# US 9,517,651 B2 · Developer for thermal recording media and thermal composition media using the same

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,517,651 B2
- Document ID: US9517651B2
- Status: Granted
- Kind: B2
- Application number: 14/865,405
- Filed: 2015-09-25
- Published: 2016-03-31
- Granted: 2016-12-13
- Earliest claimed: 2015-09-25
- Assignees: Performance Chemicals LLC; Marubeni Specialty Chemicals, Inc.
- Applicants: Ronald Q. Ruffer, Jr.
- Inventors: Ronald Q. Ruffer, Jr.
- Web page: https://patentgrep.com/patent/US9517651B2

## CPC

- B41M 5/3335: {Compounds containing phenolic or carboxylic acid groups or metal salts thereof}
- B41M 5/3275: {Fluoran compounds}
- B41M 5/3336: {Sulfur compounds, e.g. sulfones, sulfides, sulfonamides}
- B41M 5/3372: {Macromolecular compounds}
- B41M 5/3375: {Non-macromolecular compounds}
- B41M 5/3377: {Inorganic compounds, e.g. metal salts of organic acids}
- C07C 275/36: with at least one of the oxygen atoms further bound to a carbon atom of a six-membered aromatic ring, e.g. N-aryloxyphenylureas
- B41M 2205/04: Direct thermal recording [DTR]
- B41M 2205/28: Storage stability; Improved self life
- B41M: PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING, (correction of typographical errors B41J; processes for applying transfer pictures or the like B44C1/16; fluid media for correction of typographical errors by coating C09D10/00; printing textiles D06P)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

The subject invention more specifically discloses compounds which are particularly useful as a developer for thermal recording media. These compounds include p-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, m-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, o-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, p-(p-{3-[m-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, and p-(m-{3-[o-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol. The present invention also reveals a thermal recording sheet having a thermal recording layer containing a colorless or pale colored dye precursor and a color developer reactable with said dye precursor upon heating to develop a color, wherein said color developer is a compound selected from the group consisting of p-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, m-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, o-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, p-(p-{3-[m-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, and p-(m-{3-[o-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

## Claims

### Claim 1

A compound which is particularly useful as a developer for thermal recording media, said compound being selected from the group consisting of p-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, m-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, o-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, p-(p-{3-[m-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, and p-(m-{3-[o-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 2 (depends on 1)

The compound of claim 1 wherein said compound is p-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 3 (depends on 1)

The compound of claim 1 wherein said compound is m-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 4 (depends on 1)

The compound of claim 1 wherein said compound is o-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 5 (depends on 1)

The compound of claim 1 wherein said compound is p-(p-{3-[m-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 6 (depends on 1)

The compound of claim 1 wherein said compound is p-(m-{3-[o-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 7

A thermal recording sheet having a thermal recording layer containing a colorless or pale colored dye precursor and a color developer reactable with said dye precursor upon heating to develop a color, wherein said color developer is a compound selected from the group consisting of p-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, m-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, o-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, p-(p-{3-[m-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, and p-(m-{3-[o-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 8 (depends on 7)

The thermal recording sheet of claim 7 which is further comprised of an electron accepting material selected from the group consisting of 2,4′-Dihydroxydiphenylsulfone (CAS#5397-34-2), 4,4′-Dihydroxydiphenylsulfone (CAS#80-90-1), Bis-(3-allyl-4-hydroxyphenyl)sulfone (CAS#41481-66-7), 4-[4′-[(1′-methylethyloxy)phenyl]sulfonyl]phenol (CAS#191680-83-8), 4-hydroxyphenyl 4-isoprooxyphenylsulfone (CAS#95235-30-6), N-(p-Toluenesulfonyl)-N′-(3-p-toluenesulfonyloxyphenyl)urea (CAS#232938-43-1), Phenol, 4-[[4-(2-propen-1yloxy)phenyl]sulfonyl (CAS#97042-18-7), 4-Hydroxy-4′benzyloxydiphenylsulfone (CAS#63134-33-8), and 4,4′bis(N-carbamoyl-4-methylbenzenesulfonamide)diphenylmethane (CAS#151882-81-4).

### Claim 9 (depends on 7)

The thermal recording sheet of claim 7 wherein the colorless or pale colored dye precursor is selected from the group consisting of 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-(N-ethyl-N-isoamylamino)fluorine, 2-anilino-3-methyl-6-(N-ethyl-N-propylamino)fluorane, 2-anilino-3-methyl-6-di-n-amylaminofluorane, 2-anilino-3-methyl-6-(N-ethyl-N-p-tolylamino)fluorane, 2-anilino-3-methyl-6-N-ethyl-N-sec-butylaminofluorane, 3-di-(n-pentylamino)-6-methyl-7-anilinofluorane, 3-(N-isoamyl-N-ethylamino)-6-methyl-7-anilinofluorane, 3-(N-n-hexyl-N-ethylamino)-6-methyl-7-anilinofluorane, 3-[N-(3-ethoxypropyl)-N-ethylamino]-6-methyl-7-anilinofluorane, 3-di-(n-butylamino)-7-2-chloroanilino)fluorane, 3-diethylamino-7-(2-chloroanilino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane.

### Claim 10 (depends on 7)

The thermal recording sheet of claim 7 which is further comprised of a sensitizer.

### Claim 11 (depends on 10)

The thermal recording sheet of claim 10 wherein the sensitizer is selected from the group consisting of stearamide, N-hydroxymethylstearamide, N-stearylstearamide, ethylenebisstearamide, N-stearylstearamide, ethylenebisstearamide, N-stearylurea, benzyl-2-naphthyl ether, m-terpphenyl, 4-benzylbiphenyl, 4-acetylbiphenyl, 4-(4-methylphenoxy)biphenyl, 1,2-bis(3-methylphenoxy) ethane, 1,2-diphenoxyethane, 2,2′-bis(4-methoxyphenoxy)diethyl ether, diphenoxyxylene, bis(4-methoxyphenyl)ether, diphenyl adipate, dibenzyl oxalate, di(4-methylbenzyl)oxalate, di(4-chlorobenzyl)oxalate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzene sulfonic ester, diphenylsulfone, bis(4-allyloxyphenyl) sulfone, 4-acetylacetophenone, acetoacetic acid anilides, and fatty acid aniliides.

### Claim 12 (depends on 7)

The thermal recording medium of claim 7 which is further comprised of a sensitizer.

### Claim 13 (depends on 12)

The thermal recording sheet of claim 12 wherein the sensitizer is selected from the group consisting of stearamide, N-hydroxymethylstearamide, N-stearylstearamide, ethylenebisstearamide, N-stearylstearamide, ethylenebisstearamide, N-stearylurea, benzyl-2-naphthyl ether, m-terpphenyl, 4-benzylbiphenyl, 4-acetylbiphenyl, 4-(4-methylphenoxy)biphenyl, 1,2-bis(3-methylphenoxy) ethane, 1,2-diphenoxyethane, 2,2′-bis(4-methoxyphenoxy)diethyl ether, diphenoxyxylene, bis(4-methoxyphenyl)ether, diphenyl adipate, dibenzyl oxalate, di(4-methylbenzyl)oxalate, di(4-chlorobenzyl)oxalate, dimethyl terephthalate, dibenzyl terephthalate, phenyl benzene sulfonic ester, diphenylsulfone, bis(4-allyloxyphenyl) sulfone, 4-acetylacetophenone, acetoacetic acid anilides, and fatty acid anilides.

### Claim 14 (depends on 7)

The thermal recording sheet of claim 7 which is further comprised of a binder.

### Claim 15 (depends on 14)

The thermal recording sheet as specified in claim 14 wherein the binder is a polyvinyl alcohol.

### Claim 16 (depends on 14)

The thermal recording sheet as specified in claim 14 wherein the binder is selected from the group consisting of acrylic emulsions, styrene copolymer emulsions, butadiene copolymer emulsions, acrylonitrile copolymers and terpolymer emulsions, polyvinyl acetate emulsions, vinyl acetate ethylene emulsions, polyurethane emulsions, starches, and hydroxymethyl cellulose.

### Claim 17 (depends on 7)

The thermal recording sheet of claim 7 which is further comprised of a filler.

### Claim 18 (depends on 17)

The thermal recording sheet of claim 17 wherein the filler is selected from the group consisting of titanium dioxide, silica, aluminum tri-hydrate, clay, mica, calcium carbonate, talc, magnesium hydroxide, magnesium oxide, hollow plastic spheres, and polystyrene.

### Claim 19 (depends on 7)

The thermal recording sheet of claim 7 which is further comprised of a slip agent.

### Claim 20 (depends on 19)

The thermal recording sheet of claim 19 wherein the slip agent is selected from the group consisting of zinc stearate, calcium stearate, stearamide, and polyethylene wax.

### Claim 21 (depends on 7)

The thermal recording sheet of claim 7 which is further comprised of a UV absorber.

### Claim 22 (depends on 7)

The thermal recording sheet of claim 7 which is further comprised of an optical brightener.

### Claim 23

A thermal recording medium which is comprised of a substrate having thereon a recording layer containing a colorless or pale colored dye precursor and a color developer reactable with said dye precursor upon heating to develop a color, wherein said color developer is a compound selected from the group consisting of p-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, m-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, o-(p-{3-[p-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, p-(p-{3-[m-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol, and p-(m-{3-[o-(p-hydroxyphenoxy)phenyl]ureido}phenoxy)phenol.

### Claim 24 (depends on 23)

The thermal recording medium of claim 23 which is further comprised of an electron accepting material selected from the group consisting of 2,4′-Dihydroxydiphenylsulfone (CAS#5397-34-2), 4,4′-Dihydroxydiphenylsulfone (CAS#80-90-1), Bis-(3-allyl-4-hydroxyphenyl)sulfone (CAS#41481-66-7), 4-[4′-[(1′-methylethyloxy)phenyl]sulfonyl]phenol (CAS#191680-83-8), 4-hydroxyphenyl 4-isoprooxyphenylsulfone (CAS#95235-30-6), N-(p-Toluenesulfonyl)-N′-(3-p-toluenesulfonyloxyphenyl)urea (CAS#232938-43-1), Phenol, 4-[[4-(2-propen-1yloxy)phenyl]sulfonyl (CAS#97042-18-7), 4-Hydroxy-4′benzyloxydiphenylsulfone (CAS#63134-33-8), and 4,4′bis(N-carbamoyl-4-methylbenzenesulfonamide)diphenylmethane (CAS#151882-81-4).

### Claim 25 (depends on 23)

The thermal recording medium of claim 23 wherein the colorless or pale colored dye precursor is selected from the group consisting of 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-(N-ethyl-N-isoamylamino)fluorine, 2-anilino-3-methyl-6-(N-ethyl-N-propylamino)fluorane, 2-anilino-3-methyl-6-di-n-amylaminofluorane, 2-anilino-3-methyl-6-(N-ethyl-N-p-tolylamino)fluorane, 2-anilino-3-methyl-6-N-ethyl-N-sec-butylaminofluorane, 3-di-(n-pentylamino)-6-methyl-7-anilinofluorane, 3-(N-isoamyl-N-ethylamino)-6-methyl-7-anilinofluorane, 3-(N-n-hexyl-N-ethylamino)-6-methyl-7-anilinofluorane, 3-[N-(3-ethoxypropyl)-N-ethylamino]-6-methyl-7-anilinofluorane, 3-di-(n-butylamino)-7-2-chloroanilino)fluorane, 3-diethylamino-7-(2-chloroanilino)fluorane, and 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluorane.

### Claim 26 (depends on 23)

The thermal recording medium of claim 23 which is further comprised of a binder.

### Claim 27 (depends on 26)

The thermal recording medium as specified in claim 26 wherein the binder is a polyvinyl alcohol.

### Claim 28 (depends on 27)

The thermal recording medium as specified in claim 27 wherein the binder is selected from the group consisting of acrylic emulsions, styrene copolymer emulsions, butadiene copolymer emulsions, acrylonitrile copolymers and terpolymer emulsions, polyvinyl acetate emulsions, vinyl acetate ethylene emulsions, polyurethane emulsions, starches, and hydroxymethyl cellulose.

### Claim 29 (depends on 23)

The thermal recording medium of claim 23 which is further comprised of a filler.

### Claim 30 (depends on 29)

The thermal recording sheet of claim 29 wherein the filler is selected from the group consisting of titanium dioxide, silica, aluminum tri-hydrate, clay, mica, calcium carbonate, talc, magnesium hydroxide, magnesium oxide, hollow plastic spheres, and polystyrene.

### Claim 31 (depends on 23)

The thermal recording medium of claim 23 which is further comprised of a slip agent.

### Claim 32 (depends on 31)

The thermal recording medium of claim 31 wherein the slip agent is selected from the group consisting of zinc stearate, calcium stearate, stearamide, and polyethylene wax.

### Claim 33 (depends on 23)

The thermal recording medium of claim 23 which is further comprised of a UV absorber.

### Claim 34 (depends on 23)

The thermal recording medium of claim 23 which is further comprised of an optical brightener.