US3997488A
Expired / Lapsed
US
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Process for the preparation of a non-aqueous dispersion of thermoplastic resin
Assignee: Ricoh Co Ltd
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Filing: 1975-08-05
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Granted: 1976-12-14
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Expires: 1995-08-05
Abstract
Abstract This invention provides non-aqueous dispersions containing a graft-copolymer and at least one substance selected from the group consisting of wax and polyethylene in an organic solvent having a high resistivity and a low dielectric constant, said dispersions being useful for coatings, especially binders for use in electrostatic coating and toners for use in electrophotography.
Inventors
- 👤 Kazuo Tsubuko
- 👤 Eiichi Kawamura
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 01:11
CPC Classifications
C; C08; C08F; C08F285/00
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
492 words
A non-aqueous resin dispersion containing a graft-copolymer and at least one substance selected from the group consisting of wax or polyethylene having a softening point of 60° to 130° C, dispersed in an organic solvent having a high resistivity and a low dielectric constant, said non-aqueous resin dispersion having been prepared by carrying out successively the following four steps (a), (b), (c) and (d) in said organic solvent, at an elevated temperature, adding said wax or polyethylene in one of the four steps and dissolving it in the solvent, and cooling the reaction product of step (d) while stirring vigorously: a. copolymerizing from 99.9 to 80 parts by weight of a monomer having the formula (I) ##STR4## wherein R is hydrogen or methyl, A is --COOC n H 2n +1 or --OC n H 2n +1 , and n is an integer of from 6 to 20, with from 0.1 to 20 parts by weight of at least one co-monomer selected from the group consisting of an unsaturated carboxylic acid, glycidyl acrylate and glycidyl methacrylate; b. esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of glycidyl acrylate or glycidyl acrylate when said copolymer has been prepared by using an unsaturated carboxylic acid, or esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of said unsaturated carboxylic acid when said copolymer has been prepared by using glycidyl acrylate or glycidyl methacrylate; c. grafting 100 parts by weight of the esterified copolymer obtained in step (b) with from 5 to 100 parts by weight of a monomer having a vinyl group; d. polymerizing 100 parts by weight of the graft copolymer obtained in step (c) with from 0.1 to 20 parts by weight of a compound selected from the group consisting of maleic acid, furmaric acid, allylamine, vinylamine, aroyl alcohol, vinylsulfonic acid, vinyl phosphate and a vinyl monomer having the formula ##STR5## wherein R is hydrogen or methyl, and B is ##STR6## wherein m and m' are integers from 1 to 4, ##STR7## and wherein the amount of said wax or polyethylene added is as follows: when added in step (a), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the sum of the weights of said monomer (I) and said co-monomer, when added in step (b), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the copolymer obtained in step (a), when added in step (c), from 1 to 40 parts by weight of said wax or polyethylene, per 100 parts by weight of the esterified copolymer obtained in step (b), and when added in step (d), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the graft copolymer obtained in step (c).
Claim 2
Dependent Claim
492 words
A non-aqueous resin dispersion containing a graft-copolymer and at least one substance selected from the group consisting of wax or polyethylene having a softening point of 60° to 130° C, dispersed in an organic solvent having a high resistivity and a low dielectric constant, said non-aqueous resin dispersion having been prepared by carrying out successively the following four steps (a), (b), (c) and (d) in said organic solvent, at an elevated temperature, adding said wax or polyethylene in one of the four steps and dissolving it in the solvent, and cooling the reaction product of step (d) while stirring vigorously: a. copolymerizing from 99.9 to 80 parts by weight of a monomer having the formula (I) ##STR4## wherein R is hydrogen or methyl, A is --COOC n H 2n +1 or --OC n H 2n +1 , and n is an integer of from 6 to 20, with from 0.1 to 20 parts by weight of at least one co-monomer selected from the group consisting of an unsaturated carboxylic acid, glycidyl acrylate and glycidyl methacrylate; b. esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of glycidyl acrylate or glycidyl acrylate when said copolymer has been prepared by using an unsaturated carboxylic acid, or esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of said unsaturated carboxylic acid when said copolymer has been prepared by using glycidyl acrylate or glycidyl methacrylate; c. grafting 100 parts by weight of the esterified copolymer obtained in step (b) with from 5 to 100 parts by weight of a monomer having a vinyl group; d. polymerizing 100 parts by weight of the graft copolymer obtained in step (c) with from 0.1 to 20 parts by weight of a compound selected from the group consisting of maleic acid, furmaric acid, allylamine, vinylamine, aroyl alcohol, vinylsulfonic acid, vinyl phosphate and a vinyl monomer having the formula ##STR5## wherein R is hydrogen or methyl, and B is ##STR6## wherein m and m' are integers from 1 to 4, ##STR7## and wherein the amount of said wax or polyethylene added is as follows: when added in step (a), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the sum of the weights of said monomer (I) and said co-monomer, when added in step (b), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the copolymer obtained in step (a), when added in step (c), from 1 to 40 parts by weight of said wax or polyethylene, per 100 parts by weight of the esterified copolymer obtained in step (b), and when added in step (d), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the graft copolymer obtained in step (c).
Claim 3
Dependent Claim
35 words
A non-aqueous resin dispersion as claimed in claim 1, in which said unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid and maleic acid.
Claim 4
Dependent Claim
52 words
A non-aqueous resin dispersion as claimed in claim 2, in which said monomer having a vinyl group employed in step (c) is selected from the group consisting of acrylic acid, methacrylic acid, lower alkyl (C 1 to C 4 ) esters of acrylic acid or methacrylic acid, styrene, methylstyrene and vinyl acetate.
Claim 5
Dependent Claim
20 words
A non-aqueous resin dispersion as claimed in claim 3, in which said wax or polyethylene is added in step (c).
Claim 6
Dependent Claim
32 words
A non-aqueous resin dispersion as claimed in claim 3 in which said monomer having the formula (I) is selected from the group consisting of lauryl, 2-ethylhexyl, stearyl or vinylstearyl acrylates and methacrylates.
Claim 7
Dependent Claim
23 words
A non-aqueous resin dispersion as claimed in claim 1, in which said organic solvent is an aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon.
Claim 8
Dependent Claim
461 words
A process for preparing a non-aqueous resin dispersion containing a graft-copolymer which comprises carrying out successively the following four steps (a), (b), (c) and (d) in an organic solvent, at an elevated temperature, adding wax or polyethylene having a softening point of 60° to 130° C in one of the four steps and dissolving it in the solvent, and cooling the reaction product of step (d) while stirring vigorously: a. copolymerizing from 99.9 to 80 parts by weight of a monomer having the formula (I) ##STR8## wherein R is hydrogen or methyl, A is --COOC n H 2n +1 or --OC n H 2n +1 , and n is an integer of from 6 to 20, with from 0.1 to 20 parts by weight of at least one co-monomer selected from the group consisting of an unsaturated carboxylic acid, glycidyl acrylate and glycidyl methacrylate; b. esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of glycidyl acrylate or glycidyl acrylate when said copolymer has been prepared by using an unsaturated carboxylic acid, or esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of said unsaturated carboxylic acid when said copolymer has been prepared by using glycidyl acrylate or glycidyl methacrylate; c. grafting 100 parts by weight of the esterified copolymer obtained in step (b) with from 5 to 100 parts by weight of a monomer having a vinyl group; d. polymerizing 100 parts by weight of the graft copolymer obtained in step (c) with from 0.1 to 20 parts by weight of a compound selected from the group consisting of maleic acid, fumaric acid, allylamine, vinylamine, aroyl alcohol, vinyl sulfonic acid, vinyl phosphate and a vinyl monomer having the formula ##STR9## wherein R is hydrogen or methyl, and B is ##STR10## wherein m and m'are integers from 1 to 4, ##STR11## and wherein the amount of said wax or polyethylene added is as follows: when added in step (a), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the sum of the weights of said monomer (I) and said co-monomer, when added in step (b), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the copolymer obtained in step (a), when added in step (c), from 1 to 40 parts by weight of said wax or polyethylene, per 100 parts by weight of the esterified copolymer obtained in step (b), and when added in step (d), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the graft copolymer obtained in step (c).
Claim 9
Dependent Claim
461 words
A process for preparing a non-aqueous resin dispersion containing a graft-copolymer which comprises carrying out successively the following four steps (a), (b), (c) and (d) in an organic solvent, at an elevated temperature, adding wax or polyethylene having a softening point of 60° to 130° C in one of the four steps and dissolving it in the solvent, and cooling the reaction product of step (d) while stirring vigorously: a. copolymerizing from 99.9 to 80 parts by weight of a monomer having the formula (I) ##STR8## wherein R is hydrogen or methyl, A is --COOC n H 2n +1 or --OC n H 2n +1 , and n is an integer of from 6 to 20, with from 0.1 to 20 parts by weight of at least one co-monomer selected from the group consisting of an unsaturated carboxylic acid, glycidyl acrylate and glycidyl methacrylate; b. esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of glycidyl acrylate or glycidyl acrylate when said copolymer has been prepared by using an unsaturated carboxylic acid, or esterifying 100 parts by weight of the copolymer obtained in step (a) with from 0.1 to 20 parts by weight of said unsaturated carboxylic acid when said copolymer has been prepared by using glycidyl acrylate or glycidyl methacrylate; c. grafting 100 parts by weight of the esterified copolymer obtained in step (b) with from 5 to 100 parts by weight of a monomer having a vinyl group; d. polymerizing 100 parts by weight of the graft copolymer obtained in step (c) with from 0.1 to 20 parts by weight of a compound selected from the group consisting of maleic acid, fumaric acid, allylamine, vinylamine, aroyl alcohol, vinyl sulfonic acid, vinyl phosphate and a vinyl monomer having the formula ##STR9## wherein R is hydrogen or methyl, and B is ##STR10## wherein m and m'are integers from 1 to 4, ##STR11## and wherein the amount of said wax or polyethylene added is as follows: when added in step (a), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the sum of the weights of said monomer (I) and said co-monomer, when added in step (b), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the copolymer obtained in step (a), when added in step (c), from 1 to 40 parts by weight of said wax or polyethylene, per 100 parts by weight of the esterified copolymer obtained in step (b), and when added in step (d), from 5 to 50 parts by weight of said wax or polyethylene, per 100 parts by weight of the graft copolymer obtained in step (c).
Claim 10
Dependent Claim
33 words
A process as claimed in claim 7, in which said unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid and maleic acid.
Claim 11
Dependent Claim
50 words
A process as claimed in claim 8, in which said monomer having a vinyl group employed in step (c) is selected from the group consisting of acrylic acid, methacrylic acid, lower alkyl (C 1 to C 4 ) esters of acrylic acid or methacrylic acid, styrene, methylstyrene and vinyl acetate.
Claim 12
Dependent Claim
18 words
A process as claimed in claim 9, in which said wax or polyethylene is added in step (c).
Claim 13
Dependent Claim
30 words
A process as claimed in claim 9, in which said monomer having the formula (I) is selected from the group consisting of lauryl, 2-ethylhexyl, stearyl or vinylstearyl acrylates and methacrylates.
Claim 14
Dependent Claim
21 words
A process as claimed in claim 7, in which said organic solvent is an aliphatic hydrocarbon or a halogenated aliphatic hydrocarbon.
References Cited (Backward Citations)
US3665053A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1979-12-14 | 1980-06-14 | 1980-12-14 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-12-14 | 1984-06-14 | 1984-12-14 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-12-14 | 1988-06-14 | 1988-12-14 | $7700.00 | Window Closed / Lapsed |