Toner resin composition and process for preparing same

• US 5,342,722 A
• Filed: 05/06/1992
• Issued: 08/30/1994
• Est. Priority Date: 11/14/1990
• Status: Expired due to Term

• Current Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Original Assignee: Mitsubishi Rayon Company Limited (Mitsubishi Chemical Holdings Corporation)
• Inventors: Itoh, Masahiro, Ito, Hirokazu, Yoshida, Keiji, Inagaki, Motoshi, Takahiro, Syuji
• Primary Examiner(s): Welsh, Maurice J.
• Assistant Examiner(s): Dodson, Shelley A.
• Application Number:
  US07/878,910
• Time in Patent Office: 846 Days
• Field of Search: 430/106.6, 430/107, 430/109, 430/110, 430/111, 430/114, 430/904, 430/908, 430/137
• US Class Current: 430/109.2
• CPC Class Codes: G03G 9/08706 Polymers of alkenyl-aromatic compounds
• CPC Class Codes: G03G 9/08711 with esters of acrylic or methacrylic acid
• CPC Class Codes: G03G 9/08755 Polyesters
• CPC Class Codes: G03G 9/08786 Graft polymers
• CPC Class Codes: Y10S 430/105 Polymer in developer
• CPC Class Codes: Y10S 430/109 Polyester

Abstract

A toner resin composition comprising 5 to 40% by weight of a polyester (A) having a weight average molecular weight of 3,000 to 20,000 and 50 to 95% by weight of a styrene-acrylic copolymer (B). The styrene-acrylic copolymer (B) is comprised of 10 to 25% by weight of a high molecular weight polymer (B1) having a weight average molecular weight of 500,000 to 1,100,000 and 75 to 90% by weight of a low molecular weight polymer (B2) having a weight average molecular weight of 5,000 to 100,000. The high molecular weight polymer (B1) is comprised of a styrene component (b-1) and an acrylic ester and/or methacrylic ester component (b-2). The low molecular weight polymer (B2) is comprised of a styrene component (b-1), an acrylic ester and/or methacrylic ester component (b-2), 0.3 to 3 parts by weight, per 100 parts of the total weight of said component (b-1) and component (b-2), of an α-methyl styrene dimer (b-3) and 0.5 to 30 parts by weight, per 100 parts by weight of said polyester (A), of a glycidyl methacrylate component (b-4).

Claims

1. A toner resin composition comprising a uniform dispersion of 5 to 40% by weight of a linear polyester (A) having a weight average molecular weight of 3,000 to 20,000 and 50 to 95% by weight of a styrene-acrylic copolymer (B), wherein said styrene-acrylic copolymer (B) is comprised of 10 to 25% by weight of a high molecular weight polymer (B1) having a weight average molecular weight of 500,000 to 1,100,000 and 75 to 90% by weight of a low molecular weight polymer (B2) having a weight average molecular weight of 5,000 to 100,000, said high molecular weight polymer (B1) is comprised of a styrene component (b-1) and an acrylic ester and/or methacrylic ester component (b-2), and said low molecular weight polymer (B2) is comprised of a styrene component (b-1), an acrylic ester and/or methacrylic ester component (b-2), 0.3 to 3 parts by weight, per 100 parts of the total weight of said component (b-1) and component (b-2), of an α

-methyl styrene dimer (b-3) and 0.5 to 30 parts by weight, per 100 parts by weight of said polyester (A), of a glycidyl methacrylate component (b-4).

2. A composition as set forth in claim 1, which has a glass transition temperature of 40°

to 68°

C., a softening point of 100°

to 160°

C. and an acid value of 0.1 to 10 mgKOH/g.

3. A composition as set forth in claim 1, wherein said polyester (A) has a structure originating in a divalent carboxylic acid component (a-1), 0.2 to 0.7 mole, per mole of said divalent carboxylic acid, of an aromatic diol component (a-2) and 0.3 to 0.8 mole, per mole of said divalent carboxylic acid, of an aliphatic diol component (a-3).

4. A composition as set forth in claim 3, wherein said divalent carboxylic acid component (a-1) is selected from the group consisting of maleic acid, fumaric acid, itaconic acid, cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, adipic acid and sebacic acid.

5. A composition as set forth in claim 3, wherein said aromatic diol component (a-2) is selected from the group consisting of bis-phenol A, bis-phenol S, bis-phenol F, hydrogenated bis-phenol A, polyoxypropylene-(n)-polyoxyethylene-(n'"'"')-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(n'"'"')-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-(n)-2,2-bis(4-hydroxyphenyl)propane and polyoxypropylene-(n)-hydroxone (where 2≦

n and n'"'"'≦

6).

6. A composition as set forth in claim 3, wherein said aliphatic diol component (a-3) is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, cyclohexane dimethanol and neopentyl glycol.

7. A composition as set forth in claim 1, wherein said polyester (A) has a weight average molecular weight of 3,000 to 20,000, an acid value of 0.5 to 10 mgKOH/g, a glass transition temperature of 40°

to 68°

C. and a softening temperature of 80°

to 160°

C.

8. A composition as set forth in claim 1, wherein said styrene-acrylic copolymer (B) is comprised of a styrene component (b-1), an acrylic ester and/or methacrylic ester component (b-2), an α

-methyl styrene dimer (b-3) and a glycidyl methacrylate component (b-4) in amounts, per 100 parts of the total weight of said component (b-1) and component (b-2), of 50 to 90 parts by weight of said component (b-1), 10 to 50 parts by weight of said component (b-2) and 0.3 to 3 parts by weight of said dimer (b-3) and 0.5 to 30 parts by weight, per 100 parts by weight of said polyester (A), of said component (b-4).

9. A composition as set forth in claim 1, wherein said styrene component (b-1) is selected from the group consisting of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α

-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-phenylstyrene and 3,4-dichlorostyrene.

10. A composition as set forth in claim 1, wherein said acrylic ester and/or methacrylic ester component (b-2) is selected from the group consisting of ethyl acrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, ethyl methacrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.

11. A composition as set forth in claim 1, wherein the ratio of the amounts of said styrene component (b-1) to said acrylic ester and/or methacrylic ester component (b-2) is such that the amount of the component (b-1) is 50 to 90 parts by weight and the amount of the component (b-2) is 10 to 50 parts by weight with respect to 100 parts by weight of the total amounts of the component (b-1) and component (b-2).

12. A composition as set forth in claim 1, wherein said styrene-acrylic copolymer (B) has a glass transition temperature of 40°

to 68°

C. and a softening point of 100°

to 160°

C.

13. A toner resin composition comprising a uniform dispersion of:

5 to 40% by weight of a linear polyester (A) having a structure originating in a divalent carboxylic acid component (a-1), 0.2 to 0.7 mole, per mole of said divalent carboxylic acid, of an aromatic diol component (a-2) and 0.3 to 0.8 mole, per mole of said divalent carboxylic acid, of an aliphatic diol component (a-3) and having a weight average molecular weight of 3,000 to 20,000, an acid value of 0.5 to 10 mgKOH/g, a glass transition temperature of 40°

to 68°

C. and a softening temperature of 80°

to 160°

C.; and

,

60to 95% by weight of a styrene-acrylic copolymer (B) formed by using a styrene component (b-1), an acrylic ester and/or methacrylic ester component (b-2), an α

-methyl styrene dimer (b-3) and a glycidyl methacrylate component (b-4) in amounts, per 100 parts of the total weight of said component (b-1) and component (b-2), of 50 to 90 parts by weight of said component (b-1), 10 to 50 parts by weight of said component (b-2) and 0.3 to 3 parts by weight of said dimer (b-3) and 0.5 to 30 parts by weight, per 100 parts by weight of said polyester (A), of said component (b-4);

wherein said styrene-acrylic copolymer (B) is comprised of 10 to 25% by weight of a high molecular weight polymer (B1) having a weight average molecular weight of 500,000 to 1,100,000 and 75 to 90% by weight of a low molecular weight polymer having a weight average molecular weight of 5,000 to 100,000, and has a glass transition temperature of 40°

to 68°

C., a softening point of 100°

to 160°

C. and an acid value of 0.1 to 10 mgKOH/g.

14. A process for preparing a toner resin composition comprising a linear polyester (A) a styrene-acrylic copolymer (B) wherein said styrene-acrylic copolymer (B) is comprised of 10 to 25% by weight of a high molecular weight polymer (B1) having a weight average molecular weight of 500,000 to 1,100,000 and 75 to 90% by weight of a low molecular weight polymer (B2) having a weight average molecular weight of 5,000 to 100,000, which process comprises of the steps of,

subjecting 10 to 25% by weight of a styrene component (b-1) and an acrylic ester and/or methacrylic ester component (b-2) to form an emulsion of a high molecular weight polymer (B1) having a weight average molecular weight of 500,000 to 1,100,000 to emulsion polymerization, and

adding, to the obtained emulsion, 5 to 40% by weight of a polyester (A) having a weight average molecular weight of 3,000 to 20,000 and at least a styrene component (b-1), an acrylic ester and/or methacrylic ester component (b-2), 0.3 to 3 parts by weight, per 100 parts of the total weight of said component (b-1) and component (b-2), of an α

-methyl styrene dimer (b-3) and 0.5 to 30 parts by weight, per 100 parts by weight of said polyester (A), of a glycidyl methacrylate component (b-4), and subjecting the mixture to suspension polymerization.

15. A process according to claim 14, wherein the emulsion polymerization is carried out in the presence of an emulsifier and a polymerization initiator.

16. A process according to claim 15, wherein the emulsifier is selected from nonionic and anionic hydrophilic emulsifiers and lipophilic emulsifiers.

17. A process according to claim 16, wherein the emulsifier is used in an amount of 0.2 to 4 parts by weight and the polymerization initiator is used in an amount of 0.1 to 0.4 part by weight, per 100 parts by weight of the total amounts of the component (b-1) and component (b-2).

18. A process according to claim 17, wherein the emulsion polymerization is carried out at a temperature of 65°

to 75°

C.

19. A process according to claim 15, wherein the emulsifier is selected from reactive surface active agents.

20. A process according to claim 19, wherein the emulsifier is used in an amount of 0.1 to 2 parts by weight and the polymerization initiator is used in an amount of 0.1 to 0.4 part by weight, per 100 parts by weight of the total amounts of the component (b-1) and component (b-2).

21. A process according to claim 20, wherein the emulsion polymerization is carried out at a temperature of 65°

to 75°

C.

22. A process according to claim 14, wherein the suspension polymerization is carried out in the presence of deionized water, a dispersant, a polymerization stabilizer and a polymerization initiator.

23. A process according to claim 16, wherein the dispersant is used in an amount of 0.05 to 1 part by weight and the polymerization initiator is used in an amount of 3 to 10 parts by weight, per 100 parts by weight of the total amounts of the component (b-1), component (b-4) and polyester (A).

24. A process according to claim 20, wherein the suspension polymerization is carried out at a temperature of 70°

to 98°

C.