IP Library › Granted Patent US 12,151,497

Granted Patent B2

US 12,151,497 · App. 17/004,023 · Granted Nov 26, 2024

Heat sensitive recording material with non-phenolic color developers

Inventors: Erkan Kocak (Wilmington, DE); Frank Bachmann (Freiburg, DE); Priti Kulkarni (Ludwigshafen am Rhein, DE); Robert Montgomery O'Neil (Urmston, GB)

Assignee: Solenis Technologies, L.P.

B41M5/3333 B41M2205/04

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Quick Facts

Patent No.: US 12,151,497
App. No.: 17/004,023
Granted: Nov 26, 2024
Kind: B2

External Links

USPTO Patent Center↗ Full Patent PDF↗

Abstract

Heat sensitive recording material, recording sheets formed from heat sensitive recording material, and methods for forming images using heat sensitive recording material are provided. An exemplary heat sensitive recording material includes a color forming compound, a first non-phenolic color developer, and a second non-phenolic color developer.

Claims (167)

1. A heat sensitive recording material, comprising:

a) a color forming compound;

b) a first non-phenolic color developer of the formula (I)

wherein R and R1 are each, independently of each other, hydrogen; C 1 -C 18 -alkyl; C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl; (R 9 ) 2 N—C 1 -C 8 -alkyl, wherein R 9 stands for C 1 -C 8 -alkyl or C 5 -C 6 -cycloalkyl; or a radical of formula (II)

wherein R 2 , R 3 , R 4 , R 5 , R 6 are each, independently of each other, hydrogen; C 1 -C 8 -alkyl; —NH—C(═O)—R 7 or —C(═O)—NH—R 7 , wherein R 7 stands for C 1 -C 8 -alkyl; —C(═O)OR 8 , wherein R 8 stands for C 1 -C 8 -alkyl; halogen; or wherein R 2 and R 3 , or R 4 and R 5 or both, or wherein R 3 and R 4 , or R 5 and R 6 or both, or wherein R 2 and R 3 and R 5 and R 6 , stand together for a hydrocarbon diradical with three or four carbon atoms, and

wherein Q stands for a single bond or C 1 -C 8 -alkylene, which can be branched or unbranched, and

wherein the C 1 -C 8 -alkylene includes a main chain containing one or more oxygen atoms between two carbon atoms when the C 1 -C 8 -alkylene includes more than two carbon atoms, and

wherein at least one of R or R1 is a radical of formula (II); and

c) a second non-phenolic color developer.

2. The heat sensitive recording material of claim 1 , wherein the second non-phenolic color developer is a compound selected from the group consisting of:

(i) a compound represented by the following formula (N-I):

where:

R 1 , R 2 , and R 3 each independently represents a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 fluoroalkyl group, a N(R 4 ) 2 group, NHCOR 5 , an optionally substituted phenyl group, or an optionally substituted benzyl group;

R 4 represents a hydrogen atom, a phenyl group, a benzyl group, or a C 1 -C 6 alkyl group;

R 5 represents a C 1 -C 6 alkyl group;

n1 and n3 each independently represents any integer of 1 to 5; and

n2 represents any integer of 1 to 4;

(ii) a compound represented by the following formula (N-II):

where:

n2 represents any integer of 1 to 4;

n3 represents any integer of 1 to 5; and

n4 represents any integer of 1 to 7; and

(iii) a compound represented by the following formula (N-III):

where

n2 represents any integer of 1 to 4;

n3 represents any integer of 1 to 5; and

n4 represents any integer of 1 to 7.

3. The heat sensitive recording material of claim 2 , wherein the formula (N-I) is the following formula (N-IV):

where Rand R 3 each independently represents a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 fluoroalkyl group, a N(R 4 ) 2 group, NHCOR 5 , an optionally substituted phenyl group, or an optionally substituted benzyl group.

4. The recording composition according to claim 2 , wherein the formula (N-I) is the following formula (N-V):

where R 1 represents a hydrogen atom, a halogen atom, a nitro group, a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxyl group, a C 2 -C 6 alkenyl group, a C 1 -C 6 fluoroalkyl group, a N(R 4 ) 2 group, NHCOR 5 , an optionally substituted phenyl group, or an optionally substituted benzyl group.

5. The heat sensitive recording material of claim 1 , wherein the second non-phenolic color developer is a compound of the formula (P-I)

wherein

R1 is unsubstituted or substituted phenyl, or naphthyl,

R3 and R4 independently of each other are hydrogen, C 1 -C 8 alkyl, halogen-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen-substituted C 1 -C 8 alkoxy, C 1 -C 8 alkylsulphonyl, halogen, phenyl, phenoxy or phenoxycarbonyl,

X is a group of the formula

B is a linking group of formula —O—SO 2 —, —SO 2 —O—, —SO 2 —NH—, or —CO—NH—SO 2 —, and

R 2 is phenyl, which is unsubstituted or substituted by C 1 -C 8 alkyl, halogen-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen-substituted C 1 -C 8 alkoxy or halogen;

or R 2 is naphthyl or benzyl, which is substituted by C 1 -C 4 alkyl or halogen,

with the proviso, that, if B is not a linking group of formula —O—SO 2 —, then R 2 is unsubstituted or substituted phenyl, or naphthyl.

6. The heat sensitive recording material of claim 5 wherein, in the second color developer,

R1 is phenyl, which is substituted by C 1 -C 4 alkyl, and X is a group of the formula

R3 and R4 independently of each other are hydrogen, C1-C4 alkyl or halogen

B is a linking group of formula —O—SO 2 —, and

R2 is phenyl, which is unsubstituted or substituted by C1-C4 alkyl.

7. The heat sensitive recording material of claim 1 , wherein the second non-phenolic color developer is a compound of the formula (Q-I)

wherein

R 1 is phenyl or naphthyl, which is unsubstituted or substituted by C 1 -C 8 alkyl, C 1 -C 8 -alkoxy or halogen, or R 1 is C 1 -C 20 alkyl, which can be unsubstituted or substituted by C 1 -C 8 -alkoxy or halogen;

X is a group of the formula

A is unsubstituted or substituted phenylene, naphthylene or C 1 -C 12 alkylene, or is an unsubstituted or substituted heterocyclic group;

B is a linking group of formula —O—SO 2 —, —SO 2 —O—, —NH—SO 2 —, —SO 2 —NH—, —S—SO 2 —, —O—CO—NH—, —NH—CO—, —NH—CO—O—, —S—CO—NH—, —S—CS—NH—, —CO—NH—SO 2 —, —O—CO—NH—SO 2 —, —NH═CH—, —CO—NH—CO—, —S—, —CO—, —O—, —SO 2 —NH—CO—, —O—CO—O—, or —O—PO—(OR 2 ) 2 ; and

R 2 is aryl, which is unsubstituted or substituted by C 1 -C 8 alkyl, halogen-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen-substituted C 1 -C 8 alkoxy or halogen;

or R 2 is benzyl, which is unsubstituted or substituted by C 1 -C 8 alkyl, halogen-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy-substituted C 1 -C 8 alkyl, C 1 -C 8 alkoxy, halogen-substituted C 1 -C 8 alkoxy or halogen, or R 2 is C 1 -C 20 alkyl, which is unsubstituted or substituted by C 1 -C 8 alkoxy, halogen, phenyl, or naphthyl,

with the proviso, that, if B is not a linking group of formula —O—SO 2 —, then R 2 is unsubstituted or substituted phenyl, naphthyl, or C 1 -C 8 alkyl and that, if B is —O—, then R 2 is not alkyl, and with the further proviso that, if B stands for —O—SO 2 — or —SO 2 —O—, then R 2 is not C 1 -C 20 alkyl.

8. The heat sensitive recording material of claim 7 , wherein R 1 is phenyl, which is unsubstituted or substituted by C 1 -C 8 alkyl, C 1 -C 8 -alkoxy or halogen.

9. The heat sensitive recording material of claim 7 , wherein R 1 is phenyl, which is substituted by C 1 -C 8 alkyl, C 1 -C 8 -alkoxy or halogen.

10. The heat sensitive recording material of claim 7 , wherein R 1 is phenyl, which is substituted by C 1 -C 4 alkyl.

11. The heat sensitive recording material of claim 7 , wherein X is a group of the

12. The heat sensitive recording material of claim 1 wherein the heat sensitive recording material has a first non-phenolic color developer to second non-phenolic color developer ratio of from 10:90 to 90:10, in dry proportion of each non-phenolic color developer.

13. The heat sensitive recording material of claim 1 wherein the heat sensitive recording material has a first non-phenolic color developer to second non-phenolic color developer ratio of from 20:80 to 60:40, in dry proportion of each non-phenolic color developer.

14. A heat sensitive recording material, comprising:

a) a color forming compound;

b) a first non-phenolic color developer of the formula (I)

wherein Q stands for a single bond or C 1 -C 8 -alkylene, which can be branched or unbranched, and wherein the C 1 -C 8 -alkylene includes a main chain containing one or more oxygen atoms between two carbon atoms when the C 1 -C 8 -alkylene includes more than two carbon atoms;

c) a second non-phenolic color developer; and

d) at least one sensitizer selected from the group consisting of benzyl 2-naphthyl ether, stearamide, methylol stearamide, p-benzylbiphenyl, m-terphenyl, 2-benzyloxynaphthalene, 4-methoxybiphenyl, dibenzyl oxalate, di(4-methylbenzyl) oxalate, di(4-chlorobenzyl) oxalate, dimethyl phthalate, dibenzyl terephthalate, dibenzyl isophthalate, 1,2-diphenoxyethane, 1,2-bis(4-methylphenoxy) ethane, 1,2-bis(3-methyl-phenoxy)ethane, 4,4′-dimethylbiphenyl, phenyl-1-hydroxy-2-naphthoate, 4-methylphenyl biphenyl ether, 1,2-bis(3,4-dimethylphenyl) ethane, 2,3,5,6-4′-methyldiphenyl methane, 1,4-diethoxy-naphthalene, 1,4-diacetoxybenzene, 1,4-diproprionoxybenzene, o-xylylene-bis(phenyl ether), 4-(m-methylphenoxymethyl) biphenyl, p-hydroxyacetanilide, p-hydroxybutyranilide, p-hydroxynonananilide, p-hydroxylauranilide, p-hydroxyoctadecananilide, N-phenyl-phenylsulphonamide and sensitizers of the formula

wherein R and R′ are identical or different from each other and each represent a C 1 -C 6 alkyl.

15. A recording sheet comprising:

a support, and

a recording composition layer on the support, wherein the recording composition is formed from:

a) at least a color forming compound;

b) a first non-phenolic color developer of the formula (I)

wherein R and R1 are each independently of each other hydrogen, C 1 -C 18 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, (R 9 ) 2 N—C 1 -C 8 -alkyl, wherein R 9 stands for C 1 -C 8 -alkyl or C 5 -C 6 -cycloalkyl, or a radical of formula (II)

wherein R 2 , R 3 , R 4 , R 5 , R 6 are each independently of each other hydrogen, C 1 -C 8 -alkyl, —NH—C(═O)—R 7 , —C(═O)—NH—R 7 , wherein R 7 stands for C 1 -C 8 -alkyl, —C(═O)OR 8 , wherein R 8 stands for C 1 -C 8 -alkyl, halogen, or wherein R 2 and R 3 , or R 4 and R 5 or both, or wherein R 3 and R 4 , or R 5 and R 6 or both, or wherein R 2 and R 3 and R 5 and R 6 , stand together for a hydrocarbon diradical with three or four carbon atoms,

wherein Q stands for a single bond or C 1 -C 8 -alkylene, which can be branched or unbranched, and

wherein the C 1 -C 8 -alkylene includes a main chain containing one or more oxygen atoms between two carbon atoms when the C 1 -C 8 -alkylene includes more than 2 carbon atoms, and wherein at least one of R or R 1 is a radical of formula (II); and

c) a second non-phenolic color developer.

16. The recording sheet of claim 15 , wherein the second non-phenolic color developer is a compound selected from the group consisting of:

(i) a compound represented by the following formula (N-I):

where:

R 4 represents a hydrogen atom, a phenyl group, a benzyl group, or a C 1 -C 6 alkyl group;

R 5 represents a C 1 -C 6 alkyl group;

n1 and n3 each independently represents any integer of 1 to 5; and

n2 represents any integer of 1 to 4;

(ii) a compound represented by the following formula (N-II):

where:

n2 represents any integer of 1 to 4;

n3 represents any integer of 1 to 5; and

n4 represents any integer of 1 to 7; and

(iii) a compound represented by the following formula (N-III):

where

n2 represents any integer of 1 to 4;

n3 represents any integer of 1 to 5; and

n4 represents any integer of 1 to 7.

17. The recording sheet of claim 15 , wherein the second non-phenolic color developer is a compound of the formula (P-I)

wherein

R1 is unsubstituted or substituted phenyl, or naphthyl,

X is a group of the formula

B is a linking group of formula —O—SO 2 —, —SO 2 —O—, —SO 2 —NH—, or —CO—NH—SO 2 —, and

or R 2 is naphthyl or benzyl, which is substituted by C 1 -C 4 alkyl or halogen,

with the proviso, that, if B is not a linking group of formula —O—SO 2 —, then R 2 is unsubstituted or substituted phenyl, or naphthyl.

18. The recording sheet of claim 15 , wherein the second non-phenolic color developer is a compound of the formula (Q-I)

wherein

X is a group of the formula

A is unsubstituted or substituted phenylene, naphthylene or C 1 -C 12 alkylene, or is an unsubstituted or substituted heterocyclic group;

B is a linking group of formula —O—SO 2 —, —SO 2 —O—, —NH—SO 2 , —SO 2 —NH—, —S—SO 2 —, —O—CO—NH—, —NH—CO—, —NH—CO—O—, —S—CO—NH—, —S—CS—NH—, —CO—NH—SO 2 —, —O—CO—NH—SO 2 —, —NH═CH—, —CO—NH—CO—, —S—, —CO—, —O—, —SO 2 —NH—CO—, —O—CO—O—, or —O—PO—(OR 2 ) 2 ; and

19. A recording sheet comprising:

a support, and

a recording composition layer on the support, wherein the recording composition is formed from:

a) at least a color forming compound;

b) a first non-phenolic color developer of the formula (I)

wherein R and R 1 are each independently of each other hydrogen, C 1 -C 18 -alkyl, C 1 -C 8 -alkoxy-C 1 -C 8 -alkyl, (R 9 ) 2 N—C 1 -C 8 -alkyl, wherein R 9 stands for C 1 -C 8 -alkyl or C 5 -C 6 -cycloalkyl, or a radical of formula (II)

wherein Q stands for a single bond or C 1 -C 8 -alkylene, which can be branched or unbranched, and

wherein the C 1 -C 8 -alkylene includes a main chain containing one or more oxygen atoms between two carbon atoms when the C 1 -C 8 -alkylene includes more than 2 carbon atoms; and

c) a second non-phenolic color developer, wherein

(A) the second non-phenolic color developer is a compound selected from the group consisting of:

(i) a compound represented by the following formula (N-I):

where:

R 4 represents a hydrogen atom, a phenyl group, a benzyl group, or a C 1 -C 6 alkyl group;

R 5 represents a C 1 -C 6 alkyl group;

n1 and n3 each independently represents any integer of 1 to 5; and

n2 represents any integer of 1 to 4;

(ii) a compound represented by the following formula (N-II):

where:

n2 represents any integer of 1 to 4;

n3 represents any integer of 1 to 5; and

n4 represents any integer of 1 to 7; and

(iii) a compound represented by the following formula (N-III):

where

n2 represents any integer of 1 to 4;

n3 represents any integer of 1 to 5; and

n4 represents any integer of 1 to 7; or

(B) the second non-phenolic color developer is a compound of the formula (P-I)

wherein

R1 is unsubstituted or substituted phenyl, or naphthyl,

X is a group of the formula

B is a linking group of formula —O—SO 2 —, —SO 2 —O—, —SO 2 —NH—, or —CO—NH—SO 2 —, and

or R 2 is naphthyl or benzyl, which is substituted by C 1 -C 4 alkyl or halogen,

with the proviso, that, if B is not a linking group of formula —O—SO 2 —, then R 2 is unsubstituted or substituted phenyl, or naphthyl; or

wherein

X is a group of the formula

A is unsubstituted or substituted phenylene, naphthylene or C 1 -C 12 alkylene, or is an unsubstituted or substituted heterocyclic group;

Assignments (13)

SECURITY INTEREST Recorded Nov 14, 2025

From: CHEM-AQUA, INC.; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; NCH CORPORATION; NCH LIFE SCIENCES LLC; SOLENIS TECHNOLOGIES, L.P.

To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT

Reel/Frame 073570/0838 →

RELEASE OF SECURITY INTEREST Recorded Nov 14, 2025

From: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT

To: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.

Reel/Frame 073564/0864 →

RELEASE OF 2023 NOTES PATENT SECURITY INTERESTS Recorded Oct 10, 2025

From: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A.

To: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.

Reel/Frame 073074/0198 →

SECURITY AGREEMENT (NOTES) Recorded Oct 10, 2025

From: DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.

To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT

Reel/Frame 073061/0885 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 15, 2024

From: O'NEIL, ROBERT M.

To: SOLENIS TECHNOLOGIES, L.P.

Reel/Frame 067984/0037 →

SECURITY AGREEMENT (2024 NOTES) Recorded Jun 24, 2024

From: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.

To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT

Reel/Frame 067824/0278 →

2023 NOTES PATENT SECURITY AGREEMENT Recorded Jul 7, 2023

From: BIRKO CORPORATION; SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE GLOBAL CORPORATION

To: BANK OF NEW YORK MELLON TRUST COMPANY, N.A.

Reel/Frame 064225/0170 →

SECURITY AGREEMENT (NOTES) Recorded Sep 14, 2022

From: SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC

To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A. AS COLLATERAL AGENT

Reel/Frame 061432/0821 →

NOTES SECURITY AGREEMENT Recorded Nov 10, 2021

From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.

To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A.

Reel/Frame 058103/0066 →

TERM LOAN PATENT SECURITY AGREEMENT Recorded Nov 10, 2021

From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.