Toner

• US 9,897,934 B2
• Filed: 12/08/2015
• Issued: 02/20/2018
• Est. Priority Date: 12/09/2014
• Status: Active Grant

• Current Assignee: Canon Ayutthaya Limited (Canon Inc.)
• Original Assignee: Canon Ayutthaya Limited (Canon Inc.)
• Inventors: Tamura, Junichi, Ida, Hayato, Shibata, Takaho, Chimoto, Yuya, Murayama, Ryuji
• Primary Examiner(s): Chapman, Mark A
• Application Number:
  US15/532,543
• Publication Number:
  US 20170363982A1
• Time in Patent Office: 805 Days
• Field of Search: 4301094, 4301101, 4301114
• CPC Class Codes: C08L 67/025 containing polyether sequences
• CPC Class Codes: G01R 33/46 NMR spectroscopy
• CPC Class Codes: G03G 9/0819 characterised by the dimensions of the particles
• CPC Class Codes: G03G 9/0821 characterised by physical parameters magnetic parameters G03G9/083
• CPC Class Codes: G03G 9/0825 characterised by their structure; characterised by non-homogenuous distribution of components microcapsular toners G03G9/093
• CPC Class Codes: G03G 9/0827 characterised by their shape, e.g. degree of sphericity
• CPC Class Codes: G03G 9/08755 Polyesters
• CPC Class Codes: G03G 9/08797 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature

Abstract

Provided is a toner that achieves low-temperature fixability, storability and charging performance all at a high level, in which a toner containing a crystalline resin and an amorphous resin, wherein a standard deviation of hydrogen nuclear relaxation times (HT1ρ-C) of the toner as measured by solid-state ¹³C-NMR is from 0.0 to 5.0, and a hydrogen nuclear relaxation time (HT1ρ-C1) of a ¹³C peak with the longest relaxation time out of the hydrogen nuclear relaxation times (HT1ρ-C) and a hydrogen nuclear relaxation time (HT1ρ-A1) of a ¹³C peak with the shortest relaxation time out of the hydrogen nuclear relaxation times (HT1ρ-A) satisfy 3.0≦{(HT1ρ-C1)/(HT1ρ-A1)}≦6.0.

Claims

1. A toner comprising a crystalline resin and an amorphous resin,

wherein

a standard deviation of hydrogen nuclear relaxation times (HT1ρ

-C) of the toner as measured by solid-state ¹³C-NMR is at least 0.0 and not more than 5.0, and

a hydrogen nuclear relaxation time (HT1ρ

-C1) of a ¹³C peak with the longest relaxation time out of the hydrogen nuclear relaxation times (HT1ρ

-C) and

a hydrogen nuclear relaxation time (HT1ρ

-A1) of a ¹³C peak with the shortest relaxation time out of hydrogen nuclear relaxation times (HT1ρ

-A)

satisfy the following Formula (1);

3.0≦

{(HT1ρ

-C1)/(HT1ρ

-A1)}≦

6.0 

 

(Formula

     1)

the hydrogen nuclear relaxation times (HT1ρ

-C) being obtained by solid-state ¹³C-NMR (CP/MAS) measurement of ¹³C peaks derived from the crystalline resin,

the ¹³C peaks derived from the crystalline resin being obtained by;

measuring the toner using solid-state ¹³C-NMR (DD/MAS),

arranging peak intensity of ¹³C peaks derived from the crystalline resin in descending order,

selecting ¹³C peaks starting with a ¹³C peak with the highest peak intensity and ending with a ¹³C peak at which the ratio of a cumulative value of the integral intensity of the ¹³C peak to a total value of the integral intensities of all ¹³C peaks reaches 90%,

while the hydrogen nuclear relaxation times (HT1ρ

-A) being obtained by solid-state ¹³C-NMR (CP/MAS) measurement of all of ¹³C peaks derived from the amorphous resin,

the ¹³C peaks derived from the amorphous resin being obtained by measuring the toner using solid-state ¹³C-NMR (DD/MAS).

2. The toner according to claim 1,

wherein

the crystalline resin is a resin obtained by condensation polymerization of a dicarboxylic acid component containing at least one of compound selected from the group consisting of dicarboxylic acids represented by Structural Formula I below and derivatives thereof with a diol component containing at least one of compound selected from the group consisting of diols represented by Structural Formula II below and derivatives thereof, and

the amorphous resin is a resin obtained by condensation polymerization of a dicarboxylic acid component containing at least one of compound selected from the group consisting of isophthalic acid, terephthalic acid and derivatives of these with a diol component in which at least one of compound selected from the group consisting of aromatic diols represented by Structural Formula III below and derivatives thereof constitutes at least 50 mol % to the total of the diol component:

3. The toner according to claim 2,

wherein

a standard deviation of hydrogen nuclear relaxation times (HT1ρ

-C) of a toner imparted with heat history as measured by solid-state ¹³C-NMR is at least 8.0 and not more than 12.0,

the toner imparted with heat history being obtained by heating and melting the toner at a temperature 50°

C. higher than the glass transition temperature of the toner, and then cooling the toner to 25°

C. at a rate of 20°

C./minute, and

a hydrogen nuclear relaxation time (HT1ρ

-C2) of a ¹³C peak with the shortest relaxation time out of the hydrogen nuclear relaxation times (HT1ρ

-C) and

a hydrogen nuclear relaxation time (HT1ρ

-A2) of a ¹³C peak with the longest relaxation time out of the hydrogen nuclear relaxation times (HT1ρ

-A)

satisfy the following Formula (2);

−

2.0 msec≦

{(HT1ρ

-C2)−

(HT1ρ

-A2)}≦

10.0 msec 

 

(Formula

     2)

the hydrogen nuclear relaxation times (HT1ρ

-C) being obtained by solid-state ¹³C-NMR (CP/MAS) measurement of ¹³C peaks derived from the crystalline resin,

the ¹³C peaks derived from the crystalline resin being obtained by;

measuring the toner imparted with heat history using solid-state ¹³C-NMR (DD/MAS),

arranging peak intensity of ¹³C peaks derived from the crystalline resin in descending order,

selecting ¹³C peaks starting with a ¹³C peak with the highest peak intensity and ending with a ¹³C peak at which the ratio of a cumulative value of the integral intensity of the ¹³C peak to a total value of the integral intensities of all ¹³C peaks reaches 90%,

while the hydrogen nuclear relaxation times (HT1ρ

-A) being obtained by solid-state ¹³C-NMR (CP/MAS) measurement of all of ¹³C peaks derived from the amorphous resin,

the ¹³C peaks derived from the amorphous resin being obtained by measuring the toner imparted with heat history using solid-state ¹³C-NMR (DD/MAS).

4. The toner according to claim 3,

wherein

the toner contains at least 10 mass % and not more than 40 mass % of the crystalline resin.

5. The toner according to claim 3,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

6. The toner according to claim 4,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

7. The toner according to claim 2,

wherein

the toner contains at least 10 mass % and not more than 40 mass % of the crystalline resin.

8. The toner according to claim 7,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

9. The toner according to claim 2,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

10. The toner according to claim 1,

wherein

a standard deviation of hydrogen nuclear relaxation times (HT1ρ

-C) of a toner imparted with heat history as measured by solid-state ¹³C-NMR is at least 8.0 and not more than 12.0,

the toner imparted with heat history being obtained by heating and melting the toner at a temperature 50°

C. higher than the glass transition temperature of the toner, and then cooling the toner to 25°

C. at a rate of 20°

C./minute, and

a hydrogen nuclear relaxation time (HT1ρ

-C2) of a ¹³C peak with the shortest relaxation time out of the hydrogen nuclear relaxation times (HT1ρ

-C) and

a hydrogen nuclear relaxation time (HT1ρ

-A2) of a ¹³C peak with the longest relaxation time out of the hydrogen nuclear relaxation times (HT1ρ

-A)

satisfy the following Formula (2);

−

2.0 msec≦

{(HT1ρ

-C2)−

(HT1ρ

-A2)}≦

10.0 msec 

 

(Formula

     2)

the hydrogen nuclear relaxation times (HT1ρ

-C) being obtained by solid-state ¹³C-NMR (CP/MAS) measurement of ¹³C peaks derived from the crystalline resin,

the ¹³C peaks derived from the crystalline resin being obtained by;

measuring the toner imparted with heat history using solid-state 13C-NMR (DD/MAS),

arranging peak intensity of ¹³C peaks derived from the crystalline resin in descending order,

selecting ¹³C peaks starting with a ¹³C peak with the highest peak intensity and ending with a ¹³C peak at which the ratio of a cumulative value of the integral intensity of the ¹³C peak to a total value of the integral intensities of all ¹³C peaks reaches 90%,

while the hydrogen nuclear relaxation times (HT1ρ

-A) being obtained by solid-state ¹³C-NMR (CP/MAS) measurement of all of ¹³C peaks derived from the amorphous resin,

the ¹³C peaks derived from the amorphous resin being obtained by measuring the toner imparted with heat history using solid-state ¹³C-NMR (DD/MAS).

11. The toner according to claim 10,

wherein

the toner contains at least 10 mass % and not more than 40 mass % of the crystalline resin.

12. The toner according to claim 11,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

13. The toner according to claim 10,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

14. The toner according to claim 1,

wherein

the toner contains at least 10 mass % and not more than 40 mass % of the crystalline resin.

15. The toner according to claim 14,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

16. The toner according to claim 1,

wherein

a melting point of the crystalline resin is at least 50°

C. and not more than 100°

C.

17. The toner according to claim 1,

wherein

the toner is manufactured by a manufacturing method comprising;

a compatibilization step of compatibilizing the crystalline resin and the amorphous resin to obtain a compatibilized blend, and

a solvent treatment step of treating the compatibilized blend with a good solvent for the amorphous resin and a poor solvent for the crystalline resin.

18. The toner according to claim 17,

wherein

the compatibilization step is

a step of heating the crystalline resin and the amorphous resin to equal to or above a melting point of the crystalline resin to compatibilize the crystalline resin and the amorphous resin and obtain a compatibilized blend, or

a step of dissolving the crystalline resin and the amorphous resin in an organic solvent capable of dissolving the crystalline resin and the amorphous resin to compatibilize the crystalline resin and the amorphous resin and obtain a compatibilized blend.

19. The toner according to claim 17,

wherein

the good solvent for the amorphous resin is a solvent in which the amorphous resin has a solubility of at least 100 g/L at the treatment temperature used in the solvent treatment step, and

the poor solvent for the crystalline resin is a solvent in which the crystalline resin has a solubility of less than 10 g/L at the treatment temperature used in the solvent treatment step.

20. The toner according to claim 17,

wherein

the toner satisfies the following (Formula 3):

0.00≦

{Wt/(Wr×

Z/100)}≦

0.50 

 

(Formula

     3)

Wt;

An amount of heat of fusion (J/g) derived from the crystalline resin during second temperature rise in measurement of the toner by differential scanning calorimeter (DSC)

Wr;

An amount of heat of fusion (J/g) during second temperature rise in measurement of the crystalline resin by differential scanning calorimeter (DSC)

Z;

A content ratio (mass %) of the crystalline resin in the toner.