X1 and X2 do not simultaneously become nitrogen atoms, When X1 and X2 are carbon atoms, they may have substituents. Y is An oxygen atom, A sulfur atom, A substituted or unsubstituted imino group, A carbonyl group, A sulfonyl group, A substituted or unsubstituted alkylene group, Represents a substituted or unsubstituted arylene group R1 and R2 may be bonded to each other to form a heterocyclic ring. Also, R6 and R7 may be bonded to each other to form an aliphatic ring or an aromatic ring.)

[0010] (ii) The phthalide dimer compound of (i) wherein X1 and X2 are carbon atoms, (iii) The phthalide dimer compound of (i) wherein Y is a methylene group or an oxygen atom, (iv) A recording material using the reaction between an electron-donating leuco dye and an electron-accepting developer, characterized in that it contains the phthalide dimer compound according to any one of (i) to (ii) as the electron-donating leuco dye. (v) The recording material according to (iii), wherein the recording material is a thermal recording material.

Advantages of the Invention

[0011] The phthalide dimer compound of the present invention is colorless or almost colorless in the normal state, but develops a distinct cyan color by reaction (interaction) with a developer, and the developed color image has high light resistance and does not deteriorate. Therefore, it is useful as a cyan color-developing material for full-color thermal recording materials.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] Hereinafter, the present invention will be described in detail. The phthalide dimer compound of the present invention is characterized by having at least one kind in a recording material utilizing the reaction between an electron-donating leuco dye and an electron-accepting developer. First, the phthalide dimer compound will be described below.

[0013] [Phthalide Compound] The phthalide dimer compound of the present invention is represented by the following general formula (1). TIFF0007697782000002.tif83160

[0014] (In formula (1), R1 to R4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group,

[0015] R5 to R7 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an unsubstituted or substituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group.

[0016] X1 and X2 represent a carbon atom or a nitrogen atom provided that X1 and X2 do not simultaneously become nitrogen atoms, When X1 and X2 are carbon atoms, they may have substituents. Y is an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group, a carbonyl group, a sulfonyl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group R1 and R2 may be bonded to each other to form a heterocyclic ring. Also, R6 and R7 may be bonded to each other to form an aliphatic ring or an aromatic ring.

[0017] R1 to R4 are more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 25 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms is preferable. Even more preferably, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 19 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms.

[0018] Examples of these substituents are shown below. Examples of unsubstituted alkyl groups include linear or branched unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, etc.

[0019] Examples of substituted alkyl groups include For example, an alkyl group having an alkyloxy group or an alkenyloxy group, such as a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, a (2-ethylbutyloxy)methyl group, a 2-(4'-pentenyloxy)ethyl group, For example, an alkyl group having an aralkyloxy group, such as a benzyloxymethyl group, a 2-(benzyloxymethoxy)ethyl group, For example, an alkyl group having an aryloxy group, such as a phenyloxymethyl group, a 4-chlorophenyloxymethyl group, a 4-(2'-phenyloxyethoxy)butyl group, For example, an alkyl group having a thioalkyl group, such as an n-butylthiomethyl group, a 2-n-octylthioethyl group, For example, an alkyl group having a halogen atom, such as a fluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, a 4-fluorocyclohexyl group, a dichloromethyl group, a 4-chlorocyclohexyl group, a 7-chloroheptyl group, can be mentioned.

[0020] As the substituted or unsubstituted aralkyl group, For example, an unsubstituted or alkyl group-containing aralkyl group, such as a benzyl group, an α-methylbenzyl group, a phenethyl group, an α-methylphenethyl group, an α,α-dimethylbenzyl group, an α,α-dimethylphenethyl group, a 4-methylphenethyl group, a 4-methylbenzyl group, a 4-isopropylbenzyl group, For example, an aralkyl group having an aryl group or an aralkyl group, such as a 4-benzylbenzyl group, a 4-phenethylbenzyl group, a 4-phenylbenzyl group, For example, an aralkyl group having a substituted oxy group, such as a 4-methoxybenzyl group, a 4-n-tetradecyloxybenzyl group, a 4-n-heptadecyloxybenzyl group, a 3,4-dimethoxybenzyl group, a 4-methoxymethylbenzyl group, a 4-vinyloxymethylbenzyl group, a 4-benzyloxybenzyl group, a 4-phenethyloxybenzyl group. For example, an aralkyl group having a hydroxyl group, such as a 4-hydroxybenzyl group, a 4-hydroxy-3-methoxybenzyl group, For example, an aralkyl group having a halogen atom such as a 4-fluorobenzyl group, a 3-chlorobenzyl group, or a 3,4-dichlorobenzyl group, Furthermore, for example, a 2-furfuryl group, a diphenylmethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, etc. can be mentioned.

[0021] As the substituted or unsubstituted aryl group, For example, an unsubstituted aryl group such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthracenyl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 1-pyrenyl group, a 2-pyrenyl group, a 2-perylenyl group, a 3-perylenyl group, a 2-fluoranthenyl group, a 3-fluoranthenyl group, a 7-fluoranthenyl group, an 8-fluoranthenyl group, For example, an aryl group having an alkyl group such as a 1-methyl-2-pyrenyl group, a 2-methylphenyl group, a 4-ethylphenyl group, a 4-(4'-tert-butylcyclohexyl)phenyl group, a 3-cyclohexylphenyl group, a 2-cyclohexylphenyl group, a 4-ethyl-1-naphthyl group, a 6-n-butyl-2-naphthyl group, a 2,4-dimethylphenyl group, For example, an aryl group having an alkoxy group or an aryloxy group such as a 4-methoxyphenyl group, a 3-ethoxyphenyl group, a 2-ethoxyphenyl group, a 4-n-propoxyphenyl group, a 3-n-propoxyphenyl group, a 4-isopropoxyphenyl group, a 3-isopropoxyphenyl group, a 2-isopropoxyphenyl group, a 2-sec-butoxyphenyl group, a 4-n-pentyloxyphenyl group, a 4-isopentyloxyphenyl group, a 2-methyl-5-methoxyphenyl group, a 2-phenyloxyphenyl group, For example, an aryl group having an aryl group such as a 4-phenylphenyl group, a 3-phenylphenyl group, a 2-phenylphenyl group, a 2,6-diphenylphenyl group, a 4-(2'-naphthyl)phenyl group, a 2-phenyl-1-naphthyl group, a 1-phenyl-2-naphthyl group, a 7-phenyl-1-pyrenyl group,

[0022] For example, an aryl group having a halogen atom such as 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4-methoxyphenyl group, In addition, an aryl group having a halogenoalkyl group such as 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, An aryl group having an alkylthio group such as 4-methylthiophenyl group, 4-ethylthiophenyl group, Examples include an aryl group having a cyano group such as 4-cyanophenyl group, 3-cyanophenyl group, etc.

[0023] When R5 to R7 and X1 to X2 are carbon atoms, the substituents are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an unsubstituted or substituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group is preferred.

[0024] Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

[0025] As the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms and a substituted or unsubstituted aryl group having 6 to 24 carbon atoms are preferable, and more preferably, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms and a substituted or unsubstituted aryl group having 6 to 24 carbon atoms are preferable. As specific examples, those same as the specific examples of the substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group mentioned above for R1 to R4 can be mentioned. As the substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms is preferable, and a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms is more preferable.

[0026] Examples of the unsubstituted alkoxy group include For example, linear, branched or cyclic unsubstituted alkoxy groups such as methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, tert-butyloxy group, sec-butyloxy group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group, 2-methylpentyloxy group, 1,1-dimethylbutyloxy group, 1,2,2-trimethylpropyloxy group, 2-ethylbutyloxy group, 1,3-dimethylhexyloxy group, cyclohexyloxy group, methylcyclopentyloxy group, n-heptyloxy group, n-heptyloxy group, n-octyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group, 1-adamantyloxy group, n-pentadecyloxy group, etc. can be mentioned.

[0027] Examples of the substituted alkoxy group include For example, an alkoxy group substituted with an alkoxy group such as a methoxymethoxy group, an ethoxymethoxy group, an n-propyloxymethoxy group, an n-butyloxymethoxy group, an isobutyloxymethoxy group, a tert-butyloxymethoxy group, an n-pentyloxymethoxy group, a 2-methoxyethoxy group, a 2-ethoxyethoxy group, a 2-n-propyloxyethoxy group, a 2-isopropyloxyethoxy group, a 2-n-butyloxyethoxy group, a 2-isobutyloxyethoxy group, a 2-tert-butyloxyethoxy group, a 2-sec-butyloxyethoxy group, a 2-n-pentyloxyethoxy group, a 2-isopentyloxyethoxy group, a 2-tert-pentyloxyethoxy group, a 2-sec-pentyloxyethoxy group, a 2-cyclopentyloxyethoxy group, a 2-n-hexyloxyethoxy group, a 2-(4-ethylcyclohexyloxy)ethoxy group, a 2-n-nonyloxyethoxy group, a 2-(3,5,5-trimethylhexyloxy)ethoxy group, a 2-n-decyloxyethoxy group, a 2-n-dodecyloxyethoxy group, a 3-methoxypropyloxy group, a 3-ethoxypropyloxy group, a 3-(n-propyloxy)propyloxy group, a 2-isopentyloxypropyloxy group, a 2-methoxybutyloxy group, a 4-ethoxybutyloxy group, a 4-(n-propyloxy)butyloxy group, a 4-isopropyloxybutyloxy group, a 5-methoxypentyloxy group, a 5-ethoxymethoxy group, a 6-n-propylhexyloxy group, etc.

[0028] For example, an alkoxy group substituted with an alkoxyalkoxy group such as a methoxymethoxymethoxy group, an ethoxymethoxymethoxy group, a propyloxymethoxymethoxy group, a butyloxymethoxymethoxy group, a methoxyethoxymethoxy group, an ethoxyethoxymethoxy group, a propyloxyethoxymethoxy group, a methoxymethoxyethoxy group, an ethoxymethoxyethoxy group, a propyloxymethoxyethoxy group, a butyloxymethoxyethoxy group, a propyloxyethoxyethoxy group, a butyloxyethoxyethoxy group, a propyloxybutyloxyethoxy group, a methoxymethoxypropyloxy group, an ethoxymethoxypropyloxy group, a butyloxymethoxypropyloxy group, a methoxymethoxybutyloxy group, an ethoxymethoxybutyloxy group, a butyloxymethoxybutyloxy group, an ethoxyethoxybutyloxy group, a (4-ethylcyclohexyloxy)ethoxyethoxy group, a [4-(3,5,5-trimethylhexyloxy)butyloxy]ethoxy group, etc.

[0029] For example, an alkoxy group substituted with an alkoxycarbonyl group such as a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, an n-propyloxycarbonylmethoxy group, an isopropyloxycarbonylmethoxy group, a (4'-ethylcyclohexyloxy)carbonylmethoxy group, etc., an alkoxy group substituted with an alkoxycarbonyl group such as a methoxycarbonylethoxy group, an ethoxycarbonylethoxy group, an n-propyloxycarbonylethoxy group, an ethoxycarbonylpropyloxy group, etc.

[0030] For example, an alkoxy group substituted with an alkylamino group such as methylaminomethoxy group, 2-methylaminoethoxy group, 2-(2-methylaminoethoxy)ethoxy group, 4-methylaminobutyloxy group, 1-methylaminopropan-2-yloxy group, 3-methylaminopropyloxy group, 2-methylamino-2-methylpropyloxy group, 2-ethylaminoethoxy group, 2-(2-ethylaminoethoxy)ethoxy group, 3-ethylaminopropyloxy group, 1-ethylaminopropyloxy group, 2-isopropylaminoethoxy group, 2-(n-butylamino)ethoxy group, 3-(n-hexylamino)propyloxy group, 4-(cyclohexylamino)butyloxy group,

[0031] For example, an alkoxy group substituted with a dialkylamino group such as dimethylaminomethoxy group, 2-dimethylaminoethoxy group, 2-(2-dimethylaminoethoxy)ethoxy group, 4-dimethylaminobutyloxy group, 1-dimethylaminopropan-2-yloxy group, 3-dimethylaminopropyloxy group, 2-dimethylamino-2-methylpropyloxy group, 2-diethylaminoethoxy group, 2-(2-diethylaminoethoxy)ethoxy group, 3-diethylaminopropyloxy group, 1-diethylaminopropyloxy group, 2-diisopropylaminoethoxy group, 2-(di-n-butylamino)ethoxy group, 2-piperidylethoxy group, 3-(di-n-hexylamino)propyloxy group,

[0032] For example, an alkoxy group substituted with an alkylaminoalkoxy group such as methylaminomethoxymethoxy group, methylaminoethoxyethoxy group, methylaminoethoxypropyloxy group, ethylaminoethoxypropyloxy group, 4-(2'-isobutylaminopropyloxy)butyloxy group, For example, an alkoxy group substituted with a dialkylaminoalkoxy group such as dimethylaminomethoxymethoxy group, dimethylaminoethoxyethoxy group, dimethylaminoethoxypropyloxy group, diethylaminoethoxypropyloxy group, 4-(2'-diisobutylaminopropyloxy)butyloxy group,

[0033] For example, an alkoxy group substituted with an alkylthio group such as a methylthiomethoxy group, 2-methylthioethoxy group, 2-ethylthioethoxy group, 2-n-propylthioethoxy group, 2-isopropylthioethoxy group, 2-n-butylthioethoxy group, 2-isobutylthioethoxy group, (3,5,5-trimethylhexylthio) hexyloxy group, For example, an alkoxy group substituted with a heterocyclic group such as a 2-N-morpholinylethoxy group, 2-N-pyridylethoxy group, 2-N-pyrrolylethoxy group, 2-(2-furyl)ethoxy group, 2-(1-indolyl)ethoxy group, 2-(3-thienyl)ethoxy group, 3-N-morpholinylpropyloxy group, 3-N-pyridylpropyloxy group, 3-N-pyrrolylpropyloxy group, 3-(1-indolyl)propyloxy group, etc. can be mentioned.

[0034] As the substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms is preferable. Examples of the substituted or unsubstituted aryloxy group include For example, a phenyloxy group, 2-methylphenyloxy group, 4-methylphenyloxy group, 4-ethylphenyloxy group, 4-isopropylphenyloxy group, 4-isobutylphenyloxy group, 4-n-pentylphenyloxy group, 4-tert-pentylphenyloxy group, 4-cyclohexylphenyloxy group, 4-n-octylphenyloxy group, 4-n-decylphenyloxy group, 4-n-dodecylphenyloxy group, 4-n-hexadecylphenyloxy group, 2,3-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, 3,4,5-trimethylphenyloxy group, 5-indanyloxy group, 1,2,3,4-tetrahydro-6-naphthyloxy group, 3-methoxyphenyloxy group, 3-ethoxyphenyloxy group, 4-n-propoxyphenyloxy group, 4-n-butoxyphenyloxy group, 4-n-pentyloxyphenyloxy group, 4-cyclohexyloxyphenyloxy group, 4-n-octyloxyphenyloxy group, 4-n-decyloxyphenyloxy group, 4-n-dodecyloxyphenyloxy group, 4-n-hexadecyloxyphenyloxy group, 2,3-dimethoxyphenyloxy group, 2,5-dimethoxyphenyloxy group, 3,5-dimethoxyphenyloxy group, 2-methoxy-4-methylphenyloxy group, 3-methoxy-4-methylphenyloxy group, 3-methyl-4-methoxyphenyloxy group, 2-fluorophenyloxy group, 4-fluorophenyloxy group, 3-chlorophenyloxy group, 4-bromophenyloxy group, 3-trifluoromethylphenyloxy group, 3,5-difluorophenyloxy group, 3,4-dichlorophenyloxy group, 2-methyl-4-chlorophenyloxy group, 3-chloro-4-methylphenyloxy group, 3-methoxy-4-fluorophenyloxy group, 3-fluoro-4-methoxyphenyloxy group, 4-phenylphenyloxy group, 3-phenylphenyloxy group, 4-(4'-methylphenyl)phenyloxy group, 4-(4'-methoxyphenyl)phenyloxy group, 1-naphthyloxy group, 4-methyl-1-naphthyloxy group, 6-n-butyl-2-naphthyloxy group, 7-ethoxy-2-naphthyloxy group, 2-thienyloxy group, 2-pyridyloxy group, 4-pyridyloxy group and the like can be mentioned.,

[0035] As the substituted or unsubstituted alkylthio group, a substituted or unsubstituted alkylthio group having 1 to 8 carbon atoms is preferable., Examples of the unsubstituted alkylthio group include, For example, methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, isobutylthio group, tert-butylthio group, sec-butylthio group, n-pentylthio group, isopentylthio group, n-hexylthio group, 2-methylpentylthio group, 1,1-dimethylbutylthio group, 1,2,2-trimethylpropylthio group, 2-ethylbutylthio group, 1,3-dimethylhexylthio group, cyclohexylthio group, methylcyclopentylthio group, n-heptylthio group, n-heptylthio group, n-octylthio group, 3,5,5-trimethylhexylthio group, n-decylthio group, n-undecylthio group, n-dodecylthio group, 1-adamantylthio group, n-pentadecylthio group and other linear, branched or cyclic unsubstituted alkylthio groups can be mentioned.,

[0036] Examples of the substituted alkylthio group include, for example, methoxymethylthio group, ethoxymethylthio group, n-propyloxymethylthio group, n-butyloxymethylthio group, isobutyloxymethylthio group, tert-butyloxymethylthio group, n-pentyloxymethylthio group, 2-methoxyethylthio group, 2-ethoxyethylthio group, 2-n-propyloxyethylthio group, 2-isopropyloxyethylthio group, 2-n-butyloxyethylthio group, 2-isobutyloxyethylthio group, 2-tert-butyloxyethylthio group, 2-sec-butyloxyethylthio group, 2-n-pentyloxyethylthio group, 2-isopentyloxyethylthio group, 2-sec-pentyloxyethylthio group, 2-n-hexyloxyethylthio group, 2-(4-ethylcyclohexyloxy)ethylthio group, 2-n-nonyloxyethylthio group, 2-(3,5,5-trimethylhexyloxy)ethylthio group, 2-n-decyloxyethylthio group, 2-n-dodecyloxyethylthio group, 3-methoxypropylthio group, 3-ethoxypropylthio group, 3-(n-propylthio)propylthio group, 2-isopentyloxypropylthio group, 2-methoxybutylthio group, 4-ethoxybutylthio group, 4-(n-propyloxy)butylthio group, 5-methoxypentylthio group, 5-ethoxypentylthio group, 6-n-propyloxyhexylthio group, and alkylthio groups substituted with an alkoxy group such as those mentioned above.

[0037] For example, an alkylthio group substituted with an alkoxyalkoxy group such as a methoxymethoxymethylthio group, an ethoxymethoxymethylthio group, a propyloxymethoxymethylthio group, a butyloxymethoxymethylthio group, an ethoxyethoxymethylthio group, a propyloxyethoxymethylthio group, a methoxymethoxyethylthio group, an ethoxymethoxyethylthio group, a propyloxymethoxyethylthio group, a butyloxymethoxyethylthio group, a propyloxyethoxyethylthio group, a butyloxyethoxyethylthio group, a propyloxybutyloxyethylthio group, a methoxymethoxypropylthio group, an ethoxymethoxypropylthio group, a butyloxymethoxypropylthio group, a butyloxymethoxybutylthio group, an ethoxyethoxybutylthio group, a cyclohexyloxyethoxyethylthio group, a [4-(3,5,5-trimethylhexyloxy)butyloxy]ethylthio group, For example, an alkylthio group substituted with an alkoxycarbonyl group such as a methoxycarbonylmethylthio group, an ethoxycarbonylmethylthio group, an n-propyloxycarbonylmethylthio group, a methoxycarbonylethylthio group, an ethoxycarbonylethylthio group, an n-propyloxycarbonylethylthio group, an ethoxycarbonylpropylthio group,

[0038] For example, an alkylthio group substituted with an alkylamino group such as a methylaminomethylthio group, a 2-methylaminoethylthio group, a 2-(2-methylaminoethoxy)ethylthio group, a 4-methylaminobutylthio group, a 1-methylaminopropan-2-yloxy group, a 3-methylaminopropylthio group, a 2-ethylaminoethylthio group, a 2-(2-ethylaminoethoxy)ethylthio group, a 3-ethylaminopropylthio group, a 1-ethylaminopropylthio group, a 2-isopropylaminoethylthio group, a 2-(n-butylamino)ethylthio group, a 3-(n-hexylamino)propylthio group, a 4-(cyclohexylamino)butylthio group, For example, dimethylaminomethylthio group, 2-dimethylaminoethylthio group, 4-dimethylaminobutylthio group, 1-dimethylaminopropan-2-ylthio group, 3-dimethylaminopropylthio group, 2-diethylaminoethylthio group, 3-diethylaminopropylthio group, 2-diisopropylaminoethylthio group, 2-(di-n-butylamino)ethylthio group, 2-piperidylethylthio group Alkylthio groups substituted with dialkylamino groups such as 3-(di-n-hexylamino)propylthio group,

[0039] For example, alkylthio groups substituted with alkylthio groups such as methylthiomethylthio group, 2-methylthioethylthio group, 2-ethylthioethylthio group, 2-n-propylthioethylthio group, 2-isopropylthioethylthio group, 2-n-butylthioethylthio group, 2-isobutylthioethylthio group, (3,5,5-trimethylhexylthio)hexylthio group For example, alkylthio groups substituted with heterocyclic groups such as 2-N-morpholinylethylthio group, 2-N-pyridylethylthio group, 2-N-pyrrolylethylthio group, 2-(2-furyl)ethylthio group, 2-(1-indolyl)ethylthio group, 2-(3-thienyl)ethylthio group, 3-N-morpholinylpropylthio group, 3-N-pyridylpropylthio group, 3-N-pyrrolylpropylthio group, 3-(1-indolyl)propylthio group, etc. can be mentioned.

[0040] As the substituted or unsubstituted arylthio group, a substituted or unsubstituted arylthio group having 6 to 18 carbon atoms is preferable. Examples of substituted or unsubstituted arylthio groups include heteroarylthio groups, such as phenylthio group, 2-methylphenylthio group, 4-methylphenylthio group, 3-ethylphenylthio group, 4-n-propylphenylthio group, 4-n-butylphenylthio group, 4-isobutylphenylthio group, 4-tert-butylphenylthio group, 4-n-pentylphenylthio group, 4-n-hexylphenylthio group, 4-cyclohexylphenylthio group, 4-n-octylphenylthio group, 4-n-dodecylphenylthio group, 4-n-octadecylphenylthio group, 2,5-dimethylphenylthio group, 3,4-dimethylphenylthio group, 5-indanylthio group, 1,2,3,4-tetrahydro-6-naphthylthio group, 2-methoxyphenylthio group, 3-methoxyphenylthio group, 4-ethoxyphenylthio group, 4-n-propoxyphenylthio group, 2,4-dimethoxyphenylthio group, 3,5-diethoxyphenylthio group, 2-methoxy-4-methylphenylthio group, 2-methyl-4-methoxyphenylthio group, 2-fluorophenylthio group, 4-fluorophenylthio group, 2-chlorophenylthio group, 4-bromophenylthio group, 4-trifluoromethylphenylthio group, 3-trifluoromethylphenylthio group, 2,4-difluorophenylthio group, 2,4-dichlorophenylthio group, 2-chloro-4-methoxyphenylthio group, 2-naphthylthio group, 4-methyl-1-naphthylthio group, 4-ethoxy-1-naphthylthio group, 2-pyridylthio group, 4-aminophenylthio group, 4-(N,N-dimethylamino)phenylthio group, 4-(N,N-diethylamino)-1-naphthylthio group, 4-[N,N-di(4'-methylphenyl)amino]phenylthio group, 4-(N-phenoxazinyl)phenylthio group, and the like.

[0041] As the substituted amino group, an amino group substituted with a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group as a substituent is preferable. For example, monoalkylamino groups such as methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, cyclohexylamino group, 3,5,5-trimethylhexylamino group, nonylamino group, decylamino group, For example, dialkylamino groups such as dimethylamino group, diethylamino group, methylethylamino group, di-n-propylamino group, di-n-butylamino group, di-n-pentylamino group, N-methyl-N-ethylamino group, N-ethyl-N-isopropylamino group, N-ethyl-N-cyclohexylamino group, N-methyl-N-n-octylamino group,

[0042] For example, amino groups having an aryl group such as N-methyl-N-phenylamino group, N-ethyl-N-phenylamino group, N-ethyl-N-(2,4-dimethylphenyl)amino group, N-n-propyl-N-(2-ethoxyphenyl)amino group, N-methyl-N-(3-chlorophenyl)amino group, diphenylamino group, di-(p-tolyl)amino group, N-methyl-N-(2-naphthyl)amino group, For example, amino groups having an aralkyl group such as benzylamino group, phenethylamino group, 3-phenylpropylamino group, 4-ethylbenzylamino group, 4-isopropylbenzylamino group, dibenzylamino group, diphenethylamino group, bis(4-ethylbenzyl)amino group, bis(4-isopropylbenzyl)amino group, N-ethyl-N-benzylamino group, N-methyl-N-phenethylamino group, etc. can be mentioned.

[0043] As the substituted or unsubstituted alkylcarbonyl group, Examples include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, iso-valeryl group, sec-valeryl group, trimethylacetyl group, hexanoyl group, t-butylacetyl group, heptanoyl group, octanoyl group, 2-ethylhexanoyl group, nonanoyl group, decanoyl group, undecanoyl group, lauroyl group, tridecanoyl group, tetra-decanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, oleoyl group, cyclopentanecarbonyl group, cyclohexanecarbonyl group, 6-chlorohexanoyl group, 6-bromohexanoyl group, trifluoroacetyl group, pentafluoropropionyl group, per-fluorooctanoyl group, 2,2,4,4,5,5,7,7,7-nonafluoro-3,6-dioxaheptanoyl group, methoxyacetyl group, 3,6-dioxaheptanoyl group, cinnamoyl group, etc.

[0044] Examples of the substituted or unsubstituted arylcarbonyl group include benzoyl group, 2-methylbenzoyl group, 3-methylbenzoyl group, 4-methylbenzoyl group, 4-ethylbenzoyl group, 4-n-propylbenzoyl group, 4-tert-butylbenzoyl group, 2,4-dimethylbenzoyl group, 2,4,6-trimethylbenzoyl group, 2,4,5-trimethylbenzoyl group, 4-ethylbenzoyl group, 4-isopropylbenzoyl group, 4-n-butylbenzoyl group, 4-isobutylbenzoyl group, 4-sec-butylbenzoyl group, 4-tert-butylbenzoyl group, 4-n-pentylbenzoyl group, 4-isopentylbenzoyl group, 4-neopentylbenzoyl group, 4-isohexylbenzoyl group, 4-cyclohexylbenzoyl group, 4-octylbenzoyl group, 4-cyanobenzoyl group, 4-nitrobenzoyl group, 4-trifluoromethylbenzoyl group, 3-bromobenzoyl group, 2-fluorobenzoyl group, 4-chlorobenzoyl group, 2,6-dichlorobenzoyl group, 2,4-difluorobenzoyl group, naphthylcarbonyl-1-yl group, naphthylcarbonyl-2-yl group. Specific examples of the case where R1 and R2 are bonded to each other to form a heterocyclic ring include For example, a pyrrolidino group, a piperidino group, a 4-methylpiperidino group, a 4-isopropylpiperidino group, a pyrrolidino group, a 3-methylpyrrolidino group, a morpholino group, etc. may be mentioned.

[0045] Y in the general formula (1) is preferably an oxygen atom, a sulfur atom, an imino group having no substitution or an alkyl group with 1 to 12 carbon atoms, a carbonyl group, a sulfonyl group, an alkylene group with 1 to 16 carbon atoms, or a substituted or unsubstituted arylene group with 6 to 24 carbon atoms. Y is more preferably an oxygen atom, a sulfur atom, an imino group of an alkyl group with 1 to 8 carbon atoms, a carbonyl group, a sulfonyl group, an alkylene group with 1 to 12 carbon atoms, or an arylene group with 6 to 18 carbon atoms having an alkyl group, an alkenyl group, a halogen atom, a cyano group or an acyl group as a substituent. Examples of the imino group include an imino group, a methylimino group, an ethylimino group, an n-propylimino group, an isopropylimino group, an n-butylimino group, an isobutylimino group, a sec-butylimino group, a tert-butylimino group, an n-pentylimino group, an isopentylimino group, a neopentylimino group, a tert-pentylimino group, an n-hexylimino group, a 1-methylpentylimino group, a 4-methyl-2-pentylimino group, a 2-ethylbutylimino group, an n-heptylimino group, a 1-methylhexylimino group, an n-octylimino group, a 1-methylheptylimino group, a 2-ethylhexylimino group.

[0046] Examples of the alkylene group include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-2,3-diyl group, 1,1,2,2-tetramethylethane-1,2-diyl group, butane-1,2-diyl group, pentane-1,5-diyl group, pentane-1,2-diyl group, 2,4-diethylpentane-1,5-diyl group, 3-methylpentane-1,5-diyl group, cyclopentane-1,3-diyl group, hexane-1,6-diyl group, hexane-1,4-diyl group, hexane-2,4-diyl group, cyclohexane-1,4-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,2-diyl group, 2,2,3,3,4,4,5,5-octafluorhexane-1,6-diyl group, heptane-1,7-diyl group, adamantane-1,3-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, 1H,1H,10H,10H-hexadecafluorodecane-1,10-diyl group. Particularly, an alkylene group having 1 to 12 carbon atoms is preferable, and an alkylene group having 1 to 4 carbon atoms is more preferable. The substituted or unsubstituted arylene group includes a heteroarylene group. As the substituted arylene group, it preferably has an alkyl group, an alkenyl group, a halogen atom, a cyano group, or an acyl group as a substituent, and more preferably has an alkyl group as a substituent.

[0047] Examples of substituted or unsubstituted arylene groups include benzene-1,4-diyl group, benzene-1,3-diyl group, benzene-1,2-diyl group, 2-methylbenzene-1,4-diyl group, 3-methylbenzene-1,4-diyl group, 2,6-dimethylbenzene-1,4-diyl group, 2,3,5,6-tetramethylbenzene-1,4-diyl group, 2-allylbenzene-1,4-diyl group, 2-isopropylbenzene-1,4-diyl group, 2,3-dipropylbenzene-1,4-diyl group, 2-t-butylbenzene-1,4-diyl group, 3-t-butylbenzene-1,4-diyl group, 2-t-butyl-5-methylbenzene-1,4-diyl group, 2,5-di-t-butylbenzene-1,4-diyl group, 2-cyclohexylbenzene-1,4-diyl group, 3-cyclohexylbenzene-1,4-diyl group, 2-phenylbenzene-1,4-diyl group, 3-phenylbenzene-1,4-diyl group, 2-methoxybenzene-1,4-diyl group, 3-methoxybenzene-1,4-diyl group, 2-chlorobenzene-1,4-diyl group, 3-chlorobenzene-1,4-diyl group, 2-fluorobenzene-1,4-diyl group, 3-fluorobenzene-1,4-diyl group, 2,3,5,6-tetrafluorobenzene-1,4-diyl group, 2,3-dicyanobenzene-1,4-diyl group, 2-acylbenzene-1,4-diyl group, naphthalene-1,5-diyl group, anthraquinone-2,6-diyl group, benzonorbornene-3,6-diyl group. Particularly preferred are benzene-1,4-diyl group, benzene-1,3-diyl group, benzene-1,2-diyl group, 2-methylbenzene-1,4-diyl group, 3-methylbenzene-1,4-yl group, 2,6-dimethylbenzene-1,4-diyl group, 2-chlorobenzene-1,4-diyl group, 3-chlorobenzene-1,4-diyl group, 2-fluorobenzene-1,4-diyl group, 3-fluorobenzene-1,4-diyl group, 2,3,5,6-tetrafluorobenzene-1,4-diyl group, and more preferred are benzene-1,4-diyl group, 2-methylbenzene-1,4-diyl group, 3-methylbenzene-1,4-yl group, 2-fluorobenzene-1,4-diyl group, 3-fluorobenzene-1,4-diyl group.

[0048] Specific examples of the phthalide dimer compound of the general formula (1) contained in the recording material of the present invention are shown in the following table, but are not limited to these ranges.

[0049] TIFF0007697782000003.tif255166

[0050] TIFF0007697782000004.tif254165

[0051] TIFF0007697782000005.tif255166

[0052] TIFF0007697782000006.tif253165

[0053] TIFF0007697782000007.tif254165

[0054] TIFF0007697782000008.tif255167

[0055] TIFF0007697782000009.tif255166

[0056] TIFF0007697782000010.tif255168

[0057] TIFF0007697782000011.tif254167

[0058] TIFF0007697782000012.tif255167

[0059] TIFF0007697782000013.tif253164

[0060] TIFF0007697782000014.tif255166

[0061] TIFF0007697782000015.tif254165

[0062] TIFF0007697782000016.tif254165

[0063] TIFF0007697782000017.tif254166

[0064] The phthalide dimer compound of the general formula (1) of the present invention can be produced, for example, by reacting a compound represented by the general formula (2) and a compound represented by the general formula (3) in the presence of a dehydrating condensing agent.

[0065] TIFF0007697782000018.tif70156[In general formulas (2) to (3), R1 to R7, X1 to X2, and Y represent the same as R1 to R7, X1 to X2, and Y in general formula (1)]

[0066] As the dehydrating condensing agent, Acetic anhydride, glacial acetic acid / concentrated sulfuric acid mixture, polyphosphoric acid, phosphorus pentoxide, boron trifluoride, zinc chloride, etc. can be used, and acetic anhydride is particularly preferred. When acetic anhydride is used as the dehydrating condensing agent, it is preferably used in an amount of 1 mole or more per 1 mole of the general formula (2). There is no limitation on the amount of acetic anhydride used, but it is preferably used in a molar ratio of 1 to 5 economically. When an inert solvent such as toluene is used in combination, a molar ratio of 1 to 2 is sufficient.

[0067] The reaction temperature is 30 to 120 °C, particularly preferably 30 to 80 °C. The reaction time is not particularly limited, but the reaction generally completes in several hours to 24 hours. In the reaction, it is preferable to use an inert solvent such as toluene or dichloroethane in combination to allow the reaction to proceed smoothly. When acetic anhydride is used as the dehydrating condensing agent, toluene is preferably used as the solvent to be used in combination. After the reaction, the reaction solution is treated with an alkali such as an aqueous sodium hydroxide solution, and then extracted and purified with an organic solvent such as toluene. An organic solvent may also coexist during the alkali treatment. The phthalide dimer compound is produced by subjecting the organic solvent extract to hot washing, separation, concentrating the extract, preferably adding methanol, stirring under reflux, and cooling. Alternatively, the organic solvent solution obtained by further purifying the organic solvent extract by known purification such as column chromatography is concentrated, and the phthalide dimer compound is produced by performing the same treatment with methanol as described above if necessary. There are a heat-sensitive recording material that reacts and develops color using a light-converting agent such as a thermal head or laser light as a heat source and a pressure-sensitive recording material that reacts and develops color by pen pressure such as a type, as a recording material composed of a coloring compound having an electron-donating property that develops a cyan color, that is, the phthalide dimer compound of the present invention and an electron-accepting developer.

[0068] The reason why the developed image of the recording material having the phthalide dimer compound of the present invention has excellent light resistance is not clear. The dye becomes an excited state by light and an activated state in which a photofading reaction occurs. There is a possibility that the durability is improved by quickly deactivating this excited state to the ground state. The phthalide dimer compound of the present invention has a structure in which two phthalide derivatives are linked by Y in the general formula (1), and it is considered that this contributes to the relaxation to the ground state. Furthermore, by forming a dimer compound, the solubility in oil and plasticizer is lower than that of general azaphthalide compounds and phthalide compounds, and the developed image is excellent in oil resistance and plasticizer resistance.

[0069] [Thermal Recording Material] The heat-sensitive recording material can be manufactured by various known methods disclosed in, for example, Japanese Patent Publication No. 45-14039. Generally, a leuco dye, a developer, and a sensitizer are each dispersed in an aqueous solution of a water-soluble polymer such as polyvinyl alcohol using an attritor, a sand mill, etc. so that the particle size of the chemicals becomes several microns or less. The sensitizer may be dispersed simultaneously in addition to either or both of the leuco dye and the developer, or in some cases, a eutectic with the leuco dye or the developer may be prepared in advance and dispersed. These dispersions are mixed and, if necessary, a pigment, a binder, a wax, a metal soap, an antioxidant, an ultraviolet absorber, etc. are added to obtain a heat-sensitive coating solution. When the obtained heat-sensitive coating solution is applied to a support such as high-quality paper, synthetic paper, or a plastic film and smoothness is imparted by calendar treatment, heat-sensitive recording paper is obtained. Further, the heat-sensitive coating solution may be applied to a support having an undercoat layer of a plastic pigment or a heat insulating material such as silica in order to improve the color developability if necessary. Furthermore, in order to impart water resistance and chemical resistance if necessary, it is also possible to provide an overcoat layer on the heat-sensitive recording layer with an aqueous solution of a water-soluble polymer or the like.

[0070] As the developer used for the heat-sensitive recording paper, various phenolic compounds can be used. Specific examples include bisphenol A, 2,2-bis(p-hydroxyphenyl)-4-methylpentane, 1,1-bis(p-hydroxyphenyl)cyclohexane, bisphenol S, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 3,3-diallyl-4,4'-dihydroxydiphenyl sulfone, 1,5-bis(p-hydroxyphenylmercapto)-3-oxapentane, benzyl p-hydroxybenzoate, tetrabromobisphenol A, tetrabromobisphenol S, etc. Among them, bisphenol A is particularly preferably used.

[0071] Examples of the sensitizer include p-benzylbiphenyl, metaterphenyl, 2-benzyloxynaphthalene, 1,4-dibenzyloxynaphthalene, benzyl oxalate, di-p-methylbenzyl oxalate, di-p-chlorobenzyl oxalate, 1,2-diphenoxyethane, 1,2-m-tolyloxyethane, 1,2-di-p-tolyloxyethane, 1,4-diphenoxyethane, benzyl p-benzyloxybenzoate, phenyl 1-hydroxy-2-naphthoate, benzyl terephthalate, etc. Particularly, p-benzylbiphenyl, metaterphenyl, 2-benzyloxynaphthalene, di-p-methylbenzyl oxalate, 1,2-m-toloxyethane are preferably used.

[0072] As the pigment, organic and inorganic pigments can be used. Preferable specific examples include calcium carbonate, barium sulfate, titanium oxide, aluminum hydroxide, amorphous silica, urea formaldehyde resin powder, polyethylene resin powder, etc. As the binder, water-soluble polymers and water-insoluble polymers can be used. Preferable specific examples include, as water-soluble polymers, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, starches, hydrolyzates of styrene maleic anhydride copolymers, hydrolyzates of isobutylene maleic anhydride copolymers, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, polyacrylamide, etc., and as water-insoluble polymers, styrene butadiene rubber latex, acrylonitrile butadiene rubber latex, vinyl acetate emulsion, etc. Preferable specific examples of the wax include paraffin wax, carboxy-modified paraffin wax, polyethylene wax, etc. As the metal soap, higher fatty acid metal salts are used. Preferable specific examples include zinc stearate, calcium stearate, aluminum stearate, etc.

[0073] As the antioxidant, hindered phenols are used. Also, as the ultraviolet absorber, ultraviolet absorbers such as benzophenone-based and benzotriazole-based ones are used.

[0074] Note that rewritable heat-sensitive recording materials also include rewritable recording materials. The rewritable recording material forms a recording layer composed of a leuco dye, a developer or a long-chain developer which has a group having a color-developing property with respect to the leuco dye and a group having a color-fading property within the same molecule by the action of heat on a support of paper or a synthetic resin film, and a binder, etc., and has a structure in which a protective layer for improving durability, a UV protective layer, and a protective layer for resisting abrasion and hot water are laminated on the surface as necessary.

[0075] When using a developer-fading agent, when the lactone ring of the leuco dye comes into contact with a group having a color-developing property by controlling thermal energy, the lactone ring is cleaved and colored, and when it comes into contact with a group having a color-fading property, the kton ring is closed and decolorized. When using a long-chain developer, when heated above the melting point of the developer, it melts and comes into contact with the leuco dye to develop color. When gradually cooled from this state, separation and crystallization of the leuco dye and the developer occur, so it decolorizes. However, when rapidly cooled, the developer maintains its bond with the leuco dye and aggregates regularly, maintaining the colored state. Also, when heated from the colored state, the aggregated structure of the colored state collapses, and at a temperature lower than the coloring temperature, the developer becomes a stable crystalline state alone and separates from the leuco dye, decolorizing.

[0076] Examples of the leuco dye include phthalide compounds, azaphthalide compounds, diazaaphthalide compounds, fluoran compounds, etc. Examples of the developer-fading agent include amphoteric compounds having at least one phenolic hydroxyl group and a carboxyl group and having an amino group as a functional group or as part of a salt compound, or salts or complex salts of compounds having at least one phenolic hydroxyl group and / or a carboxyl group and aliphatic amines. For example, aliphatic amines, aminobenzoic acids, hydroxyaminobenzoic acids, or ester compounds thereof can be mentioned. Examples of the long-chain developer include compounds having a group having a color-developing property with respect to the leuco dye, such as a phenolic hydroxyl group, a carboxyl group, etc., within the molecule, and a group that controls the intermolecular cohesive force, such as a group linked to a long-chain hydrocarbon group.

Example

[0077] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples.

[0078] [Example 1] Production of Specific Example Compound (2) 5.7 g of Compound (A), 3.0 g of Compound (B), 7.2 g of acetic anhydride, and 7 mL of toluene were stirred at 65 - 70 °C for 3 hours. After cooling, 200 mL of toluene and 100 mL of 20% aqueous sodium hydroxide solution were added. After stirring under reflux for 30 minutes, the toluene layer was separated, washed with hot water, filtered, and concentrated. 30 mL of methanol was added to the residue and stirred under reflux for 30 minutes. After cooling, the precipitate was collected by filtration, washed with 30 mL of methanol, and dried. 7.2 g of (Specific Example Compound (2)) of the following structural formula was obtained as a white powder. Pyrolysis temperature (TG - 5%); 301.8 °C Thermogravimetric differential thermal analysis was carried out, and the temperature at which the weight decreased by 5% was defined as the pyrolysis temperature (TG - 5%). Hereinafter, it is the same. The obtained compound was confirmed to be the target compound from the following analysis results.

[0079] TIFF0007697782000019.tif72170·ESI - Mass: 917(M + H) + ·Elemental analysis values: Measured values (C: 79.78%, H: 7.01%, N: 6.15%); Theoretical values (C: 79.88%, H: 7.03%, N: 6.11%)

[0080] [Example 2] Production of Specific Example Compound (4) 7.5 g of Compound (C), 3.0 g of Compound (B), 7.2 g of acetic anhydride, and 7.5 mL of toluene were stirred at 65 - 70 °C for 3.5 hours. After cooling, 200 mL of toluene and 100 mL of 20% aqueous sodium hydroxide solution were added. After stirring under reflux for 30 minutes, the toluene layer was separated, washed with hot water, filtered, and concentrated. 30 mL of methanol was added to the residue and stirred under reflux for 30 minutes. After cooling, the precipitate was collected by filtration, washed with 30 mL of methanol, and dried. 7.8 g of (Specific Example Compound (4)) of the following structural formula was obtained as a pale blue-white powder. Thermal decomposition temperature (TG-5%); 296.9 °C The obtained compound was confirmed to be the target compound from the following analysis results.

[0081] TIFF0007697782000020.tif71170·ESI-Mass: 981 (M+H) + ·Elemental analysis values: Measured values (C: 74.62%, H: 6.53%, N: 5.75%); Theoretical values (C: 74.66%, H: 6.57%, N: 5.71%)

[0082] [Example 3] Production of Specific Example Compound (15) 12.3 g of Compound (A), 6.0 g of Compound (D), 15.9 g of acetic anhydride, and 16 mL of toluene were stirred at 65 - 70 °C for 3 hours. After cooling, 200 mL of toluene and 100 mL of 20% aqueous sodium hydroxide solution were added. After stirring under reflux for 30 minutes, the toluene layer was separated, washed with hot water, filtered, and concentrated. 100 mL of methanol was added to the residue, and the mixture was stirred under reflux for 30 minutes. After cooling, the precipitated product was collected by filtration, washed with 50 mL of methanol, and dried. 12.0 g of (Specific Example Compound (15)) of the following structural formula was obtained as a light green-white powder. Thermal decomposition temperature (TG-5%); 304.7 °C The obtained compound was confirmed to be the target compound from the following analysis results.

[0083] TIFF0007697782000021.tif67170·ESI-Mass: 919 (M+H) + ·Elemental analysis values: Measured values (C: 78.36%, H: 6.68%, N: 6.13%); Theoretical values (C: 78.40%, H: 6.80%, N: 6.10%)

[0084] [Example 4] Production of Specific Example Compound (108) 9.9 g of compound (E), 3.0 g of compound (B), 10.8 g of acetic anhydride, and 10 mL of toluene were stirred at 65 - 70 °C for 3.5 hours. After cooling, 200 mL of toluene and 100 mL of 20% aqueous sodium hydroxide solution were added. After stirring under reflux for 30 minutes, the toluene layer was separated, washed with hot water, filtered, and concentrated. 30 mL of methanol was added to the residue, and the mixture was stirred under reflux for 30 minutes. After cooling, the precipitate was collected by filtration, washed with 30 mL of methanol, and dried. 5.7 g of (specific example compound (108)) of the following structural formula was obtained as a pale greenish - white powder. Thermal decomposition temperature (TG - 5%); 280.0 °C The obtained compound was confirmed to be the target compound based on the following analysis results.

[0085] TIFF0007697782000022.tif62170·ESI - Mass: 975(M + H) + ·Elemental analysis values: measured values (C: 77.55%, H: 7.19%, N: 8.65%); theoretical values (C: 77.59%, H: 7.23, N: 8.62%)

[0086] [Example 5] Preparation of specific example compound (124) 9.6 g of compound (F), 4.0 g of compound (B), 10.6 g of acetic anhydride, and 10 mL of toluene were stirred at 65 - 70 °C for 3 hours. After cooling, 200 mL of toluene and 100 mL of 20% aqueous sodium hydroxide solution were added. After stirring under reflux for 30 minutes, the toluene layer was separated, washed with hot water, filtered, and concentrated. 100 mL of methanol was added to the residue, and the mixture was stirred under reflux for 30 minutes. After cooling, the precipitate was collected by filtration, washed with 50 mL of methanol, and dried. 9.4 g of (specific example compound (124)) of the following structural formula was obtained as a pale green powder. Thermal decomposition temperature (TG - 5%); 301.4 °C The obtained compound was confirmed to be the target compound based on the following analysis results.

[0087] TIFF0007697782000023.tif69170·ESI-Mass: 1017(M+H) + ·Elemental analysis values: measured values (C: 81.41%, H: 6.70%, N: 5.55%); theoretical values (C: 81.46%, H: 6.74%, N: 5.51%)

[0088] [Example 6] Preparation of Specific Example Compound (133) 4.8 g of Compound (F), 2.0 g of Compound (D), 5.3 g of acetic anhydride, and 5.3 mL of toluene were stirred at 65 - 70 °C for 3 hours. After cooling, 200 mL of toluene and 100 mL of 20% aqueous sodium hydroxide solution were added. After stirring under reflux for 30 minutes, the toluene layer was separated, washed with hot water, filtered, and concentrated. 100 mL of methanol was added to the residue, and the mixture was stirred under reflux for 30 minutes. After cooling, the precipitate was collected by filtration, washed with 50 mL of methanol, and dried. 5.8 g of (Specific Example Compound (133)) with the following structural formula was obtained as a pale blue-white powder. Thermal decomposition temperature (TG-5%); 303.9 °C It was confirmed that the obtained compound was the target compound from the following analysis results.

[0089] TIFF0007697782000024.tif62170·ESI-Mass: 1019(M+H) + ·Elemental analysis values: measured values (C: 80.11%, H: 6.50%, N: 5.52%); theoretical values (C: 80.13%, H: 6.53%, N: 5.50%)

[0090] [Example 7] Preparation of Thermal Recording Material 5 g of the specific example compound (2) produced in Example 1 was pulverized using a sand mill together with 45 g of a 2.5% aqueous polyvinyl alcohol solution so that the average particle size became 1 micron, and a dispersion was prepared. On the other hand, 10 g of bisphenol A and 10 g of parabenzyl biphenyl were pulverized using a sand mill together with 80 g of a 2.5% aqueous polyvinyl alcohol solution so that the average particle size became 3 microns, and a dispersion was prepared. After mixing the two types of dispersions thus prepared, 30 g of a 50% calcium carbonate dispersion and a 30% paraffin wax dispersion were added and mixed well to prepare a heat-sensitive coating liquid. The heat-sensitive coating liquid thus prepared was applied to high-quality paper with a basis weight of 50 g / m 2 so that the solid content coating amount became 5 g / m 2 . After drying, calendering was performed so that the Bekk smoothness of the heat-sensitive recording surface became 400 to 500 seconds, and a white heat-sensitive recording material was produced.

[0091] [Example 8] Production of heat-sensitive recording material Example 7 A white heat-sensitive recording material was produced in the same manner as in Example 7 , except that 5 g of the specific example compound (4) produced in Example 2 was used instead of 5 g of the specific example compound (2) used in Example [Example 9] Production of heat-sensitive recording material Example 7 A white heat-sensitive recording material was produced in the same manner as in Example 7 , except that 5 g of the specific example compound (15) produced in Example 3 was used instead of 5 g of the specific example compound (2) used in Example

[0092] [Example 10] Production of heat-sensitive recording material Example 7 A white heat-sensitive recording material was produced in the same manner as in Example 7 , except that 5 g of the specific example compound (108) produced in Example 4 was used instead of 5 g of the specific example compound (2) used in Example [Example 11] Production of heat-sensitive recording material Example 7Except for using 5 g of the specific example compound (124) produced in Example 5 instead of 5 g of the specific example compound (2) used in Example 7 A white heat-sensitive recording material was produced in the same manner. [Example 12] Production of Heat-Sensitive Recording Material Example 7 Except for using 5 g of the specific example compound (133) produced in Example 6 instead of 5 g of the specific example compound (2) used in Example 7 A white heat-sensitive recording material was produced in the same manner.

[0093] [Comparative Example 1] Production of Heat-Sensitive Recording Material Example 7 Except for using 5 g of the following Comparative Example Compound (H) instead of 5 g of the specific example compound (2) used in Example 7 A white heat-sensitive recording material was produced in the same manner. TIFF0007697782000025.tif53155

[0094] [Comparative Example 2] Production of Heat-Sensitive Recording Material Example 7 Except for using 5 g of the following Comparative Example Compound (I) instead of 5 g of the specific example compound (2) used in Example 7 A white heat-sensitive recording material was produced in the same manner. TIFF0007697782000026.tif50158

[0095] [Quality Performance Test of Heat-Sensitive Recording Material] Base white degree, base stability test, and color-developed image stability test of the heat-sensitive recording materials produced in Examples 7 to 12 and Comparative Examples 1 to 2 Measurement of base light resistance: After irradiating the heat-sensitive recording material with a 20,000 lux fluorescent lamp for 72 Hr, the base coloring density (OD value) was measured with a reflection densitometer RD-914.

[0096]

Table 1

[0097] Base paper whiteness: The smaller the value, the higher the whiteness. Base paper storage stability: The smaller the value after each test, the higher the stability of the base paper. Next, the thermal papers prepared in Examples 7 to 12 and Comparative Examples 1 and 2 were also colored at a pulse width of 0.95 ms using a printing device TH-PMD (manufactured by Okura Electric Co., Ltd.), and the color density (OD value) of the colored image was measured using an RD-914 manufactured by Macbeth. The stability test was conducted according to the following method.

[0098] Measurement of image resistance to moisture and heat: After exposing the colored image to 50 °C and 90% RH for 72 hours, the density (OD value) of the image was measured with a reflection densitometer RD-914. Measurement of image heat resistance: After exposing the colored image to 60 °C and 20% RH for 72 hours, the density (OD value) of the image was measured with a reflection densitometer RD-914. Measurement of image lightfastness: After irradiating the colored image with a fluorescent lamp of 20,000 lux for 72 hours, the density (OD value) of the image was measured with a reflection densitometer RD-914. Each image fastness was expressed by the following formula.

[0099] [Number]

[0100] These results are shown in Table 2. [Quality Performance Test of Thermal Recording Material] [Table 2] [Industrial Applicability]

[0101] The recording material using the phthalide dimer compound of the present invention is excellent in various performances such as the whiteness of the base paper, storage stability, and image fastness, and a clear cyan-colored image can be obtained. Therefore, it is very useful as a color former for full-color thermal recording materials.

Claims

1. A phthalide dimer compound represented by the following general formula (1). (In formula (1), R １ ~R ４ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, R ５ ~R ７ each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an unsubstituted or substituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group. X １ , X ２ represents a carbon atom or a nitrogen atom, provided that they do not both represent nitrogen atoms simultaneously. When X 1 , X ２ represents a carbon atom, it may have a substituent. Y represents an oxygen atom, a sulfur atom, a substituted or unsubstituted imino group, a carbonyl group, a sulfonyl group, an alkylene group, an arylene group, and R １ and R ２ may be bonded to each other to form a heterocyclic ring. Also, R ６ and R ７ may be bonded to each other to form an aliphatic ring or an aromatic ring.)

2. X 1 , X ２ The phthalide dimer compound according to claim 1, wherein X

3. The phthalide dimer compound according to claim 1 or 2, wherein Y is an unsubstituted alkylene group or an oxygen atom.

4. A recording material using the reaction between an electron-donating leuco dye and an electron-accepting color developer, characterized in that it contains the phthalide dimer compound according to any one of claims 1 to 3 as the electron-donating leuco dye.

5. The recording material according to claim 4, wherein the recording material is a heat-sensitive recording material

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