Thermosensitive recording material

• US 5,444,036 A
• Filed: 01/07/1994
• Issued: 08/22/1995
• Est. Priority Date: 01/08/1993
• Status: Expired due to Fees

• Current Assignee: New Oji Paper Co., Ltd.
• Original Assignee: New Oil Paper Company Limited
• Inventors: Uchida, Kyoko, Iwasaki, Akiko, Fujino, Masatoshi, Toyofuku, Kunitaka
• Primary Examiner(s): HESS, BRUCE H
• Application Number:
  US08/178,830
• Time in Patent Office: 592 Days
• Field of Search: 427/150, 503/208, 503/209, 503/216, 503/225
• US Class Current: 503/209
• CPC Class Codes: B41M 5/3333 Non-macromolecular compounds
• CPC Class Codes: B41M 5/3375 Non-macromolecular compounds

Abstract

A thermosensitive recording material for recording thereon clear colored images having an excellent storage persistency over a long time, comprises a thermosensitive colored image-forming layer formed on a substrate and comprising a colorless dye precursor, a binder and a color developing agent comprising at least one compound having at least one group of the formula (I): ##STR1## wherein R = unsubstituted aromatic group or substituted aromatic group having at least one substituent selected from alkyl, alkoxyl and halogen, and the thermosensitive colored image-forming layer further comprises an additive comprising at least one member selected from the compounds of the formulae (II) and (III): ##STR2## wherein R¹, R², R³ = alkyl, alkoxyl, aralkyl, aryl, aryloxy, nitro, acetylamino, acetoacetylamino, halogen or hydrogen; and Ar₁, Ar₂ = unsubstituted phenyl or naphthyl or substituted phenyl or naphthyl with 1 to 3 substituent selected from aryl, alkyl, alkoxyl, nitro, alkylamino, allyloxy, aryloxy and aralkyloxy groups and halogen atoms, one of Ar₁ and Ar₂ having a substituent selected from alkoxyl, allyloxy, phenoxy and benzyloxy groups.

Claims

1. A thermosensitive recording material comprising:

a substrate sheet; and

a thermosensitive colored image-forming layer formed on a surface of the substrate sheet and comprising a substantially colorless dye precursor, a color developing agent reactive with the dye precursor upon heating to thereby develop a color, and a binder,

said color developing agent comprising at least one compound comprising, per molecule thereof, at least one arylsulfonylureido group of the formula (I);

##STR7## wherein R represents a member selected from the group consisting of unsubstituted aromatic groups and substituted aromatic groups having at least one substituent selected from the group consisting of lower alkyl groups, lower alkoxyl groups and halogen atoms, and

said thermosensitive colored image-forming layer further comprising a thermally fusible additive comprising at least one compound selected from the group consisting of;

(1) acetoacetanilide compounds of the formula (II);

##STR8## wherein R¹, R² and R³ respectively and independently from each other represent a member selected from the group consisting of alkyl groups, alkoxyl groups, aralkyl groups, aryl groups, aryloxy groups, nitro group, acetylamino group, acetoacetylamino group, hydrogen atom and halogen atoms; and

(2) sulfonamide compounds of the formula (III);

space="preserve" listing-type="equation">Ar.sub.1 --SO.sub.2 NH--Ar.sub.2 (III)

wherein Ar₁ and Ar₂ respectively and independently from each other represent a member selected from the group consisting of unsubstituted phenyl and naphthyl groups, and substituted phenyl and naphthyl groups each having 1 to 3 substituents selected from the group consisting of aryl groups, alkyl groups, alkoxyl groups, nitro group, halogen atoms, alkylamino groups, allyloxy group, aryloxy groups, and aralkyloxy groups, and one of Ar₁ and Ar₂ has at least one substituent selected from the group consisting of alkoxyl groups, allyloxy group, phenoxy group and benzyloxy group.

2. The thermosensitive recording material as claimed in claim 1, wherein the compound comprising the arylsulfonylureido group of the formula (I) is selected from the group consisting of:

N-(p-toluenesulfonyl )-N'"'"'-phenylurea,

N-(p-toluenesulfonyl )-N'"'"'-(p-methoxyphenyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(o-tolyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(m-tolyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(p-tolyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(p-n-butylphenyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(o-chlorophenyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(m-chlorophenyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(2,4-dichlorophenyl)urea,

N-(p-toluenesul fonyl )-N'"'"'-benzylurea,

N-(p-toluenesulfonyl )-N'"'"'-(1-naphthyl)urea,

N-(p-toluenesulfonyl )-N'"'"'-(1-(2-methylnaphthyl))urea,

N-(benzenesulfonyl)-N'"'"'-phenylurea,

N-(p-chlorobenzenesul fonyl)-N'"'"'-phenylurea,

N-(o-toluenesulfonyl)-N'"'"'-phenylurea,

N-(p-toluenesulfonyl)-N'"'"'-methylurea,

N-(p-toluenesulfonyl)-N'"'"'-ethylurea,

N-(p-toluenesulfonyl)-N'"'"'-(2-phenoxyethyl)urea,

N,N'"'"'-bis(p-toluenesulfonyl)urea,

N-(p-toluenesulfonyl)-N'"'"'-(o-diphenyl)urea,

N-(p-toluenesulfonyl)-N'"'"'-(p-ethoxycarbonylphenyl)urea,

N-(p-toluenesulfonyl)-N'"'"'-butylurea,

N-(p-chlorobenzenesulfonyl)-N'"'"'-propylurea,

N-(p-methoxybenzenesulfonyl)-N'"'"'-phenylurea,

bis((p-toluenesulfonyl)ureido)ketone,

5. The thermosensitive recording material as claimed in claim 1, wherein the acetoacetanilide compound of the formula (II) is selected from the group consisting of:

p-chloroacetoacetanilide,

o-chloroacetoacetanilide,

acetoacetanilide,

o-methylacetoacetanilide,

p-methylacetoacetanilide,

o-methoxyacetoacetanilide,

p-methoxyacetoacetanilide,

p-ethoxyacetoacetanilide,

p-acetylaminoacetoacetanilide,

2,4-dimethylacetoacetanilide,

5-chloro-2-methoxyacetoacetanilide,

2,4-dimethoxyacetoacetanilide,

2,5-dimethoxyacetoacetanilide,

4-chloro-2,5-dimethoxyacetoacetanilide,

o-nitroacetoacetanilide,

m-nitroacetoacetanilide,

p-nitroacetoacetanilide,

2-methoxy-5-methylacetoacetanilide,

2-methoxy-4-nitroacetoacetanilide,

2,5-dichloroacetoacetanilide,

7. The thermosensitive recording material as claimed in claim 1, wherein the arylsulfonamide compound of the formula (III) is selected from the group consisting of:

4'"'"'-methoxy-p-toluenesulfonanilide,

2'"'"'-methoxy-p-toluenesulfonanilide,

4'"'"'-ethoxy-p-toluenesulfonanilide,

2'"'"'-ethoxy-p-toluenesulfonanilide,

4'"'"'-methoxy-benzenesulfonanilide,

3'"'"'-methoxy-benzenesulfonanilide,

2'"'"'-methoxy-benzenesulfonanilide,

4'"'"'-ethoxy-benzenesulfonanilide,

2'"'"'-ethoxy-benzenesulfonanilide,

4'"'"'-methoxy-p-chlorobenzenesulfonanilide,

2'"'"'-methoxy-p-chlorobenzenesulfonanilide,

4'"'"'-ethoxy-p-chlorobenzenesulfonanilide,

4'"'"'-methoxy-p-bromobenzenesulfonanilide,

4'"'"'-methoxy-p-ethylbenzenesulfonanilide,

2'"'"'-methoxy-p-ethylbenzenesulfonanilide,

4'"'"'-methoxy-2,5-dimethylbenzenesulfonanilide,

4'"'"'-methoxy-naphthalene-2-sulfonanilide,

4'"'"'-methoxy-naphthalene-1-sulfonanilide,

2'"'"'-methoxy-naphthalene-2-sulfonanilide,

2'"'"'-allyloxy-p-toluenesulfonanilide,

2'"'"'-n-propoxy-p-toluenesulfonanilide,

2'"'"'-n-butoxy-p-toluenesulfonanilide,

4'"'"'-methoxy-o-toluenesulfonanilide,

2'"'"'-methoxy-o-toluenesulfonanilide,

'"'"' -ethoxy-o-toluenesulfonanilide,

2'"'"'-ethoxy-o-toluenesulfonanilide,

2'"'"'-methoxy-5'"'"'-chloro-p-toluenesulfonanilide,

2'"'"',5'"'"'-dimethoxy-4'"'"'-chloro-benzenesulfonanilide,

2'"'"',5'"'"'-dimethoxy-benzenesulfonanilide,

2'"'"',4'"'"'-dimethoxy-benzenesulfonanilide,

3'"'"',5'"'"'-dimethoxy-benzenesulfonanilide,

4'"'"'-nitro-2'"'"'-methoxy-benzenesulfonanilide,

5'"'"'-nitro-2'"'"'-methoxy-benzenesulfonanilide,

2'"'"'-nitro-4'"'"'-methoxy-benzenesulfonanilide,

3'"'"',4'"'"',5'"'"'-trimethoxy-benzenesulfonanilide,

4'"'"'-chloro-2'"'"'-methoxy-5'"'"'-methyl-benzenesulfonanilide,

2'"'"'-methoxy-5'"'"'-methyl-benzenesulfonanilide,

4'"'"'-nitro-2'"'"'-methoxy-5'"'"'-methyl-benzenesulfonanilide,

4'"'"'-nitro-2'"'"'-ethoxy-5'"'"'-methyl-benzenesulfonanilide,

4-methoxybenzenesulfonanilide,

4'"'"'-methoxy-p-toluenesulfonanilide,

2-methoxybenzenesulfonanilide,

4-ethoxybenzenesulfonanilide,

2-ethoxybenzensulfonanilide,

3,4-dimethoxybenzenesulfonanilide,

6'"'"'-methoxy-2'"'"'-nitro-m-toluenesulfonanilide,

p-toluenesulfonyl-N-4-(methoxy-2-naphthyl)amide,

4,4'"'"'-dimethoxy-benzenesulfonanilide,

4-methoxy-4'"'"'-methyl-benzenesulfonanilide,

2'"'"'-benzyloxy-p-toluenesulfonanilide,

3'"'"'-benzyloxy-p-toluenesulfonanilide,

2'"'"'-phenoxy-p-toluenesulfonanilide,

4'"'"'-phenoxy-p-toluenesulfonanilide,

4'"'"'-phenyl-4-methoxybenzenesulfonanilide, and

4'"'"'-dimethylamino-4-methoxybenzenesulfonanilide.

8. The thermosensitive recording material as claimed in claim 1, wherein the acetoacetanilide compound of the formula (II) and the sulfonamide compound of the formula (III) have a melting temperature of 60°

C. to 180°

C.

9. The thermosensitive recording material as claimed in claim 1, wherein the color-developing compound having at least one arylsulfonylureido group is present in an amount of 5 to 50% based on the dry weight of the thermosensitive colored image-forming layer.

10. The thermosensitive recording material as claimed in claim 1, wherein the thermally fusible additive is present in an amount of 5 to 50% based on the dry weight of the thermosensitive colored image-forming layer.

3. 2-bis(N'"'"'-(p-toluenesulfonyl)ureido)ethane,

1,1,6,6,-tetra(N'"'"'-(p-toluenesulfonyl)ureido)heptane,

1,5-bis(N'"'"'-(p-toluenesulfonyl)ureido)-3-oxapentane,

1,5-bis(N'"'"'-(p-toluenesulfonyl)ureido)-3-thiopentane,

1,3-bis(N'"'"'-(p-toluenesulfonyl)ureido)-2-propane,

1,5-bis(N'"'"'-(p-toluenesulfonyl)ureido)-3-(2'"'"'-(N'"'"'-(p-toluenesulfonyl)ureido)ethyl)-3-azapentane,

4,4'"'"'-bis(N'"'"'-(p-toluenesulfonyl)ureido)-diphenylmethane,

4,4'"'"'-bis(N'"'"'-(o-toluenesulfonyl)ureido)-diphenylmethane,

4,4'"'"'-bis(benzenesulfonylureido)-diphenylmethane,

4,4'"'"'-bis(1-naphthalenesulfonylureido)-diphenylmethane,

2,2-bis(4'"'"',4"-(N'"'"'-(p-toluenesulfonyl)ureido)-phenyl)propane,

1,2-bis(4'"'"'-(N'"'"'-(p-toluenesulfonyl)ureido)-phenyloxy)ethane,

2,5-bis((N'"'"'-(p-toluenesulfonyl)ureido)methyl)-furan,

1,3-bis(N'"'"'-(p-toluenesulfonyl)ureido)benzene,

1,4-bis(N'"'"'-(p-toluenesulfonyl)ureido)benzene,

1,5-bis(N'"'"'-(p-toluenesulfonyl)ureido)-naphthalene,

1,8-bis(N'"'"'-(p-toluenesulfonyl)ureido)-naphthalene,

4. 4'"'"'-bis(N'"'"'-(p-toluenesulfonyl)ureido)-diphenylether,

3,3'"'"'-bis(N'"'"'-(p-toluenesulfonyl)ureido)-diphenylsulfone,

4,4'"'"'-bis(N'"'"'-(p-toluenesulfonyl)ureido)-diphenylsulfone,

2,4-bis(N'"'"'-(p-toluenesulfonyl)ureido)-toluene,

2,6-bis(N'"'"'-(p-toluenesulfonyl)ureido)-toluene,

4,4'"'"'-bis(N'"'"'-(p-toluenesulfonyl)ureido)-diphenylsulfide, and

3,4'"'"'-bis(N'"'"'-(p-toluenesulfonyl)ureido)-diphenylether.

6. 3-bis(acetoacetylamino)benzene,

1,4-bis(acetoacetylamino)benzene,

o-ethylacetoacetanilide,

2-chloro-4-methylacetoacetanilide,

4-methoxy-2-nitroacetoacetanilide,

2,4-dimethoxy-5-chloroacetoacetanilide,

2,5-diethoxy-4-chloroacetoacetanilide, and

o-ethoxyacetoacetanilide.