Toner compositions

• US 5,348,832 A
• Filed: 06/01/1993
• Issued: 09/20/1994
• Est. Priority Date: 06/01/1993
• Status: Expired due to Term

• Current Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Original Assignee: Xerox Corporation (Xerox Holdings Corp.)
• Inventors: Sacripante, Guerino G., Patel, Raj D., Kmiecik-Lawrynowicz, Grazyna E.
• Primary Examiner(s): GOODROW, JOHN L
• Application Number:
  US08/069,792
• Time in Patent Office: 476 Days
• Field of Search: 430/137, 430/105, 430/109
• US Class Current: 430/109.4
• CPC Class Codes: C08G 63/6886 Dicarboxylic acids and dihydroxy compounds
• CPC Class Codes: G03G 9/08755 Polyesters

Abstract

A toner composition comprised of pigment, and a sulfonated polyester of the formula or as essentially represented by the formula ##STR1## wherein M is an ion independently selected from the group consisting of hydrogen, ammonium, an alkali metal ion, an alkaline earth metal ion and a metal ion; R is independently selected from the group consisting of aryl and alkyl; R'"'"' is independently selected from the group consisting of alkyl and oxyalkylene; and wherein n and o represent random segments; and wherein the sum of n and o are equal to 100 mole percent.

Claims

1. A toner composition consisting essentially of pigment, and a sulfonated polyester of the formula or as essentially represented by the formula ##STR4## wherein M is an ion independently selected from the group consisting of hydrogen, ammonium, an alkali metal ion, an alkaline earth metal ion and a metal ion;

R is independently selected from the group consisting of aryl and alkyl;

R'"'"' is independently selected from the group consisting of alkyl and oxyalkylene; and

wherein n and o represent random segments; and

wherein the sum of n and o are equal to 100 mole percent.

2. A toner in accordance with claim 1 wherein the sulfonated polyester is derived from at least one dicarboxylic acid, at least one diol and at least one component of a sulfonated ion attached to a dicarboxylic acid or diol component.

3. A toner in accordance with claim 1 wherein R is selected from the group consisting of terephthalyl, isophthalyl, phthalyl, xylyl, 1,4-cyclohexyl, 1,3-cyclohexyl, 1,2-cyclohexyl, 1,4-naphthyl, 1,7-naphthyl, 1,6-naphthyl, 1,3 naphthyl, 1,2-naphthyl, 1,8-naphthyl, and biphenyl.

4. A toner in accordance with claim 1 wherein R'"'"' is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, stearyl, lauryl, neopentyl, 1,2-propyl, 1,2-butyl, 1,3-butyl, 2-pentyl, 2,2-dimethylpropyl, and an oxyalkylene of diethyleneoxide, dipropyleneoxide, triethyleneoxide, and mixture thereof.

5. A toner in accordance with claim 2 wherein the sulfonated polyester is derived from dimethyl terephthalate, dimethyl-5-sulfo-isophthalate sodium salt, 1,2-propanediol and diethylene glycol.

6. A toner in accordance with claim 2 wherein the dicarboxylic acid or diester is selected from the group consisting of terephthalic acid, phthalic acid, isophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, succinic anhydride, succinic anhydride, dodecylsuccinic acid, dodecylsuccinic anhydride, glutaric acid, glutaric anhydride, adipic acid, pimelic acid, suberic acid, azelic acid, dodecanediacid, dimethyl terephthalate, diethyl terephthalate, dimethylisophthalate, diethylisophthalate, dimethylphthalate, phthalic anhydride, diethylphthalate, dimethylsuccinate, dimethylfumarate, dimethylmaleate, dimethylglutarate, dimethyladipate, dimethyl dodecylsuccinate, and mixtures thereof.

7. A toner in accordance with claim 2 wherein the diol is selected from the group consisting of ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, hexanediol, 2,2-dimethylpropanediol, 2,2,3-trimethylhexanediol, heptanediol, dodecanediol, bis(hyroxyethyl)-bisphenol A, bis(2-hyroxypropyl)-bisphenol A, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, xylenedimethanol, cyclohexanediol, diethylene glycol, bis(2-hydroxyethyl) oxide, dipropylene glycol, dibutylene, and mixtures thereof.

8. A toner in accordance with claim 2 wherein the sulfonated component is comprised of hydrogen, ammonium, lithium, sodium, potassium, cesium, berylium, magnesium, calcium, barium, strontium, iron, copper, vanadium, chromium, manganese, and cobalt of the sulfonated difunctional monomer dimethyl-5-sulfo-isophthalate, dialkyl-5-sulfo-isophthalate-4-sulfo-1,8-naphthalic anhydride, 4-sulfo-phthalic acid, dimethyl-4-sulfo-phthalate, dialkyl-4-sulfo-phthalate, 4-sulfophenyl-3,5-dicarbomethoxybenzene, 6-sulfo-2-naphthyl-3,5-dicarbomethoxybenzene, sulfo-terephthalic acid, dimethyl-sulfo-terephthalate, 5-sulfo-isophthalic acid, dialkyl-sulfo-terephthalate, sulfoethanediol, 2-sulfopropanediol, 2-sulfobutanediol, 3-sulfopentanediol, 2-sulfohexanediol, 3-sulfo-2-methylpentanediol, 2-sulfo-3,3-dimethylpentanediol, sulfo-p-hydroxybenzoic acid, N,N-bis(2-hydroxyethyl)-2-amino ethane sulfonate, or mixtures thereof.

9. A toner in accordance with claim 2 wherein the sulfonated component is dimethyl 5-sulfo-isophthalate sodium salt.

10. A toner in accordance with claim 1 wherein the sulfonated polyester is comprised of M+ ions of random copoly(ethylene-terephthalate)-copoly-(ethylene-5-sulfo-isophthalate), copoly(propylene-terephthalate)-copoly-(propylene-5-sulfo-isophthalate), copoly(diethylene-terephthalate)-copoly-(diethylene-5-sulfo-isophthalate), copoly(propylene-diethylene-terephthalate)-copoly-(propylene-diethylene-5-sulfoisophthalate), copoly(propylene-butylene-terephthalate)-copoly(propylene-butylene-5-sulfo-isophthalate), copoly(propoxylated bisphenol-A-fumarate)-copoly(propoxylated bisphenol A-5-sulfo-isophthalate), copoly(ethoxylated bisphenol-A-fumarate)-copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), copoly(ethoxylated bisphenol-A-maleate)copoly(ethoxylated bisphenol-A-5-sulfo-isophthalate), and mixtures thereof.

21. A toner in accordance with claim 1 wherein the pigment is carbon black, cyan, magenta, or yellow.

22. A toner in accordance with claim 1 wherein the toner average volume particle diameter size is from about 3 to about 21 microns.

23. A toner in accordance with claim 1 wherein the number average molecular weight of the sulfonated polyester is from about 2,000 grams per mole to about 150,000 gram per mole, and the weight average molecular weight is from about 4,000 gram per mole to about 300,000 gram per mole.

24. A toner in accordance with claim 1 wherein the alkali or alkaline earth metal ion is lithium, sodium, potassium, cesium, berylium, magnesium, calcium, barium, or strontium.

25. A toner in accordance with claim 1 wherein the metal ion is iron, copper, vanadium, chronium, manganese, cobalt, or mixtures thereof.

26. A toner in accordance with claim 1 wherein o is present in an amount of from about 0.5 to about 8 mole percent.

27. A toner in accordance with claim 1 wherein alkyl contains from 1 to about 25 carbon atoms;

aryl contains from 6 to about 24 carbon atoms; and

oxyalkylene contains from 1 to about 20 carbon atoms.

28. A developer composition comprised of the toner of claim 1, and carrier particles.

11. An in situ process for the preparation of toner compositions which comprises the dispersion of a sulfonated polyester of the formula or as essentially represented by the formula ##STR5## wherein M is an ion independently selected from the group consisting of hydrogen, ammonium, an alkali metal ion, an alkaline earth metal ion and a metal ion;

R is independently selected from the group consisting of aryl and alkyl;

R'"'"' is independently selected from the group consisting of alkyl and oxyalkylene; and

wherein n and o represent random segments; and

wherein the sum of n and o are equal to 100 mole percent in a vessel containing an aqueous media of an anionic surfactant, and a nonionic surfactant at a temperature of from about 100°

C. to about 180°

C. thereby obtaining suspended particles of about 0.05 micron to about 2 microns in volume average diameter;

subsequently homogenizing the resulting suspension at ambient temperature;

followed by aggregating the mixture by adding thereto a mixture of cationic surfactant and pigment particles to effect aggregation of said pigment and sulfonated polyester particles;

followed by heating the pigment-sulfonated polyester particle aggregates above the glass transition temperature of the sulfonated polyester causing coalescence of the aggregated particles to provide toner particles with an average particle volume diameter of from between 3 to 21 microns.

12. An in situ process in accordance with claim 11 wherein the dispersion of the polyester is accomplished by homogenization operated at from about 2,000 revolutions per minute to about 10,000 revolutions per minute for a duration of from about 1 minute to about 300 minutes.

13. A process in accordance with claim 11 wherein the anionic surfactant is selected from the group consisting of sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium dodecyl naphthalene sulfate, sodium lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, sodium alkyl naphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium alkyl diphenyl ether disulfonate, potassium salt of alkylphosphate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl sodium alkane sulfonate, and potassium alkylsulfonate;

and which surfactant is selected in an effective amount of from about 0.1 to about 5 percent by weight of the aqueous mixture.

14. A process in accordance with claim 11 wherein the pigment is carbon black.

15. A process in accordance with claim 11 wherein the nonionic surfactant is selected from the group consisting of polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octyphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, and polyoxyethylene nonylphenyl ether;

and which surfactant is selected in an effective amount of from about 0.1 to about 5 percent by weight of the aqueous fraction.

16. A process in accordance with claim 11 wherein the pigment is cyan, magenta, or yellow.

17. A process in accordance with claim 11 wherein there is added to the toner product surface additives of metal salts, metal salts of fatty acids, silicas, or mixtures thereof.

18. A process in accordance with claim 11 wherein the pigment is present in an amount of from about 0.1 to about 10 weight percent.

19. A process in accordance with claim 11 wherein there is formed aggregated pigment-sulfonated polyester particles of from about 3 to about 21 microns in volume average diameter size.

20. A process in accordance with claim 11 wherein there are formed coalesced toner particles of from about 3 to about 21 microns in volume average diameter size.