JP6460904B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method or a toner jet method.

  In recent years, from the viewpoints of miniaturization and energy saving of electrophotographic apparatuses such as copiers and printers, there is a demand for toners that are excellent in low-temperature fixability and storage stability and can maintain excellent image quality over a long period of time.

  Various toners are being studied for that requirement. Patent Document 1 discloses a toner containing a crystalline polyester resin, two types of specific amorphous resins, and a composite resin including four or more types of binder resins including a condensation polymerization resin unit and an addition polymerization resin unit. Have been described. It is described that the toner has excellent low-temperature fixability and good storage stability.

  Patent Document 2 describes that a toner having excellent fixability and chargeability can be obtained by containing a cyclic phenol sulfide and an amorphous polyester resin having a softening point of 120 ° C. or higher as a binder resin.

  Patent Document 3 includes a binder resin including a non-crystalline polyester resin, a crystalline polyester resin, and a polyurethane-type thermoplastic elastomer, so that the low-temperature fixability is maintained and the bending resistance and the scratch resistance are improved. A method for obtaining an excellent toner is described.

JP 2013-76997 A JP 2010-60610 A JP 2013-160801 A

  However, as a result of the study by the present inventors, the toners described in Patent Documents 1 to 3 have room for improvement in terms of both low-temperature fixability and storage stability and maintaining long-term image stability. there were.

  An object of the present invention is to provide a toner that is excellent in low-temperature fixability and storage stability, and has little image defects such as fog in long-term use and use in a high-temperature and high-humidity environment or a low-temperature and low-humidity environment. is there.

The present invention is a toner having toner particles containing a styrene acrylic resin A, a polymer B having a structure b represented by the following formula (1), and a crystalline polyester resin C:
The styrene acrylic resin A contains 60% by mass or more of units derived from styrene monomers based on the units derived from all monomers constituting the styrene acrylic resin A.
The weight average molecular weight (Mw) of the polymer B is 1,000 or more and 100,000 or less,
The crystalline polyester resin C has a polyester moiety represented by the following formula (2),
The melting point of the crystalline polyester resin C is 55 ° C. or higher and 95 ° C. or lower,
The crystalline polyester resin C has a weight average molecular weight (Mw) of 8000 to 45,000.

(In Formula (1), R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms. F is an integer of 0 to 3 inclusive. Or when it is 3, R ¹ may be the same or different, * is the binding site in the polymer.)

(In the formula, m and n are each independently an integer of 4 or more and 16 or less.)

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and storage stability, and has less image defects such as fog when used for a long period of time and in a high-temperature and high-humidity environment or a low-temperature and low-humidity environment. it can.

  Hereinafter, the present invention will be described in detail.

  The toner of the present invention has toner particles containing a styrene acrylic resin A, a polymer B having a structure b represented by the following formula (1), and a crystalline polyester resin C. And the crystalline polyester resin C has the polyester site | part shown by following formula (2).

(In Formula (1), R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms. F is an integer of 0 to 3 inclusive. Or, when it is 3, R ¹ may be the same or different, * is a bonding site in the polymer, and when f is 0, it represents a hydrogen atom.)

(In formula (2), m and n are each independently an integer of 4 or more and 16 or less.)

  About the reason why the effect of the present invention is manifested when the toner of the present invention contains the specific styrene acrylic resin A, the polymer B having the structure b represented by the formula (1), and the specific crystalline polyester resin C. The present inventors consider as follows.

  The carboxy group or hydroxy group in the structure b of the polymer B having the structure b represented by the formula (1) interacts with the carboxy group of the dicarboxylic acid, which is the monomer material of the crystalline polyester resin C, or the hydroxy group of the diol. it seems to do. In this state, it is considered that the polymer B functions as a dispersant for the crystalline polyester resin C in the toner. One of the factors is that the benzene ring in the structure b of the polymer B and the benzene ring derived from styrene of the styrene acrylic resin A interact with each other by π-π interaction. That is, this is because the structure b of the polymer B having an affinity for the benzene ring in the styrene acrylic resin A acts so as to mediate the styrene acrylic resin A and the crystalline polyester resin C.

  By such an action, the crystalline polyester resin C can be distributed in a moderately stable state in the toner, so that the dispersed particle size of the crystalline polyester resin C can be distributed in a small state. Thereby, when the crystalline polyester resin C and the styrene acrylic resin A are rapidly melted and compatible at the time of fixing, the melt viscosity is lowered, the fixing property is improved, and the low temperature fixing property and the storage stability are improved. Conceivable.

  Further, the crystalline polyester resin C may be a block polymer (vinyl-modified resin) having a polyester moiety and a vinyl polymer moiety represented by the above formula (2). In this case, since the benzene ring in the vinyl polymer site and the benzene ring derived from styrene of the styrene acrylic resin A also interact with each other, the affinity can be further increased.

  From the viewpoint of achieving both low temperature fixability and storage stability of the toner, the styrene acrylic resin A has 60 mass units derived from the styrene monomer based on the units derived from all monomers constituting the styrene acrylic resin A. % Or more. Preferably, the unit derived from the styrene monomer is 70% by mass or more.

  When the unit derived from the styrene monomer is 60% by mass or more, a π-π interaction occurs between the benzene ring in the structure b or the benzene ring in the vinyl polymer portion of the block polymer and the benzene ring derived from the styrene of the styrene acrylic resin A. Is expressed. Thereby, the dispersibility of the crystalline polyester resin C in the toner becomes good, and the low-temperature fixability and the storage stability become good.

  From the viewpoint of storage stability, the polymer B has a weight average molecular weight (Mw) of 1,000 or more and 100,000 or less. Preferably, it is 4000 or more and 50000 or less. When the weight average molecular weight of the polymer B is 1000 or more, the number of molecules containing the structure b in one molecule of the polymer B increases, so that the interaction with the crystalline polyester resin C is likely to occur, and fixing. Sexuality improves. Further, if the weight average molecular weight of the polymer B is 100,000 or less, the fixing property and the compatibility with the resin components (styrene acrylic resin A and crystalline polyester resin C) of the toner particles are sufficient, and the fixing property is improved. In particular, when toner particles are produced in an aqueous medium, the distribution of each raw material in the toner becomes uniform, which is desirable in terms of image density and chargeability.

  From the viewpoint of low-temperature fixability and storage stability, the crystalline polyester resin C has a weight average molecular weight (Mw) of 8000 to 45,000. Preferably, the weight average molecular weight (Mw) is 8000 or more and 40000 or less. When the weight average molecular weight of the crystalline polyester resin C is 8000 or more, crystallinity is exhibited and storage stability is improved. Further, if it is 45000 or less, the crystalline polyester resin C is appropriately dispersed in the toner, the crystalline polyester resin C and the styrene acrylic resin A are compatible with each other at the time of fixing, and the melt viscosity is sufficiently lowered to improve the fixing property. Turn into. The weight average molecular weight of the crystalline polyester resin C can be controlled by various production conditions such as the condensation reaction time in the production of the crystalline polyester resin C. The method for measuring the weight average molecular weight of the crystalline polyester resin C will be described later.

  When the crystalline polyester resin C has a polyester moiety represented by the above formula (2), the crystalline polyester resin C is excellent in crystallinity and has an appropriate crystal melting point, so that it has excellent storage stability and low-temperature fixability. . In addition, if either of the values of m and n in the above formula (2) is 3 or less, the melting point (Tm) is low, which is not desirable in terms of storage stability. Further, if the value of m or n in the formula (2) is 17 or more, the melting point (Tm) is high, which is not desirable in terms of low-temperature fixability.

  From the above, the melting point of the crystalline polyester resin C is 55 ° C. or higher and 95 ° C. or lower. Preferably, it is 60 degreeC or more and 85 degrees C or less. When the temperature is lower than 55 ° C., toner blocking (fusing of toners) hardly occurs, and the storage stability is not sufficient. On the other hand, if the melting point is higher than 95 ° C., the low-temperature fixability is not sufficient.

(Polymer B)
The polymer B of the present invention has a structure b represented by the above formula (1).

  The structure b represented by the formula (1) is more preferably a structure represented by the following formula (3).

(In formula (3), R ² represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms. R ³ represents a hydrogen atom, a hydroxy group, or 1 to 18 carbon atoms. The following alkyl groups or alkoxyl groups having 1 to 18 carbon atoms are shown: g is an integer of 1 to 3 and h is an integer of 0 to 3. When h is 2 or 3, R ² may be the same or different, * is a bonding site in the polymer, and when h is 0, it represents a hydrogen atom.)

Polymer B, by having a structure represented by the formula (3), Equation (3) in the - (CH 2) site and the affinity of the crystalline polyester resin (C) of the _g- increases, crystallinity It is considered that the dispersibility of the polyester resin is improved and the fixing property is further improved.

  Furthermore, when producing toner particles in an aqueous medium, the carboxy group or hydroxy group in structure b is coordinated to the carboxy group of dicarboxylic acid, which is the monomer material of the crystalline polyester resin C, or the hydroxy group of diol. As a result, the polarity of the crystalline polyester resin C decreases. This is because the carboxy group and hydroxy group are not exposed. As a result, it is desirable because the toner exhibits more excellent performance in terms of storage stability and chargeability.

  The polymer B is more preferably a polymer having a site represented by the following formula (4).

(In formula (4), R ⁴ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms. R ⁵ represents a hydrogen atom, a hydroxy group, or 1 to 18 carbon atoms. The following alkyl groups or alkoxyl groups having 1 to 18 carbon atoms are shown: R ⁶ represents a hydrogen atom or a methyl group, i is an integer of 1 to 3, and j is 0 or more (It is an integer of 3 or less. When j is 2 or 3, R ⁴ may be the same or different. When j is 0, it represents a hydrogen atom.)

When the polymer has a structure (site) represented by the above formulas (3) and (4), the π-π interaction with the styrene-derived benzene ring of the styrene acrylic resin A becomes stronger. This is because the benzene ring connected to the salicylic acid moiety via — (CH ₂ ) g-(— (CH ₂ ) i—) in addition to the benzene ring at the salicylic acid moiety of the polymer B is derived from styrene of the styrene acrylic resin A. This is because π-π interacts with the benzene ring. _{Also, - (CH 2) g -} (- (CH 2) i-) unit for become appropriate spacer, can not occur, such as steric hindrance, the interaction of styrene from benzene ring of the styrene-acrylic resin A is It is thought that it occurs efficiently.

  Furthermore, at the site represented by the formula (4), the main chain is a vinyl main chain, so that the toner particles having a vinyl resin such as a styrene acrylic resin are easily compatible with each other and have low temperature fixability. Tends to be good.

  The polymer B having the structure b is obtained by copolymerizing a polymerizable monomer derived from the structure represented by the formula (1) or (3) and another polymerizable monomer.

  Specific examples of the polymerizable monomer that can be used as the copolymer include the following. Styrene; α-methyl styrene, β-methyl styrene, o-methyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl Styrene derivatives such as styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate , Iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate Acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, acrylic polymerizable monomers such as 2-benzoyloxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso- Propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl Examples include methacrylic polymerizable monomers such as phosphate ethyl methacrylate.

  Specific examples of the polymerizable monomer derived from the structure represented by the formula (1) or (3) include the following. 3-vinylsalicylic acid, 4-vinylsalicylic acid, 5-vinylsalicylic acid, 6-vinylsalicylic acid, 3-vinyl-5-isopropylsalicylic acid, 3-vinyl-5-t-butylsalicylic acid, 4-vinyl-6-t- Examples include butylsalicylic acid, 3-isopropenyl-5-t-butylsalicylic acid, and the like. Moreover, the following can be mentioned as a specific example of the polymerizable monomer derived from the structure shown by Formula (1).

  The content ratio of the structure b to the polymer (B) is preferably 10 μmol / g or more and 1500 μmol / g or less. When the structure b is contained in the above range, the effect of the present invention is easily exhibited, and the fixing property and the storage stability are improved.

  The content ratio of the structure b to the toner is preferably 0.10 μmol / g or more and 200.0 μmol / g or less. When the structure b is contained in the above range, the interaction with the styrene acrylic resin A and the crystalline polyester resin C becomes moderate, and the polymer B containing the structure b is uniformly present in the toner, so that the storage stability is improved. It becomes good.

  Further, when the toner particles are produced in an aqueous medium, the acid value of the polymer B is preferably 3.0 mgKOH / g or more and 35.0 mgKOH / g or less. When the acid value of the polymer B is in the above range, the interaction with the crystalline polyester resin C is likely to be exerted strongly, and the polymer B and the crystalline polyester resin C are less likely to be distributed on the aqueous medium side. This makes it difficult to expose the toner surface.

  The molecular weight distribution of the polymer B is preferably narrow. The ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn calculated by gel permeation chromatography is preferably 1.0 or more and 6.0 or less. More preferably, it is 1.0 or more and 4.0 or less.

<Molecular weight and molecular weight distribution of the polymer (B)>
The molecular weight and molecular weight distribution of the polymer B are calculated in terms of polystyrene by gel permeation chromatography (GPC). When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group. Therefore, it is necessary to prepare a sample in which the acid group is capped in advance. Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.

The molecular weight is measured by GPC as follows. First, a measurement sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

  In calculating the molecular weight of the measurement sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F −10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ”manufactured by Tosoh Corporation) are used.

(Crystalline polyester C)
The toner of the present invention contains a crystalline polyester resin C in order to improve the low-temperature fixability. “Crystallinity” means having a clear endothermic peak in the differential scanning calorimetry (DSC) measurement described below. On the other hand, a resin that does not have a clear endothermic peak means amorphous.

The crystalline polyester resin C has a polyester moiety represented by the above formula (2), and this polyester moiety is obtained by polycondensation of an aliphatic dicarboxylic acid and an aliphatic diol. Specifically, the aliphatic dicarboxylic acid and the aliphatic diol are a linear aliphatic dicarboxylic acid represented by the following formula (5) and a linear aliphatic diol represented by the following formula (6).
_{HOOC- (CH 2) p -COOH ···} (5)
(In Formula (5), p is an integer of 4 or more and 16 or less.)
HO— (CH ₂ ) _q —OH (6)
(In formula (6), q is an integer of 4 or more and 16 or less.)

  As described above, the melting point of the crystalline polyester resin C is 55 ° C. or higher and 90 ° C. or lower. The melting point of the crystalline polyester resin C can be adjusted by the type, blending ratio, degree of polymerization, ester group concentration, etc. of the aliphatic dicarboxylic acid or aliphatic diol used.

  The polyester portion of the crystalline polyester resin C more preferably has a unit represented by the following formula (7) and a unit represented by the following formula (8). Such a polyester part is obtained by polycondensing a dicarboxylic acid represented by the following formula (9) and a diol represented by the following formulas (10) and (11).

(In formulas (7) and (8), p is an integer of 4 or more and 14 or less. Q is an integer of 4 or more and less than r. R is an integer of q or more and 16 or less.)
_{HOOC- (CH 2) p -COOH ···} (9)
(In the formula, p is an integer of 4 or more and 14 or less.)
HO— (CH ₂ ) _q —OH (10)
(In the formula, q is an integer of 4 or more and less than r.)
HO— (CH ₂ ) _r —OH (11)
(In the formula, r is an integer from q to 16)

  As described above, when two kinds of diol components are used as the constituent components of the crystalline polyester resin C, the crystallinity is high and the hydrophobicity is appropriately high as compared with the case where one kind of diol component is used. Therefore, it is more preferable in terms of storage stability, fusion to a toner layer regulating member or toner carrier, and charging properties.

  In terms of crystallinity of the crystalline polyester resin C, the content of the aliphatic dicarboxylic acid in the polycarboxylic acid component is preferably 80 mol% or more, more preferably 90 mol% or more, and more preferably 100 mol. % Is more preferable. Further, in terms of crystallinity of the crystalline polyester, the content of the aliphatic diol component in the polyol component is preferably 80 mol% or more, more preferably 90 mol% or more, and 100 mol%. More preferably it is. If necessary, a monovalent acid such as acetic acid or benzoic acid or a monovalent alcohol such as cyclohexanol benzyl alcohol can be used for the purpose of adjusting the acid value or the hydroxyl value.

  The crystalline polyester resin C can be produced by a normal polyester synthesis method. For example, it can be obtained by subjecting a dicarboxylic acid component and a diol component to an esterification reaction or a transesterification reaction, and then subjecting the dicarboxylic acid component and a diol component to a polycondensation reaction according to a conventional method under reduced pressure or by introducing nitrogen gas.

  Moreover, it is possible to control the acid value of the crystalline polyester resin C by sealing the carboxy group of the polymer terminal. Monocarboxylic acid and monoalcohol can be used for end-capping.

  The crystalline polyester resin C may also be a copolymer (hybrid crystalline polyester) obtained by copolymerizing (modifying) other components at a ratio of 60% by weight or less with respect to the polyester portion.

  Further, the crystalline polyester resin C is preferably a block polymer having a polyester moiety represented by the above formula (2) and a vinyl polymer moiety. In this block polymer, the weight average molecular weight (Mw) of the vinyl polymer portion is preferably 4000 or more and 15000 or less. When the Mw is 4000 or more and 15000 or less, the surface exposure of the crystalline polyester resin C is suppressed due to the interaction between the styrene acrylic resin A and the polymer B, which is preferable in terms of heat resistant storage stability. The weight average molecular weight (Mw) of the vinyl polymer portion can be controlled by the production conditions such as the amount of both reactive monomers added during the production of the crystalline polyester resin C, the vinyl monomer polymerization reaction time, the amount of initiator, and the reaction temperature. In addition, the measuring method of the weight average molecular weight (Mw) of a vinyl polymer site | part is mentioned later.

  From the viewpoint of chargeability, the acid value of the crystalline polyester resin C is preferably 5.0 mgKOH / g or less. The acid value of the crystalline polyester resin C can be controlled by the ratio between the alcohol component and the acid component constituting the crystalline polyester resin C, the type of monomer, and the end group treatment of the crystalline polyester resin C. The method for measuring the acid value of the crystalline polyester resin C will be described later.

  As a method for producing the polyester portion of the block polymer, for example, there is a method of introducing reactive functional groups at both ends of the polymer. Specifically, an initiator that can give methyl carboxylate to both ends of the polymer is used when producing the vinyl polymer portion. Using the introduced functional group as a reactive base point, a polyester site is prepared in the presence of a catalyst. Alternatively, after preparing the polyester portion, a reactive material such as bromo is introduced into the polymer terminal. Thereafter, a vinyl polymer site is prepared starting from the introduction group. Furthermore, when producing a vinyl polymer site | part, the method of advancing a polymerization reaction under a pressurized environment is also mentioned. Specifically, the following methods are mentioned. Transesterification reaction between a hydroxy group contained in a polyester moiety and a (meth) acrylic acid ester contained in a vinyl polymer moiety. Esterification reaction between a hydroxy group contained in a polyester moiety and a carboxy group contained in a vinyl polymer moiety. Esterification reaction between a carboxy group contained in polyester and a hydroxy group contained in a vinyl polymer moiety. Examples include a method in which radicals are generated in a polyester site by a hydrogen abstraction reaction, a vinyl monomer is added, and polymerization is performed in a pressurized environment. At that time, the degree of pressurization is preferably 0.20 MPa or more and 0.45 MPa or less.

  A known monofunctional polymerizable monomer or polyfunctional polymerizable monomer can be used as the vinyl monomer used for producing the vinyl polymer portion of the block polymer. Examples of the monofunctional polymerizable monomer include styrene, an acrylic polymerizable monomer, and a methacrylic polymerizable monomer obtained by changing the acrylic polymerizable monomer to methacrylate.

  An oil-soluble initiator and / or a water-soluble initiator can be appropriately used as the polymerization initiator used for polymerizing the polymerizable monomer described above when producing the block polymer. For example, examples of the oil-soluble initiator include azo compounds and peroxides. In particular, it is preferably a peroxide, and when the polyester resin is vinyl-modified by a hydrogen abstraction reaction, the 10-hour half-life temperature is preferably 70 ° C. or higher and 170 ° C. or lower, and 75 ° C. or higher and 130 ° C. or lower is used. It is more preferable because it has moderate reactivity.

  The content of the crystalline polyester resin C with respect to the styrene acrylic resin A is preferably 2.0% by mass or more and 40.0% by mass or less. More preferably, it is 3.0 mass% or more and 25.0 mass% or less. When the content is 2.0% by mass or more and 40.0% by mass or less, the low-temperature fixability is further improved and offset is less likely to occur.

In the toner of the present invention, the solubility parameter (SP value) of the polymer B is D ((cal / cm ³ ) ^1/2 ), and the SP value of the crystalline polyester resin C is E ((cal / cm ³ ) ^1/2. ), The absolute value of the difference between D and E is preferably 0.10 or more and 1.00 or less. This is because when the absolute value of the difference between D and E is 0.10 or more and 1.00 or less, the difference in SP value is small, the affinity between the crystalline polyester resin C and the polymer B is high, and the phase at the time of fixing is high. Large melting effect. Thereby, the fixing property is improved.

  Further, the SP value D of the crystalline polyester resin C is preferably 9.40 or more and 9.85 or less. The higher the SP value, the higher the hydrophilicity of the crystalline polyester resin. Therefore, when the D of the crystalline polyester resin C is 9.40 or more and 9.85 or less, the degree of hydrophilicity becomes appropriate, and the influence of humidity is moderate. In particular, when toner particles are produced in an aqueous medium, the distribution of the crystalline polyester resin C in the toner particles is optimized, which is desirable in terms of storage stability, fixability, and chargeability. Furthermore, it is desirable because contamination to the member is suppressed. In order to make the SP value 9.40 or more and 9.85 or less, the type of diol component and dicarboxylic acid component in the polyester part, the mixing ratio, the mass ratio of the polyester part and vinyl polymer part, the type of vinyl monomer are adjusted. It can be controlled by doing.

<SP value calculation method>
The SP value in the present invention was determined using the Fedors equation (3). The values of Δei and Δvi here are the “Basic Science of Coating”, pages 54 to 57, and the evaporation energy and molar volume (25 ° C.) of atoms and atomic groups according to Tables 3 to 9 of 1986 (Tsubaki Shoten). I referred to it.
δi = [Ev / V] ^1/2 = [Δei / Δvi] ^1/2 formula (3)
Ev: Evaporation energy V: Molar volume Δei: Evaporation energy of atom or atomic group of i component Δvi: Molar volume of atom or atomic group of i component For example, hexanediol is atomic group (—OH) × 2 + (— CH 2) It is comprised from * 6 and calculation SP value is calculated | required by a following formula.

δi = [Δei / Δvi] ^1/2 = [{(5220) × 2 + (1180) × 6} / {(13) × 2 + (16.1) × 6}] ^1/2
The SP value (δi) is 11.95.

  The block polymer of the present invention preferably has a mass-based ratio of the polyester portion represented by the formula (2) of the block polymer and the vinyl polymer portion of 40/60 or more and 80/20 or less. Within this range, the fixability is good.

  It is preferable that the weight average molecular weight (Mw) of the block polymer of this invention is 15000 or more and 45000 or less. Within this range, the low-temperature fixability and storage stability are good.

(Styrene acrylic resin A)
The styrene acrylic resin A contains 60% by mass or more of units derived from styrene monomers based on units derived from all monomers. As described above, the ratio of the styrene monomer unit of the styrene acrylic resin A is calculated using ¹ H-NMR and ¹³ C-NMR.

  The styrene acrylic resin A is desirably 50% by mass or more based on the total mass of the styrene acrylic resin A and the crystalline polyester resin C.

  As the styrene acrylic resin A, a known resin can be used. Specific examples include styrene-methacrylic acid copolymers and styrene-acrylic acid copolymers.

  When obtaining toner particles using the suspension polymerization method, styrene acrylic resin A is prepared by copolymerizing styrene and (meth) acrylic acid as a polymerizable monomer during the suspension polymerization reaction. It doesn't matter.

  Specific examples of the polymerizable monomer that can be used are as follows. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- styrene derivatives such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n -Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-buty methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, Diethyl phosphate ethyl methacrylate, dibutyl phosphate Such methacrylic polymerizable monomers of methacrylate.

  When the polymerizable monomer used for the styrene acrylic resin A and the polymer B is copolymerized, various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used. Things can be used. Examples of the peroxide polymerization initiator that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other examples include t-butyl peroxyallyl monocarbonate and the like. It is. Examples of the azo polymerization initiator that can be used include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate), etc. Illustrated.

  If necessary, two or more of these polymerization initiators can be used simultaneously. The amount of the polymerization initiator used at this time is preferably 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the polymerizable monomer. As the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be used, and it is not particularly limited.

<Measurement of Content of Structure b of Polymer B>
The content (μmol / g) of the structure b represented by the formula (1) in the polymer B is determined based on the amount of the hydroxyl group (hydroxy group) derived from the structure b of the polymer by quantifying the hydroxyl value. The content (μmol / g) of structure b in the polymer is calculated.

In the case where the polymer B has a hydroxyl group at a site other than the structure b, the hydroxyl value of the compound (for example, polyester resin) immediately before the structure b is subjected to addition reaction when the polymer is prepared is measured in advance. deep. The addition amount of structure (b) can be calculated by the difference from the hydroxyl value of the polymer after the addition reaction.
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Add 25.0 g of special grade acetic anhydride to a 100 mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Titration is performed using a 1.0 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.). 100 mL of 1.0 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with a potassium hydroxide solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 1.0 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

  The measurement conditions for the hydroxyl value measurement are shown below.

Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview

The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration mode: Total titration Maximum titration: 80 mL
Waiting time before titration: 30 seconds Titration direction: Automatic Control parameter End point determination potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.5 mL
main exam;

2.00 g of the measurement sample of the pulverized polymer B is precisely weighed in a 200 mL round bottom flask, and 5.00 mL of the acetylating reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.
Place a small funnel in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole. After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1.00 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5.00 mL of ethyl alcohol. The obtained sample is transferred to a 250 mL tall beaker, and 100 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Using the potentiometric titrator, titration is performed using a potassium hydroxide ethyl alcohol solution.

Blank test;
A titration similar to the above operation is performed except that the measurement sample sample of the polymer B is not used.

The obtained results are substituted into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A is the hydroxyl value (mgKOH / g), B is the addition amount (mL) of the potassium hydroxide solution of the blank test, C is the addition amount (mL) of the potassium hydroxide solution of the test, and f is potassium hydroxide. The factor of the solution, S is a measurement sample sample (g) of the polymer B, and D is the acid value (mgKOH / g) of the polymer B.

<Measurement of Acid Values of Polymer B and Crystalline Polyester Resin C>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with a potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As 0.100 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

  The measurement conditions for the acid value measurement are shown below.

Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview

The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration mode: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic Control parameter End point judgment potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL

main exam;
A sample sample (polymer B or crystalline polyester resin C) (0.100 g) is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Using the potentiometric titrator, titration is performed using a potassium hydroxide ethyl alcohol solution.

Blank test;
Titration similar to the above operation is performed except that the sample sample of polymer B or crystalline polyester resin C is not used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A is the acid value (mgKOH / g), B is the addition amount (mL) of the potassium hydroxide solution in the blank test, C is the addition amount (mL) of the potassium hydroxide solution in the test, and f is potassium hydroxide. The factor of the solution, S, indicates the sample sample (g).

<Structural analysis of polymer B, styrene acrylic resin A and crystalline polyester resin C>
The structure determination of each polymerizable monomer of the polymer B, the styrene acrylic resin A, and the crystalline polyester resin C is performed using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum. be able to. The apparatus used below will be described. Each resin sample may be collected from the toner and analyzed.
(I) ¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)
(Ii) FT-IR spectrum Thermo Fisher Scientific Inc. Made AVATAR360FT-IR

<Weight average molecular weight and number average molecular weight of crystalline polyester resin>
After 0.03 g of crystalline polyester is dispersed in 10 ml of o-dichlorobenzene and dissolved, the mixture is shaken with a shaker at 135 ° C. for 24 hours, filtered through a 0.2 μm filter, and the filtrate is used as a sample. Analyze under conditions.

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71

  In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

<Weight Average Molecular Weight of Vinyl Polymer Part in Crystalline Polyester Resin C>
The molecular weight of the vinyl polymer portion in the crystalline polyester resin C is measured by hydrolyzing the polyester portion of the crystalline polyester resin C. Specifically, 5 ml of dioxane and 1 ml of a 10% by weight aqueous potassium hydroxide solution are added to 30 mg of crystalline polyester resin C, and the polyester part is hydrolyzed by shaking at a temperature of 70 ° C. for 6 hours. Thereafter, the solution is dried to prepare a sample for measuring the molecular weight of the vinyl polymer site.

  0.03 g of the sample for measurement was dispersed in 10 ml of o-dichlorobenzene and dissolved, then shaken with a shaker at 135 ° C. for 24 hours, filtered with a 0.2 μm filter, and the filtrate was used as a sample. Perform analysis at

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene Mobile phase flow rate: 1.0 ml / min.
Sample concentration: 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71

  In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

<Measurement of ratio of polyester part and vinyl polymer part of crystalline polyester resin>
The mass ratio of the polyester part and the vinyl polymer part of the crystalline polyester resin is determined using nuclear magnetic resonance spectroscopy (1H-NMR) [400 MHz, CDC13, room temperature (25 ° C.)]. From the integral value of the obtained spectrum, the mass ratio of the polyester part to the vinyl polymer part (is calculated.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times

<Melting point Tm of crystalline polyester resin C>
The melting point (Tm) of the crystalline polyester resin C is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, 5 mg of the crystalline polyester resin C is precisely weighed, put in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature is raised within a measurement temperature range of 30 to 200 ° C. Measurement is performed at a temperature rate of 10 ° C./min. In the measurement, the temperature is once raised to 200 ° C., then cooled to 30 ° C. at a temperature lowering rate of 10 ° C./min, and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point (Tm) in the DSC measurement of the crystalline polyester resin C.

  The toner of the present invention may further contain a wax. In that case, at least one of the waxes preferably has a melting point (a temperature corresponding to the maximum endothermic peak of the DSC endothermic curve in the temperature range of 20 to 200 ° C.) of 30 ° C. or more and 120 ° C. or less, and 60 ° C. or more and 100 ° C. The following is more preferable. Further, it is preferably a wax that is solid at room temperature, and in particular, a solid wax having a melting point of 60 ° C. or higher and 100 ° C. or lower is preferable from the viewpoint of toner blocking resistance, multi-sheet durability, low-temperature fixability, and offset resistance.

  Examples of the wax include paraffin wax, polyolefin wax, polymethylene wax such as microcrystalline wax and Fischer-Tropsch wax, petroleum wax such as amide wax and petrolatum and derivatives thereof, montan wax and derivatives thereof, carnauba wax and candelilla wax. Use of known waxes such as natural waxes and derivatives thereof, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, higher fatty acids, long chain alcohols, ester waxes, ketone waxes and derivatives thereof such as graft compounds and block compounds Is possible. These can be used alone or in combination.

  The content of the wax in the toner is preferably 3 parts by mass or more and 30 parts by mass or less, and preferably 4 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the binder resin (the total of the styrene acrylic resin A and the crystalline polyester resin C). Part or less is more preferable. When the wax content is within this range, the effect of preventing offset is not lowered, the anti-blocking effect is not lowered, and the anti-offset effect is hardly adversely affected.

  A known charge control agent can be used for the toner of the present invention. The content of the charge control agent is preferably 0.01 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin (the total of the styrene acrylic resin A and the crystalline polyester resin C). More preferably, they are 5 to 10 mass parts.

  The toner of the present invention contains a pigment as a colorant. As a pigment used for a cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, and a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3 and 15: 4.

  As the pigment used for the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds can be used. Specific examples include the following. C. I. Pigment violet 19, C.I. I. Pigment Red 31, 122, 150 and 269.

  As the pigment used for the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds can be used. Specific examples include the following. C. I. Pigment Yellow 74, 93, 120, 151, 155, 180 and 185.

  As the black colorant, carbon black, a magnetic material, and a color tone adjusted to black using the yellow, magenta, and cyan colorants can be used.

  The addition amount of these pigments is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

  An external additive may be added to the toner particles in order to impart various properties to the toner. Examples of the external additive for improving the fluidity of the toner include inorganic fine particles such as silica fine particles, titanium oxide fine particles, and double oxide fine particles thereof.

  Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, wet silica produced from water glass, and sol-gel silica produced by a sol-gel method. The dry silica may be composite fine particles of silica and another metal oxide by using a metal halogen compound such as aluminum chloride, titanium chloride or the like together with a silicon halogen compound in the production process.

  Since the surface of inorganic fine particles can be hydrophobized with a treatment agent, adjustment of the triboelectric charge amount of toner, improvement of environmental stability, and improvement of fluidity under high temperature and high humidity can be achieved. It is preferable to use inorganic fine particles that have been hydrophobized.

  Treatment agents for hydrophobizing inorganic fine particles include unmodified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and And organic titanium compounds. Of these, silicone oil is preferred. These treatment agents may be used alone or in combination.

  The amount of the external additive added is preferably 0.5 parts by mass or more and 5.0 parts by mass or less, more preferably 1.0 parts by mass with respect to 100.0 parts by mass of the toner particles before the external additive is processed. It is not less than 2.5 parts by mass.

  The weight average particle diameter (D4) of the toner is preferably 4.0 μm or more and 12.0 μm or less, and more preferably 4.0 μm or more and 9.0 μm or less.

<Weight average particle diameter (D4) and number average particle diameter (D1) of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water so as to have a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

Prior to measurement and analysis, the dedicated software is set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked. In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Put 200 mL of the aqueous electrolytic solution into a 250 mL round bottom beaker made exclusively for Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 mL of the electrolytic aqueous solution into a glass 100 mL flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.3 mL of a diluted solution obtained by diluting 3) with ion-exchanged water.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank. (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and number average particle diameter (D1), volume-based median diameter, and number-based median diameter are calculated. When the graph / volume% is set by the dedicated software, the “average diameter” on the “analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the “median diameter” is The volume-based median diameter (Dv50). In addition, when the graph / number% is set with the dedicated software, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1), and the “median diameter” is This is the number-based median diameter (Dn50).

<Glass transition temperature (Tg) of toner>
The glass transition temperature (Tg) of the toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, 5 mg of toner is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and a modulation measurement is performed at a measurement range of 20 ° C. to 140 ° C. with the following settings. Do.
Temperature rising rate 1 ° C / min
Amplitude temperature range ± 0.318 ° C / min

  In this temperature raising process, a specific heat change is obtained in the temperature range of 20 ° C to 140 ° C. The glass transition temperature Tg of the toner is defined as an intersection point between the baseline intermediate line and the differential heat curve before and after the specific heat change of the reversible specific heat change curve. The maximum endothermic peak temperature in the specific heat change curve is the melting point of the crystalline material contained in the toner. In order to identify the endothermic peak of the crystalline polyester resin (C), the crystalline polyester resin (C) may be separated from the toner using preparative GPC or the like.

  Next, a method for producing the toner of the present invention will be described. Examples of the method for producing the toner of the present invention include a pulverization method, suspension polymerization method, dispersion polymerization method, dissolution suspension method, and emulsion aggregation method. In particular, since the production process is simple and the desired toner can be easily obtained, it is preferable to produce the toner by suspension polymerization. Compared with the pulverization method, it is preferable because exposure of the wax to the toner surface is suppressed, and a toner having excellent image quality can be obtained.

  The toner production method by the suspension polymerization method is as follows, for example. The above-mentioned polymerizable monomer for producing the styrene acrylic resin A, the crystalline polyester resin C, the polymer B, and, if necessary, a colorant, wax, and other additives, a homogenizer, a ball mill, an ultrasonic dispersion It is dissolved or dispersed uniformly by a dispersing machine such as a machine. A polymerization initiator is dissolved in this, and a polymerizable monomer composition is prepared. Next, toner particles are manufactured by suspending the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer and performing polymerization.

  The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Further, immediately after granulation, a polymerization initiator dissolved in a polymerizable monomer or solvent may be added before starting the polymerization reaction.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, all parts and% are based on mass unless otherwise specified.

<Production example of polymerizable monomer M-1>
The polymerizable monomer (M-1) described in Table 1 was obtained as follows.

  Dissolve 100.0 g of 2,5-dihydroxybenzoic acid in 2 L of methanol, add 88.3 g of potassium carbonate, and heat to 67 ° C. To this solution, 102.0 g of 4- (chloromethyl) styrene is dropped over 22 minutes, and the mixture is reacted at 67 ° C. for 12 hours. The resulting reaction solution is cooled, methanol is distilled off under reduced pressure, and washed with hexane. The residue is dissolved in methanol, dropped into water, reprecipitated, and the precipitate is filtered. This reprecipitation operation was repeated twice, and the residue was dried at 80 ° C. to obtain a polymerizable monomer M-1 shown in Table 1.

<Production example of polymerizable monomer M-3>
100.0 g of 2,5-dihydroxybenzoic acid and 1441.0 g of 80% sulfuric acid are mixed while heating to 50 ° C., and 144.0 g of tert-butyl alcohol is added to the mixture, followed by stirring at 50 ° C. for 30 minutes. Next, an operation of adding 144.0 g of tert-butyl alcohol to the mixed solution and stirring for 30 minutes at 50 ° C. is performed three times. After cooling the reaction solution to room temperature, it is gradually poured into 1.0 kg of ice water and the precipitate is filtered. The precipitate is washed with water and further washed with hexane. The precipitate obtained here is dissolved in 200 mL of methanol and reprecipitated using 3.6 L of water. After filtration, it is dried at 80 ° C. to obtain 74.9 g of a salicylic acid intermediate represented by the following formula (10).

  25.0 g of the salicylic acid intermediate represented by the above formula (10) is dissolved in 150 mL of methanol. To this solution, 36.9 g of potassium carbonate is added and heated to 65 ° C. A solution obtained by mixing and dissolving 18.7 g of 4- (chloromethyl) styrene and 100 mL of methanol is prepared, and this solution is dropped into a solution containing a salicylic acid intermediate and reacted at 65 ° C. for 3 hours. The obtained reaction solution is cooled and then filtered, and methanol in the filtrate is distilled off under reduced pressure to obtain a precipitate. The precipitate is dispersed in 1.5 L of water at pH = 2, and extracted with ethyl acetate. Thereafter, it is washed with water, dried over magnesium sulfate, and ethyl acetate is distilled off under reduced pressure to obtain a precipitate. The precipitate is washed with hexane and then recrystallized with toluene / ethyl acetate to obtain 20.1 g of a polymerizable monomer M-3 shown in Table 1.

<Synthesis example of polymerizable monomer M-2, M-4 to 7>
The polymerizable monomers listed in Table 1 in the same manner as the synthesis of monomer M-3 (Step 2) except that 2,5-dihydroxybenzoic acid and 4- (chloromethyl) styrene are appropriately changed. The bodies M-2 and M-4 to 7 were obtained.

<Synthesis Example of Polymerizable Monomer M-8>
The polymerizable monomer M-8 shown in Table 1 is produced using the method described in JP-A-63-270060, Journal of Polymer Science: Polymer Chemistry Edition 18, 2755 (1980).

<Synthesis Example of Polymerizable Monomer M-9>
Monomer M-9 described in Table 1 is produced using the method described in JP-A-62-2187429.

<Production example of polymer B-1>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube is charged with 60.0 parts of toluene and refluxed under a nitrogen stream.

Next, the following polymerizable monomer and solvent are mixed to prepare a monomer mixture.
Polymerizable monomer M-3 20.0 parts Styrene 80.0 parts Toluene 60.0 parts

  In addition, 6.6 parts of t-butylperoxyisopropyl monocarbonate (75% hydrocarbon solvent diluted product) as a polymerization initiator is further mixed with this polymerizable monomer mixed solution and added dropwise to the reaction vessel over 30 minutes. To do. Stir at 60 ° C. for 8 hours and cool to room temperature. The resulting polymer-containing composition is dropped into a mixed solution of 1400.0 parts of methanol and 10.0 parts of acetone over 10 minutes with stirring to precipitate and crystallize the polymer composition. The resulting polymer composition is filtered and washed twice with 200.0 parts of methanol. The resulting polymer powder is dried at 60 ° C. under reduced pressure for 10 hours to obtain polymer B-1. Table 2 shows the composition ratio and molecular weight of the polymer B-1.

<Production Example of Polymers B-2 to 13>
In the same manner as in the production example of polymer B-1, except that the monomer composition, the mixing ratio, and the number of parts of t-butylperoxyisopropyl monocarbonate as a polymerization initiator are changed as shown in Table 2, the polymer B-2 to 13 were obtained. It shows in Table 2 about the composition ratio and molecular weight of polymer B-2-13.

<Production Example of Crystalline Polyester Resin C>
(Production Example of Crystalline Polyester Resin 1)
To a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device, 100.0 parts of sebacic acid and 93.5 parts of 1,10-decanediol were added and stirred at a temperature of 130 ° C. Until heated. After adding 0.7 part of titanium (IV) isopropoxide as an esterification catalyst, the temperature is raised to 160 ° C. and polycondensation is performed over 5 hours. Then, it heated up at the temperature of 180 degreeC, it was made to react until it became a desired molecular weight, making it reduce pressure, and polyester (1) was obtained. The weight average molecular weight (Mw) of the polyester (1) was 19000, and the melting point (Tm) was 83 ° C.

  Next, 100.0 parts of polyester (1) and 440.0 parts of dehydrated chloroform were added and completely dissolved in a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, and then 5.0 parts of triethylamine was added. While cooling with ice, 15.0 parts of 2-bromoisobutyryl bromide was gradually added. Thereafter, the mixture was stirred at room temperature (25 ° C.) for a whole day and night.

  The resin solution was gradually added dropwise to a container containing 550.0 parts of methanol to reprecipitate the resin component, followed by filtration, purification and drying to obtain polyester (2).

  Next, 100.0 parts of the polyester (2) obtained above in a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 300.0 parts of styrene, 3.5 parts of copper (I) bromide, and penta While adding 8.5 parts of methyldiethylenetriamine and stirring, the polymerization reaction was conducted at a temperature of 110 ° C. When the desired molecular weight was reached, the reaction was stopped, and reprecipitation, filtration and purification were performed with 250.0 parts of methanol to remove unreacted styrene and catalyst. Then, it dried with the vacuum dryer set to 50 degreeC, and obtained the crystalline polyester resin 1 which has a polyester site | part and a vinyl polymer site | part. The composition of the obtained crystalline polyester resin 1 is shown in Table 3, and the physical properties are shown in Table 6.

(Crystalline polyester resin 4, 9, 11, 14)
Crystalline polyester resins 4, 9, 11, and 14 were obtained in the same manner as the method for producing crystalline polyester resin 1 except that crystalline polyester resin 1 was changed to the raw materials and production conditions shown in Table 3. Table 6 shows the physical properties of the obtained crystalline polyester resins 4, 9, 11, and 14.

(Production example of crystalline polyester resin 2)
To a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device, 100.0 parts of sebacic acid and 93.5 parts of 1,12-dodecanediol were added and stirred at a temperature of 130 ° C. Until heated. After adding 0.7 parts of titanium (IV) isopropoxide, the temperature was raised to 160 ° C. and polycondensation was performed over 5 hours. 100.0 parts of styrene was added dropwise over 1 hour. Stirring was continued for 1 hour while maintaining the temperature at 160 ° C., and then the monomer of the styrene resin component was removed at 8.3 kPa for 1 hour. Thereafter, the temperature was raised to 210 ° C., and the reaction was performed until a desired molecular weight was obtained, whereby a crystalline polyester resin 2 was obtained. The composition of the obtained crystalline polyester resin 2 is shown in Table 4, and the physical properties are shown in Table 6.

(Crystalline polyester resin 6, 10, 12, 15, 16, 20)
The crystalline polyester resins 6, 10, 12, 15, 16, and 20 were changed in the same manner as the production method of the crystalline polyester resin 2 except that the crystalline polyester resin 2 was changed to raw materials and production conditions as shown in Table 4. Obtained. Table 6 shows the physical properties of the obtained crystalline polyester resins 6, 10, 12, 15, 16, and 20.

(Production Example of Crystalline Polyester Resin 3)
100.0 parts of sebacic acid, 100.0 parts of 1,9-nonanediol and 0.3 part of tetrabutyl titanate were placed in a reactor equipped with a stirrer, a thermometer, and an outflow cooler and reacted at 180 ° C. for 6 hours. Went. Thereafter, the temperature was raised to 200 ° C., the pressure inside the system was gradually reduced, and the reaction was performed under reduced pressure for 5 hours to obtain a crystalline polyester resin 3. The composition of the obtained crystalline polyester resin 3 is shown in Table 5, and the physical properties are shown in Table 6.

(Crystalline polyester resin 7, 8, 13, 17, 18, 19)
The crystalline polyester resins 7, 8, 13, 17, 18, and 19 were changed in the same manner as the production method of the crystalline polyester resin 3 except that the crystalline polyester resin 3 was changed to the raw materials and production conditions as shown in Table 5. Obtained. Table 6 shows the physical properties of the obtained crystalline polyester resins 7, 8, 13, 17, 18, and 19.

(Production Example of Crystalline Polyester Resin 5)
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device, 100.0 parts by mass of xylene was heated while being purged with nitrogen, and refluxed at a liquid temperature of 140 ° C. A mixture of 100.0 parts by mass of styrene and 6.0 parts by mass of dimethyl 2,2′-azobis (2-methylpropionate) was added dropwise to the solution over 3 hours. After completion of the addition, the solution was stirred for 3 hours. Thereafter, xylene and residual styrene were distilled off at 160 ° C. and 1 hPa to obtain a vinyl polymer (1).

  Subsequently, 100.0 parts by mass of the vinyl polymer (1) obtained above in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, 80.0 parts by mass of xylene as an organic solvent, Then, 0.4 part by mass of titanium (IV) isopropoxide as an esterification catalyst was added to 83.0 parts by mass of 1,6-hexanediol, and reacted at 150 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, 100.0 parts by mass of 1,12-dodecanedioic acid was added and reacted at 150 ° C. for 3 hours and at 180 ° C. for 4 hours. Then, it was made to react until it became desired Mw at 180 degreeC and 1 hPa, and the crystalline polyester resin 5 was obtained. The composition of the obtained crystalline polyester resin 5 is shown in Table 3, and the physical properties are shown in Table 6.

<Production Example of Styrene Acrylic Resin A-1>
Heat 100.0 parts of propylene glycol monomethyl ether while replacing with nitrogen and reflux at a liquid temperature of 120 ° C. or higher, to which 225.0 parts of styrene, 75.0 parts of n-butyl acrylate, and tert-butyl peroxybenzoate [Organic peroxide polymerization initiator, manufactured by NOF Corporation, trade name “Perbutyl Z”] 1.0 part was added dropwise over 3 hours. After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. The solid matter was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain styrene acrylic resin A-1. The physical properties of the obtained styrene acrylic resin A-1 are shown below. Weight average molecular weight (Mw) = 25000, Mw / Mn = 2.4, glass transition temperature (Tg) = 57 ° C.

<Production Example of Styrene Acrylic Resin A-2>
100.0 parts of propylene glycol monomethyl ether is heated while being purged with nitrogen, and is refluxed at a liquid temperature of 120 ° C. or higher, to which 156.0 parts of styrene, 76.0 parts of n-butyl acrylate, 15.0 parts of acrylic acid, A mixture of 94.0 parts of hydroxyethyl methacrylate and 1.3 parts of tert-butyl peroxybenzoate [trade name “Perbutyl Z”] was added dropwise over 3 hours. After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. The solid matter was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain styrene acrylic resin A-2. The physical properties of the obtained styrene acrylic resin A-2 are shown below. Weight average molecular weight (Mw) = 15000, Mw / Mn = 2.4, acid value = 24.0 (mgKOH / g), hydroxyl value = 20.0 (mgKOH / g).

<Manufacture of amorphous polyester resin 1>
The following materials are mixed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and reacted for 25 hours at 220 ° C. under a nitrogen atmosphere and normal pressure. The reaction was carried out for 1 hour under a reduced pressure of 20 mmHg.
・ Terephthalic acid: 45.0 parts ・ Isophthalic acid: 3.0 parts ・ Trimellitic acid: 0.5 part ・ Bisphenol A-propylene oxide 2 mol adduct: 55.0 parts ・ Bisphenol A-propylene oxide 3 mol adduct : 64.0 parts ・ Dibutyltin oxide: 0.03 parts Thereafter, the temperature was lowered to 170 ° C., 0.09 part of trimellitic anhydride was added, and the mixture was allowed to react at 170 ° C. for 1.5 hours. 1 was obtained. The physical properties of the obtained amorphous polyester resin 1 are shown below. Weight average molecular weight (Mw) = 10000, Mw / Mn = 3.3, acid value = 10.0 (mgKOH / g), hydroxyl value = 24.0 (mgKOH / g).

<Production of hydrophobic silica 1>
Hydrophobic silica 1 was obtained by treating 100.0 parts of silica (AEROSIL 200CF, Nippon Aerosil Co., Ltd.) with 10.0 parts of hexamethyldisilazane and further with 20.0 parts of dimethyl silicone oil. The primary particle diameter of hydrophobic silica 1 was 12 nm, and the degree of hydrophobicity was 97.

<Production of hydrophobic titanium oxide 1>
100.0 parts of titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was treated with 20.0 parts of γ-mercaptopropyltrimethoxysilane in toluene, filtered and dried to obtain hydrophobic titanium oxide 1. The primary particle diameter of hydrophobic titanium oxide 1 was 25 nm, and the degree of hydrophobicity was 60.

(Toner Production Example 1)
In 1000.0 parts of ion-exchanged water, 15.3 parts of sodium phosphate and 4.9 parts of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . T.A. K. Using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 8.5 parts of calcium chloride is dissolved in 10.0 parts of ion-exchanged water is added and dispersed. An aqueous medium containing a stabilizer was prepared.

Next, the following materials were mixed in an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) and dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm to obtain a master batch dispersion.
Styrene 48.0 parts Copper phthalocyanine (CI Pigment Blue 15: 3, manufactured by Dainichi Seika Kogyo Co., Ltd.)
6.8 parts Polymer B-3 1.0 part

The following materials were further added to the master batch dispersion.
Styrene 32.0 parts n-Butyl acrylate 20.0 parts Crystalline polyester resin 1 10.0 parts Amorphous polyester resin 1 2.5 parts Paraffin wax (melting point: 78 ° C.) 9.0 parts

  This was kept at 69 ° C. K. Using a homomixer, it was uniformly dissolved and dispersed at 500 rpm. In this, 2.5 parts of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) is dissolved and polymerized. A functional monomer composition was prepared.

The polymerizable monomer composition was charged into the aqueous medium, 65 ° C., under N ₂ purge, T. K. The mixture was stirred with a homomixer at 10,000 rpm for 5 minutes, and granulated at pH 5.5. Then, it was made to react at 65 degreeC for 6 hours, stirring with a paddle stirring blade, and it heated up at 90 degreeC, and was made to react for another 6 hours. After completion of the polymerization reaction, the reaction vessel was cooled. Thereafter, the toner particles were obtained by washing with ion exchange water, drying and air classification.

  0.3 parts of hydrophobic titanium oxide 1 was added to 100.0 parts of the obtained toner particles, and mixed with a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.). Next, 1.5 parts of hydrophobic silica 1 was added and mixed with a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain a toner 1 having an external additive. In the DSC measurement of the obtained toner 1, an endothermic peak derived from the crystalline polyester C was observed. Table 8 shows the obtained physical properties and the like. In the differential scanning calorimetry of the obtained toner, it was recognized that it had an endothermic peak derived from the crystalline polyester C.

(Toner Production Examples 2-32)
Toners 2 to 32 having external additives were produced in the same manner as in Toner Production Example 1 except that the type and content of each raw material were changed as shown in Table 7. Table 8 shows the physical properties and the like of the obtained toners 2 to 32.

(Toner Production Example 33)
The following materials were premixed in a container, and then dispersed with a bead mill for 4 hours while maintaining the temperature at 20 ° C. or lower to prepare a toner composition mixed solution.
Styrene acrylic resin A-2 100.0 parts Polymer B-1 1.0 part Crystalline polyester resin 1 10.0 parts Copper phthalocyanine (CI Pigment Blue 15: 3) 5.0 parts Paraffin wax (melting point: 78 ° C.) 8.0 parts Amorphous polyester resin 1 5.0 parts Ethyl acetate 100.0 parts

78 parts of 0.1 mol / L Na ₃ PO ₄ aqueous solution is added to 240.0 parts of ion-exchanged water, heated to 60 ° C., and a precision dispersion and emulsifier manufactured by M Technique Co., Ltd. (trade name: CLEARMIX) ) Was used under the condition of 14,000 rpm. To this, 12.0 parts of a 1.0 mol / L-CaCl ₂ aqueous solution was added to obtain a dispersion medium (aqueous medium) containing Ca ₃ (PO ₄ ) ₂ . Furthermore, 1.0 part by mass of carboxymethylcellulose (trade name: Serogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for 10 minutes.

While the temperature of the dispersion medium prepared in the container of the precision dispersing / emulsifying machine is adjusted to 30 ° C. and stirring, 180 parts of the toner composition mixed solution adjusted to a temperature of 30 ° C. is added. After stirring for a minute, the operation was stopped to obtain a toner composition dispersion suspension. While stirring the obtained toner composition dispersion suspension, the temperature is kept constant at 40 ° C., the gas phase on the surface of the suspension is forcibly renewed by an exhaust device, and is maintained for 17 hours to remove the solvent. did. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water and dried to obtain toner particles. Thereafter, a toner 33 having an external additive was obtained in the same manner as in the toner 1 production example. Table 8 shows the physical properties and the like of the obtained toner 33.

(Toner Production Examples 34 to 35)
Toners 34 to 35 having external additives were produced in the same manner as in Toner Production Example 33 except that the type and content of each raw material were changed as described in Table 7. Table 8 shows the physical properties and the like of the obtained toners 34 to 35.

(Toner Production Example 36)
-Production of styrene acrylic resin dispersion Styrene 78.0 parts n-Butyl acrylate 22.0 parts Polymer B-3 1.0 part Dodecanediol 6.0 parts Carbon tetrabromide 1.0 part Nonionic in flask 4001.5 parts of surfactant Nonipol and 2.5 parts of anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) were dissolved in 140.0 parts of ion-exchanged water.

  Next, 10 parts of ion-exchanged water in which 1.0 part of ammonium persulfate was dissolved was added thereto while the above materials were mixed and dissolved in a flask, emulsified and slowly mixed for 10 minutes. .

  Next, while performing nitrogen substitution, the flask was heated with an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion having a central diameter of 145 nm was obtained.

-Production of Crystalline Polyester Resin Dispersion The following materials were mixed, heated to 80 ° C and dissolved, and dispersed with a homogenizer (trade name: Ultra Turrax T50) manufactured by IKA.

Crystalline polyester resin 1 100.0 parts Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) 5.0 parts Ion-exchanged water 300.0 parts Thereafter, dispersion treatment is performed with Gorin homogenizer (manufactured by Renwa Shoji). The crystalline polyester resin dispersion having a center diameter of 180 nm was obtained by carrying out dispersion treatment 20 times under the conditions of 90 ° C. and 550 kg / cm ² .

-Preparation of Pigment Dispersion Solution The following materials were mixed, dissolved, and dispersed by ultrasonic irradiation with a homogenizer (trade name: Ultra Tarrax) manufactured by IKA to obtain a pigment dispersion solution having a center particle size of 140 nm.
Copper phthalocyanine (CI Pigment Blue 15: 3: manufactured by Dainichi Seika Kogyo Co., Ltd.) 100.0 parts Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) 10.0 parts Ion-exchanged water 400.0 Part / wax dispersion

The following materials were mixed, heated to 97 ° C., and then dispersed with an IKA homogenizer (Ultra Turrax T50).
Paraffin wax (melting point: 78 ° C.) 100.0 parts Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) 5.0 parts Ion-exchanged water 300.0 parts Thereafter, with Gorin homogenizer (manufactured by Renwa Shoji) Dispersion treatment was carried out 20 times under the conditions of 105 ° C. and 550 kg / cm ² to obtain a release agent dispersion having a center diameter of 190 nm.

Production of toner particles Resin dispersion (resin particle solid content 25.0 mass%) 400.0 parts Crystalline polyester resin dispersion (resin particle solid content 20.0 mass%) 50.0 parts Pigment dispersion (aromatic 21.0 parts Wax dispersion 30.0 parts Sanisol B50 (manufactured by Kao Corporation) 2.0 parts

  The above materials were mixed and dispersed in a round stainless steel flask using Ultra Turrax T50, and then heated to 48 ° C. while stirring the flask in an oil bath for heating. Further, the temperature of the heating oil bath was raised and held at 50 ° C. for 1 hour. Thereafter, 3.0 parts of Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) was added thereto. Thereafter, the stainless steel flask was sealed, heated to 105 ° C. while continuing stirring using a magnetic seal, and held for 3 hours. After cooling, it was filtered, washed with ion exchange water, and then dried to obtain toner particles.

  The obtained toner particles were classified to obtain a toner 36 having an external additive in the same manner as in the toner 1 production example. Table 8 shows the physical properties of Toner 36 thus obtained.

(Toner Production Example 37)
A toner 36 having an external additive was produced in the same manner as in Toner Production Example 36 except that the type and content of each raw material were changed as shown in Table 7. Table 8 shows the physical properties and the like of the obtained toner 37.

(Toner Production Example 38)
Styrene acrylic resin A-1 100.0 parts Carbon black (manufactured by Orion Engineered Carbons, trade name “Printex35”) 7.0 parts Polymer B-3 1.0 part Crystalline polyester resin 9 10.0 parts Synthetic wax ( (Manufactured by Schumann Sasol, Sasol SPRAY30, melting point: 98 ° C.)
3.0 parts The above materials were mixed in a Mitsui Henschel mixer. After that, melt kneading is performed at 125 ° C. with a twin-screw kneading extruder, the kneaded product is gradually cooled to room temperature, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and air classification. Thus, black colored particles were produced.

  To 100 parts of the resulting black colored particles, 0.3 part of hydrophobic titanium oxide 1 was added and mixed with a Mitsui Henschel mixer. Further, 1.5 parts of hydrophobic silica 1 was added and further mixed with a Mitsui Henschel mixer to prepare a toner 38 having an external additive. Table 8 shows the physical properties and the like of the obtained toner 38.

(Toner Production Examples 39, 41, 43)
Toners 39, 41, and 43 having external additives were produced in the same manner as in Toner Production Example 1 except that the type and content of each raw material were changed as shown in Table 7. Table 8 shows the physical properties and the like of the obtained toner.

(Toner Production Examples 40 and 42)
Toners 40 and 42 having external additives were produced in the same manner as in Toner Production Example 33 except that the type and content of each raw material were changed as shown in Table 7. Table 8 shows the physical properties and the like of the obtained toner.

(Examples 1-38)
Each of the toners 1 to 38 was subjected to various image evaluations using an evaluation machine.

  Table 16 shows the results of various image evaluations.

(Comparative Examples 1-5)
Each of the toners 39 to 43 was subjected to various image evaluations using an evaluation machine.

  Table 16 shows the results of various image evaluations.

  Various image evaluations were performed as follows.

(Evaluation machine)
As the evaluators of Examples 1 to 38 and Comparative Examples 1 to 5, the following were used. The process speed of LBP-2710 manufactured by Canon Inc. was modified to 220 mm / s, the toner was extracted from the magenta cartridge, and the inside was cleaned by air blow. Thereafter, 260 g of the toner of the present invention was filled, and other cyan, yellow and black cartridges were used after the toner was removed and inserted into each station.

<Fog>
For the measurement of fog, the above-described evaluation machine is used as an image forming apparatus, and an image forming test is repeatedly performed in a system in which the printing is paused for 1 minute every time two sheets are printed at a printing rate of 1% under the following environment. After printing, it was left for 6 days in each environment.

  The fog amount of the first image sample after that was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. and calculated from the following formula. A4 size plain paper (manufactured by Canon Marketing Japan Inc., GF-C081A4) was used as the recording material used in the repeated image formation test.

  Fog amount (%) = (whiteness of recording material before printing out) − (whiteness of non-image forming portion (white background portion) of recording material after printing)

<Image density>
The initial image density is a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and the amount of toner on the paper is 0.38 (mg / cm ² ) using the evaluation machine described above. 1) was printed, and the image density of each image was measured. The density of the image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. A4 size plain paper (manufactured by Canon Marketing Japan Inc., GF-C081A4) was used as the recording material.

<Fixability>
In a low-temperature and low-humidity environment (L / L: temperature 15 ° C., humidity 10% RH), using the above-described evaluation machine, the evaluation machine and the cartridge filled with the toner are familiar with the environment (after leaving in that environment for 24 hours) ) Was turned on. Immediately after the weight-up, a 200 μm-wide horizontal line pattern (width 200 μm, interval 200 μm) was printed out, and the 50th printed image was used for evaluation of fixability. The fixing property was evaluated by rubbing the image with Sylbon paper at a load of 100 g for 5 reciprocations, and peeling of the image was evaluated by the average of the reduction rate (%) of the reflection density.

  For the evaluation, bond paper having a surface smoothness of 10 [sec] or less was used. The evaluation criteria are shown below. Ranks A, B, and C were levels at which the effects of the present invention were obtained.

<Offset resistance>
Offset resistance is normal temperature and humidity environment (N / N: temperature 23.5 ° C, humidity 60% RH), high temperature and humidity environment (H / H: temperature 32.5 ° C, humidity 80% RH). Evaluation was performed using the above-described evaluation machine. Turn on the power after the evaluation machine and toner-filled cartridge are familiar with the environment (after leaving it in the environment for 24 hours), and print out 100 solid images immediately after weighting up and evaluate the image samples. It was.

  For the evaluation, an OHP film (CG3700, manufactured by Sumitomo 3M Limited) was used. The evaluation criteria are shown below.

<Fusion and adhesion of toner to toner layer regulating member>
The toner is fused and fixed to the toner layer regulating member in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C.). , Humidity 80% RH), using the above-mentioned evaluation machine. Each time two sheets were printed at a printing rate of 1%, an image formation test was repeatedly carried out by pausing for 1 minute, and the 8000th image sample from the initial stage was visually evaluated. As the recording material, A4-sized plain paper (Canon Marketing Japan, GF-C081A4) was used. The evaluation criteria are shown below.

<Filming to latent image carrier>
Filming on the latent image carrier is performed in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). Using the above-described evaluation machine, repeated image formation tests were performed by continuous printing at a printing rate of 1%. The 2000th image sample from the beginning was visually evaluated. As the recording material, A4-sized plain paper (Canon Marketing Japan, GF-C081A4) was used. The evaluation criteria are shown below.

<Flip off>
In a non-high temperature and high humidity environment (SH / H: temperature 40 ° C., humidity 95% RH), the toner-filled cartridge is allowed to stand for two weeks, and then two sheets are printed at a printing rate of 2% using the evaluation machine described above. The image formation test was repeatedly performed by a method of pausing for 1 minute each time printing was performed. The 1000th image sample from the beginning was visually evaluated. As the recording material, A4-sized plain paper (Canon Marketing Japan, GF-C081A4) was used. The evaluation criteria are shown below.

<Evaluation of storage stability of toner>
The storage stability of the toner was evaluated by weighing 10 g of toner in a 100 ml polycup, leaving it in a constant temperature layer at 50 ° C. for 3 days, and then evaluating it with a 200 mesh (opening) sieving property. As a measuring apparatus, a powder tester (manufactured by Hosokawa Micron Co., Ltd.) having a digital vibrometer (manufactured by DEGIBILATIONMETERMODEL 1332 SHOWA SOKKI CORPORATION) was used.

  As a measuring method, a toner for evaluation is placed on a set 200 mesh sieve (aperture 75 μm), and the displacement value of the digital vibrometer is adjusted to 0.50 mm (peak-to-peak) for 30 seconds. Vibration was applied. Thereafter, the storage stability was evaluated from the state of the aggregate of toner remaining on each sieve. The evaluation criteria are shown below.

Claims (11)

A toner having toner particles containing a styrene acrylic resin A, a polymer B having a structure b represented by the following formula (1), and a crystalline polyester resin C,
The styrene acrylic resin A contains 60% by mass or more of units derived from styrene monomers based on the units derived from all monomers constituting the styrene acrylic resin A.
The weight average molecular weight (Mw) of the polymer B is 1,000 or more and 100,000 or less,
The crystalline polyester resin C has a polyester moiety represented by the following formula (2),
The melting point of the crystalline polyester resin C is 55 ° C. or higher and 95 ° C. or lower,
The toner according to claim 1, wherein the crystalline polyester resin C has a weight average molecular weight (Mw) of 8000 to 45,000.

(In Formula (1), R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms. F is an integer of 0 to 3 inclusive. Or when it is 3, R ¹ may be the same or different, * is the binding site in the polymer.)

(In formula (2), m and n are each independently an integer of 4 or more and 16 or less.) The toner according to claim 1, wherein the structure b represented by the formula (1) is a structure represented by the following formula (3).

(In formula (3), R ² represents an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 18 carbon atoms. R ³ represents a hydrogen atom, a hydroxy group, or 1 to 18 carbon atoms. The following alkyl groups or alkoxyl groups having 1 to 18 carbon atoms are shown: g is an integer of 1 to 3 and h is an integer of 0 to 3. When h is 2 or 3, R ² may be the same or different, and * is a bonding site in the polymer.) The toner according to claim 1, wherein the polymer B is a polymer having a site represented by the following formula (4).

(In formula (4), R ⁴ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms. R ⁵ represents a hydrogen atom, a hydroxy group, or 1 to 18 carbon atoms. The following alkyl groups or alkoxyl groups having 1 to 18 carbon atoms are shown: R ⁶ represents a hydrogen atom or a methyl group, i is an integer of 1 to 3, and j is 0 or more And an integer of 3 or less, and when j is 2 or 3, R ⁴ may be the same or different.   4. The toner according to claim 1, wherein a content ratio of the structure b to the polymer B is 10 μmol / g or more and 1500 μmol / g or less.   The toner according to claim 1, wherein a content ratio of the structure b to the toner is 0.10 μmol / g or more and 200.0 μmol / g or less.   6. The toner according to claim 1, wherein a content of the crystalline polyester resin C with respect to the styrene acrylic resin A is 2.0% by mass or more and 40.0% by mass or less. The SP value of the crystalline polyester resin C is D ((cal / cm ³ ) ^1/2 ),
When the SP value of the polymer B is E ((cal / cm ³ ) ^1/2 ),
The toner according to any one of claims 1 to 6, wherein an absolute value of a difference between D and E is 0.10 or more and 1.00 or less.   The toner according to claim 7, wherein the crystalline polyester resin C has an SP value D of 9.40 or more and 9.85 or less. The crystalline polyester C is a block polymer having a polyester moiety represented by the formula (2) and a vinyl polymer moiety,
The weight average molecular weight (Mw) of the block polymer is from 15000 to 45000,
9. The toner according to claim 1, wherein the vinyl polymer moiety has a weight average molecular weight (Mw) of 4,000 to 15,000.   The toner according to claim 9, wherein a mass-based ratio of the polyester part represented by the formula (2) of the block polymer and the vinyl polymer part is 40/60 or more and 80/20 or less. The toner according to any one of claims 1 to 8, wherein the polyester portion of the crystalline polyester resin C has a unit represented by the following formula (7) and a unit represented by the following formula (8).

(In formulas (7) and (8), p is an integer of 4 or more and 14 or less. Q is an integer of 4 or more and less than r. R is an integer of q or more and 16 or less.)