JP2018041068A - Toner and method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that satisfies good low-temperature fixability, excellent hot offset resistance, and fluidity after a long-term storage even when an ethylene-vinyl acetate copolymer is used as a binder resin, and a method for manufacturing the toner.SOLUTION: A toner contains a binder resin including an ethylene-vinyl acetate copolymer, a polysiloxane derivative A represented by a specific structural formula, and a polysiloxane derivative B represented by a specific structural formula.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system and a toner manufacturing method.

In the electrophotographic method, a heat fixing method is generally employed in which a toner image formed on an image forming member by development is transferred to a recording medium such as paper and then heated. Among the heat fixing methods, a fixing method using a heating roller as a heating means has been widely used in recent years because of its high heat transfer efficiency.
However, in this method, the toner image and the surface of the fixing roller are in pressure contact with each other in a heated and melted state, so a part of the toner adheres to the surface of the fixing roller and moves onto the next recording medium and becomes dirty on the recording medium. May cause a so-called hot offset phenomenon.
Therefore, as a method for dealing with this problem, proposals have been made to contain an olefinic compound such as an alkyl wax as a release agent in the toner, or to contain silicone oil (Patent Documents 1 to 4).
On the other hand, in recent years, with the increasing demand for energy saving in image formation, efforts have been made to lower the toner fixing temperature. As a method for improving the low-temperature fixability, it has been proposed to lower the fixing temperature by using a resin having a low glass transition temperature. Toners containing an ethylene-vinyl acetate copolymer as a resin having a low glass transition temperature have been proposed (Patent Documents 5 to 9).
As a method for producing a toner, an emulsion aggregation method has attracted attention from the viewpoint that the particle size distribution, particle size and shape of the toner can be easily controlled. The emulsion aggregation method is a production method in which toner particles are formed by aggregating particles in a dispersion liquid containing resin fine particles in an aqueous medium to form aggregate particles, and then heating and aggregating the aggregate particles (Patent Document 10). To 11).

JP 2007-264333 A JP 2001-166524 A Japanese Patent Laid-Open No. 11-316472 Japanese Patent Laid-Open No. 2-3073 JP 59-18854 A JP 2011-107261 A JP-A-11-202555 JP-A-8-184986 JP-A-4-21860 Japanese Patent Laying-Open No. 2015-175938 Japanese Patent Laid-Open No. 11-311877

In order to improve the low-temperature fixability, the present inventors tried to develop a toner using an ethylene-vinyl acetate copolymer as a binder resin, but the ethylene-vinyl acetate copolymer was used as the binder resin. Then, it became clear that the hot offset resistance was lower than that of a normal toner.
In general, as a method for improving the hot offset resistance of a toner, by including a release agent in the toner, the release agent oozes out to the interface between the fixing member and the toner at the time of fixing, thereby improving the hot offset resistance. It is known.
However, as a result of investigations by the present inventors, when an ethylene-vinyl acetate copolymer is used as a binder resin, the ethylene-vinyl acetate copolymer is highly hydrophobic and is generally used for toners such as alkyl waxes. Compatibility with wax did not improve hot offset resistance. In particular, it became more prominent when the ethylene-vinyl acetate copolymer accounted for 50% by mass or more of the binder resin.
Therefore, the present inventors examined the addition of a polysiloxane derivative represented by the following structural formula 1, which can be expected to have a release effect without being compatible with the ethylene-vinyl acetate copolymer.
However, since the polysiloxane derivative is liquid and has an extremely low affinity with the ethylene-vinyl acetate copolymer, the polysiloxane derivative exudes to the toner surface layer during long-term storage, and the fluidity of the toner is reduced. .
In addition, an attempt was made to produce a toner by an emulsion aggregation method that can easily control the particle size and particle size distribution of the toner. As a result, since the polysiloxane derivative has a low affinity with the ethylene-vinyl acetate copolymer, it was difficult to contain the polysiloxane derivative in the toner in such an amount as to sufficiently exhibit the release effect.
The present invention is a toner satisfying good low-temperature fixability, excellent hot offset resistance, and fluidity after long-term storage, even when an ethylene-vinyl acetate copolymer is used as a binder resin, and It is to provide a method for producing the toner.

(In Structural Formula 1, R _{1 to} R ₁₀ each independently represent a methyl group or a phenyl group, and l, m, and n each independently represent an integer of 1 or more.)

The present invention is a toner containing a binder resin containing an ethylene-vinyl acetate copolymer, a polysiloxane derivative A represented by the following structural formula 1, and a polysiloxane derivative B represented by the following structural formula 2.
The present invention also provides:
A step of emulsifying a polysiloxane derivative A represented by the following structural formula 1 and a polysiloxane derivative B represented by the following structural formula 2 to obtain emulsified particles of the polysiloxane derivative A and the polysiloxane derivative B;
A step of micronizing a binder resin containing an ethylene-vinyl acetate copolymer to obtain resin microparticles;
A step of agglomerating the emulsified particles and the resin fine particles to obtain an aggregate; and
A fusion step of fusing the aggregates;
A method for producing a toner having the following.

(In Structural Formula 1, R _{1 to} R ₁₀ each independently represent a methyl group or a phenyl group, and l, m, and n each independently represent an integer of 1 or more.)

(In Structural Formula 2, at least one of R _{11 to} R ₂₀ has a C _4-30 alkyl group, a C _4-30 alkoxy group, an acrylic group, an amino group, a methacryl group, or a carboxy group. (It is an organic group, and the others independently represent a methyl group or a phenyl group, and p, q, and r each independently represent an integer of 1 or more.)

  According to the present invention, it is possible to provide a toner that satisfies satisfactory low-temperature fixability, excellent hot offset resistance, and fluidity after long-term storage, and a method for producing the toner.

(A) And (b) is explanatory drawing of the introduction | transduction rate measurement of a polysiloxane derivative.

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
The toner of the present invention contains a binder resin containing an ethylene-vinyl acetate copolymer, a polysiloxane derivative A represented by the above structural formula 1, and a polysiloxane derivative B represented by the above structural formula 2. Features.
As a result of intensive studies by the present inventors, an ethylene-vinyl acetate copolymer, a polysiloxane derivative A represented by the above structural formula 1 (hereinafter also simply referred to as polysiloxane derivative A), and a polysiloxane represented by the above structural formula 2 are used. It has been found that by using in combination with siloxane derivative B (hereinafter also simply referred to as polysiloxane derivative B), the hot offset resistance can be remarkably improved without lowering the fluidity after long-term storage. .

When only the polysiloxane derivative A is used, the polysiloxane derivative A has a very low affinity with the ethylene-vinyl acetate copolymer and is a liquid, so that the polysiloxane derivative A in the toner is stored during long-term storage. The toner surface oozes out and the fluidity of the toner decreases.
Further, when only the polysiloxane derivative B is used, the polysiloxane derivative B has an organic group site having a high affinity with the ethylene-vinyl acetate copolymer, so that it is difficult to seep out to the toner surface layer even after long-term storage. There is. However, the high affinity organic group site plasticizes the ethylene-vinyl acetate copolymer and cannot improve hot offset resistance.
On the other hand, when the polysiloxane derivative A and the polysiloxane derivative B are used in combination, the organic group portion having high affinity with the ethylene-vinyl acetate copolymer and the siloxane portion having high affinity with the polysiloxane derivative A are combined. The polysiloxane derivative B serves to keep the polysiloxane derivative A inside the toner. Therefore, hot offset resistance can be improved without reducing the fluidity after long-term storage.

In addition, when only the polysiloxane derivative A is used in the production of the toner using the emulsion aggregation method, the affinity between the polysiloxane derivative A and the ethylene-vinyl acetate copolymer is low, so that the hot offset resistance is improved. It is difficult to sufficiently contain the polysiloxane derivative A. This is because the polysiloxane derivative A escapes from the toner in a process such as aggregation, fusion, or washing described later.
However, when the polysiloxane derivative A and the polysiloxane derivative B are used in combination, the polysiloxane derivative B also functions as an introduction aid for the polysiloxane derivative A, and the polysiloxane derivative A can be sufficiently contained in the toner. .

The content of the ethylene-vinyl acetate copolymer in the binder resin is preferably 50% by mass or more and 100% by mass or less, and preferably 70% by mass or more and 90% by mass or less from the viewpoint of low temperature fixability at high speed output. More preferably, it is 70% by mass or more and 80% by mass or less.
Since the ethylene-vinyl acetate copolymer has a glass transition temperature of 0 ° C. or less, the low-temperature fixability at high-speed output is improved by containing 50% by mass or more in the binder resin.

The content of the monomer unit derived from vinyl acetate in the ethylene-vinyl acetate copolymer is preferably 5% by mass or more and 20% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. In addition, a monomer unit means the form which the monomer substance in a polymer or resin reacted.
When the content of the monomer unit derived from vinyl acetate is 20% by mass or less, the chargeability as a toner is improved. On the other hand, when the content is 5% by mass or more, the adhesion to paper is improved and the low-temperature fixability is improved.

From the viewpoint of toner strength and blocking resistance after long-term storage, the melt flow rate of the ethylene-vinyl acetate copolymer is preferably 30 [g / 10 min] or less.
Further, from the viewpoint of impact resistance and pressure resistance when using the toner, the melt flow rate is more preferably 20 [g / 10 min] or less.
On the other hand, from the viewpoint of image glossiness, the melt flow rate is preferably 5 [g / 10 min] or more.
When an ethylene-vinyl acetate copolymer having a melt flow rate of 30 [g / 10 min] or less is used at 50% by mass or more of the binder resin, it is difficult to pulverize the toner. Is difficult to manufacture. Therefore, the method for producing the toner is preferably an emulsion aggregation method.

In the present invention, the melt flow rate is measured under the conditions of 190 ° C. and 2160 g load based on JIS K 7210.
The melt flow rate can be controlled by changing the molecular weight of the ethylene-vinyl acetate copolymer. For example, the melt flow rate can be lowered by increasing the molecular weight.
The weight average molecular weight of the ethylene-vinyl acetate copolymer is preferably 50,000 or more and 500,000 or less, more preferably 100,000 or more and 500,000 or less, from the viewpoint of adjusting the melt flow rate and the gloss of the image. .
The breaking elongation of the ethylene-vinyl acetate copolymer is preferably 300% or more, and more preferably 500% or more. The upper limit is not particularly limited, but is preferably 1500% or less.
When the breaking elongation is 300% or more, the bending resistance of the fixed product is improved.
The elongation at break can be increased by increasing the molecular weight of the ethylene-vinyl acetate copolymer.

The ethylene-vinyl acetate copolymer may be an ethylene-vinyl acetate copolymer modified to such an extent that its properties are not substantially impaired.
As a modification method of the ethylene-vinyl acetate copolymer, a method of mixing a part of other monomers in addition to ethylene and vinyl acetate at the time of polymerization, a method of saponifying a part of the ethylene-vinyl acetate copolymer, etc. Is mentioned.

The toner may contain other polymer or resin as the binder resin in addition to the ethylene-vinyl acetate copolymer.
For example, the following polymers or resins can be used.
Styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Styrene copolymers such as acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer; polyvinyl chloride, phenol resin, natural resin-modified phenol resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, Polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin, and polypropylene resin.

Among these, it is preferable to contain a modified polyethylene resin and / or a crystalline polyester resin having a melting point of 50 ° C. or higher and 100 ° C. or lower.
For example, when a modified polyethylene resin having a carboxy group is contained as a binder resin, the carboxy group of the modified polyethylene resin forms a hydrogen bond with a hydroxyl group on the paper surface, and the adhesion between the toner and the paper surface is increased, thereby improving the fixability. To do.
The modified polyethylene resin is a resin in which other components are randomly copolymerized, block copolymerized, or graft copolymerized with a polyolefin resin mainly composed of polyethylene, and those resins modified by a polymer reaction. Sure.
Examples of the component to be copolymerized include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. Specifically, an ethylene-acrylic acid copolymer and an ethylene-methacrylic acid copolymer can be suitably exemplified.

The acid value of the modified polyethylene resin is preferably 50 mgKOH / g or more and 300 mgKOH / g or less, from the viewpoint of improving the adhesion between the toner and paper, and from the viewpoint of improving the chargeability, and 80 mgKOH / g. More preferably, it is 200 mgKOH / g or less.
Further, the content of the modified polyethylene resin in the binder resin is preferably 10% by mass or more and 30% by mass or less.
When the content of the modified polyethylene resin is in the above range, the adhesion to paper can be improved without reducing the charging property.

From the viewpoint of blocking resistance after long-term storage of the toner, the melt flow rate of the modified polyethylene resin is preferably 200 [g / 10 min] or less.
Further, from the viewpoint of adhesion between the toner and paper, the melt flow rate of the modified polyethylene resin is preferably 10 [g / 10 min] or more.
The melt flow rate of the modified polyethylene resin can be measured by the same method as the melt flow rate of the ethylene-vinyl acetate copolymer.

The melting point of the modified polyethylene resin is preferably 50 ° C. or higher and 100 ° C. or lower from the viewpoint of low-temperature fixability and storage stability. When the melting point is 100 ° C. or lower, the low-temperature fixability is further improved. Further, when the melting point is 90 ° C. or lower, the low-temperature fixability is further improved. On the other hand, when the melting point is 50 ° C. or higher, the storage stability is improved.
The melting point of the modified polyethylene resin can be measured using a differential scanning calorimeter (DSC). Specifically, a 0.01 to 0.02 g sample is precisely weighed in an aluminum pan, and heated from 0 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min to obtain a DSC curve. The peak temperature of the maximum endothermic peak in the obtained DSC curve is the melting point.

As a binder resin, when containing a crystalline polyester resin, even if it contains an ethylene-vinyl acetate copolymer having a low melt flow rate, it is possible to reduce the kinematic viscosity at the time of heat melting of the toner, An image having high glossiness can be obtained.
In addition, when the toner contains a colorant, the crystalline polyester resin acts as a colorant dispersant, which increases the dispersibility of the colorant in the ethylene-vinyl acetate copolymer and obtains a fixed product having a high image density. be able to. Further, the crystalline polyester resin acts as a crystal nucleating agent for the ethylene-vinyl acetate copolymer, and the blocking resistance and chargeability after long-term storage are improved.
The content of the crystalline polyester resin in the binder resin is preferably 10% by mass or more and 30% by mass or less. When the content of the crystalline polyester resin is in the above range, the kinematic viscosity reducing effect and the effect as a crystal nucleating agent can be sufficiently obtained without lowering the chargeability.

The crystalline polyester resin is not particularly limited, but contains a monomer unit derived from alcohol and a monomer unit derived from carboxylic acid.
In addition, from the viewpoint of ester group concentration and melting point, the crystalline polyester resin comprises a monomer unit derived from an aliphatic diol having 4 to 20 carbon atoms and a monomer unit derived from an aliphatic dicarboxylic acid having 4 to 20 carbon atoms. It is preferable to contain.
The crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).
Specific examples of the diol include the following.
Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane Diol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eico Sundiol, 2-methyl-1,3-propanediol, cyclohexanediol, cyclohexanedimethanol. These may be used alone or in combination of two or more.
Specific examples of the dicarboxylic acid include the following.
Oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1 , 18-octadecanedicarboxylic acid. These may be used alone or in combination of two or more.

The acid value of the crystalline polyester resin is preferably 5 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of improving pigment dispersibility and improving chargeability in a high humidity environment.
The acid value of the crystalline polyester resin can be measured in the same manner as the acid value of the modified polyethylene resin.
The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 5000 or more and 50000 or less, and more preferably 5000 or more and 20000 or less.
By setting the weight average molecular weight (Mw) of the crystalline polyester resin to 50000 or less, the ethylene-vinyl acetate copolymer can be plasticized and can be easily made into a toner by the method described later, and the low-temperature fixability is also improved. To do. Further, when the weight average molecular weight (Mw) is 5000 or more, the strength as a toner can be increased.
The weight average molecular weight (Mw) of the crystalline polyester resin can be easily controlled by various known production conditions for the crystalline resin.

The melting point of the crystalline polyester resin is preferably 50 ° C. or higher and 100 ° C. or lower, and more preferably 50 ° C. or higher and 90 ° C. or lower, from the viewpoint of low-temperature fixability and storage stability.
The melting point of the crystalline polyester resin can be measured using a differential scanning calorimeter (DSC). Specifically, a 0.01 to 0.02 g sample is precisely weighed in an aluminum pan, and heated from 0 ° C. to 200 ° C. at a temperature rising rate of 10 ° C./min to obtain a DSC curve. From the obtained DSC curve, the peak temperature of the maximum endothermic peak is the melting point.
The crystallinity of the crystalline polyester resin is preferably 10% or more and 60% or less, and more preferably 20% or more and 60% or less. When the degree of crystallinity is 10% or more, the crystalline polyester resin becomes a crystal nucleating agent for the ethylene-vinyl acetate copolymer, thereby improving the overall crystallinity of the toner and preventing blocking during storage.

The polysiloxane derivative A is a compound represented by the following structural formula 1.

(In Structural Formula 1, R _{1 to} R ₁₀ each independently represent a methyl group or a phenyl group, and l, m, and n each independently represent an integer of 1 or more.)

The content of the polysiloxane derivative A is preferably 5 parts by mass or more and 30 parts by mass or less, and more preferably 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.
When the content of the polysiloxane derivative A is in the above range, the hot offset resistance can be sufficiently improved.
Moreover, kinematic viscosity at 25 ° C. of the polysiloxane derivative A is plasticized suppression of the binder resin, and, from the viewpoint of speedup seeping into the surface layer during the heat fixation of the toner, 5 mm 2 / ^s or more 3000 mm ² / preferably s or less, ^{5 mm} 2 / s or more 1000 mm ² / more preferably s or less, more preferably at most 50 mm ² / s or more ^{1000mm 2 / s, 50mm 2 /} s or more 300 mm ² / It is particularly preferred that it is s or less.
Examples of the polysiloxane derivative A include dimethylpolysiloxane, methylphenylpolysiloxane, and diphenylpolysiloxane, and dimethylpolysiloxane is preferable.

The polysiloxane derivative B is a compound represented by the following structural formula 2.

(In Structural Formula 2, at least one of R _{11 to} R ₂₀ has a C _4-30 alkyl group, a C _4-30 alkoxy group, an acrylic group, an amino group, a methacryl group, or a carboxy group. (It is an organic group, and the others independently represent a methyl group or a phenyl group, and p, q, and r each independently represent an integer of 1 or more.)

Specific examples of the polysiloxane derivative B include a compound having an organic group in a part of a side chain of dimethylpolysiloxane, a compound having an organic group at both ends of dimethylpolysiloxane, or either one of dimethylpolysiloxane. The compound which introduce | transduced the organic group into the terminal is mentioned. Moreover, as this organic group, what has a group chosen from a long chain ( _C4-30 ) alkyl group, a long chain ( _C4-30 ) alkoxy group, an acryl group, an amino group, a methacryl group, or a carboxy group. Can be mentioned. The organic group is a C _1-8 carboxyalkyl, or acrylic acid-acrylic acid (C _4-30 ) alkyl ester copolymer, acrylic acid-methacrylic acid (C _4-30 ) alkyl ester copolymer. The polymer may be a methacrylic acid-acrylic acid (C _4-30 ) alkyl ester copolymer, a methacrylic acid-methacrylic acid (C _4-30 ) alkyl ester copolymer, or the like.
More specifically, stearoxymethicone / dimethylpolysiloxane copolymer, acrylic polymer / dimethylpolysiloxane copolymer, carboxyl-modified silicone oil, polyether-modified silicone oil and the like can be mentioned.

The content of the polysiloxane derivative B is preferably 5 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polysiloxane derivative A.
When the content of the polysiloxane derivative B satisfies the above range, the content of the polysiloxane derivative A in the toner can be sufficient, and the binder resin can be prevented from being excessively plasticized to improve blocking resistance. Can be made.
Further, when the polysiloxane derivative B has a melting point, the organic group portion of the polysiloxane derivative B is crystallized in the toner, and excessive plasticization of the binder resin can be prevented.
The melting point of the polysiloxane derivative B is preferably 20 ° C. or higher and 70 ° C. or lower, and more preferably 30 ° C. or higher and 60 ° C. or lower, from the viewpoint of low-temperature fixability.
The melting point of polysiloxane derivative B can be measured in the same manner as the melting point of crystalline polyester resin.
When the polysiloxane derivative B is a liquid, the kinematic viscosity at 25 ° C. of the polysiloxane derivative B is preferably 5 mm ² / s to 3000 mm ² / s, and more preferably 50 mm ² / s to 1000 mm ^2. / S or less.

The compatibility between the binder resin and the polysiloxane derivative can be evaluated using the softening point (Tm).
The softening point is measured by using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device.
In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point.
The melting temperature in the 1/2 method is calculated as follows.
First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of descending piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.
For the measurement, about 1.2 g of a sample is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 60 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000cm2
Test load (piston load): 5.0 kgf
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm
The softening point of the binder resin was Tm ₀ (° C.), and the softening point of the mixture obtained by heating and kneading the binder resin and polysiloxane derivative A at a mass ratio of 100: 10 was Tm ₁ (° C.). Sometimes, it is preferable to satisfy the relationship of 0.0 ≦ [Tm ₀ −Tm ₁ ] ≦ 3.0, and more preferably satisfy the relationship of 0.0 ≦ [Tm ₀ −Tm ₁ ] ≦ 2.0. preferable.
When [Tm ₀ -Tm ₁ ] is in the above range, the polysiloxane derivative A inside the toner tends to ooze out to the toner surface layer during heat fixing, and the hot offset resistance is further improved.
On the other hand, when the softening point of a mixture obtained by heating and kneading the binder resin and the polysiloxane derivative B at a mass ratio of 100: 10 is Tm ₂ (° C.), 5.0 ≦ [Tm ₀ -Tm ₂ ] ≦ 12.0, preferably 5.0 ≦ [Tm ₀ −Tm ₂ ] ≦ 9.0.
When [Tm ₀ -Tm ₂ ] is in the above range, the affinity between the binder resin and the organic group part of the polysiloxane derivative B is sufficient, and the polysiloxane derivatives A and B can be sufficiently introduced. Moreover, excessive plasticization of the binder resin can be prevented.

The toner may contain an aliphatic hydrocarbon compound having a melting point of 50 ° C. or higher and 100 ° C. or lower.
The content of the aliphatic hydrocarbon compound is preferably 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the binder resin from the viewpoint of low temperature fixability and chargeability. It is more preferable that the amount is not more than part by mass.
When the aliphatic hydrocarbon compound is heated, the ethylene-vinyl acetate copolymer can be plasticized. Therefore, by containing an aliphatic hydrocarbon compound in the toner, the ethylene-vinyl acetate copolymer forming the matrix at the time of heat fixing of the toner is plasticized, and the low-temperature fixability can be further improved.
Furthermore, an aliphatic hydrocarbon compound having a melting point of 50 ° C. or higher and 100 ° C. or lower can also act as a crystal nucleating agent for an ethylene-vinyl acetate copolymer. Therefore, the micro mobility of the ethylene-vinyl acetate copolymer is suppressed, and the chargeability is improved.
Examples of the aliphatic hydrocarbon compound include aliphatic hydrocarbons having 20 to 60 carbon atoms, such as hexacosane, triacontane, and hexatriacontane.

The toner may contain a colorant. Examples of the colorant include known organic pigments or oil-based dyes, carbon black, and magnetic substances.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like.
Specifically, C.I. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. And CI Pigment Blue 66.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.
Specifically, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 254 and the like.
Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
Specifically, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. And CI Pigment Yellow 194.
Examples of the black colorant include carbon black, a magnetic material, or a material that is toned in black using the yellow colorant, magenta colorant, and cyan colorant.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in the toner.
The content of the colorant 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.

The toner preferably has a volume-based median diameter of 3.0 μm or more and 10.0 μm or less, and more preferably 4.0 μm or more and 7.0 μm or less from the viewpoint of obtaining a high-definition image.
The volume-based median diameter of the toner may be measured by using a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter Co.) by the Coulter method.

As a method for producing the toner, any method can be used, but an emulsion aggregation method capable of easily controlling the particle diameter and particle size distribution of the toner is preferable.
The toner production method of the present invention (hereinafter also simply referred to as the production method of the present invention)
A step of emulsifying the polysiloxane derivative A represented by the structural formula 1 and the polysiloxane derivative B represented by the structural formula 2 to obtain emulsified particles of the polysiloxane derivative A and the polysiloxane derivative B;
A step of micronizing a binder resin containing an ethylene-vinyl acetate copolymer to obtain resin microparticles;
A step of agglomerating the emulsified particles and the resin fine particles to obtain an aggregate; and
A fusion step of fusing the aggregates;
It is characterized by having.
The emulsion aggregation method is a production method for producing toner particles by preparing in advance a resin fine particle dispersion sufficiently small with respect to a target particle diameter and aggregating the resin fine particles in an aqueous medium.
Hereinafter, the toner production method using the emulsion aggregation method will be specifically described, but the present invention is not limited thereto.

<Step of obtaining emulsified particles of polysiloxane derivative>
In this step, the polysiloxane derivative is emulsified in an aqueous medium to prepare emulsified particles of the polysiloxane derivative.
The emulsified particles of the polysiloxane derivative are prepared by a known method. For the preparation, for example, a rotary type homogenizer, a ball mill, a sand mill, an attritor or other media type disperser, a high pressure opposed collision type disperser, or the like may be used.
Specifically, after mixing a polysiloxane derivative in an aqueous medium in which a surfactant is dissolved, the above-mentioned dispersing machine is used to apply shear force to the aqueous medium containing the polysiloxane derivative to emulsify the polysiloxane. An emulsion containing emulsion particles of the derivative may be prepared.
The polysiloxane derivative may be subjected to an emulsification step alone, but since the polysiloxane derivative B assists the introduction of the polysiloxane derivative A into the binder resin, before the emulsification, the polysiloxane derivative A And a step of mixing the polysiloxane derivative B.
In addition, when a polysiloxane derivative has melting | fusing point, it is preferable to perform an emulsification process, after heating an aqueous medium and a polysiloxane derivative more than this melting | fusing point.
Moreover, it is preferable that the addition amount of a polysiloxane derivative shall be 5 to 40 mass% in an aqueous medium.
The surfactant is not particularly limited, but anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap; amine salt type, And cationic surfactants such as quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols.
These surfactants may be used alone or in combination of two or more.
The volume-based median diameter of the emulsion particles of the polysiloxane derivative in the emulsion of the polysiloxane derivative is preferably 0.05 μm or more and 0.5 μm or less, and 0.05 μm or more and 0 or less.
. More preferably, it is 4 μm or less.
The volume-based median diameter may be measured using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso).

<Step of obtaining resin fine particles>
Although the resin fine particles can be produced by a known method, for example, it may be produced by the following method.
A binder resin containing an ethylene-vinyl acetate copolymer, for example, an ethylene-vinyl acetate copolymer and, if necessary, a modified polyethylene resin and / or a crystalline polyester resin, are dissolved in an organic solvent and uniformly dissolved. Form a liquid.
Thereafter, a basic compound and, if necessary, a surfactant are added to prepare a mixed solution. Further, an aqueous medium is added to the mixed solution to form resin fine particles.
Finally, the organic solvent is removed to prepare a resin fine particle dispersion in which resin fine particles are dispersed in an aqueous medium.
When resin fine particles are formed by co-emulsification of an ethylene-vinyl acetate copolymer and a modified polyethylene resin and / or crystalline polyester resin, the modified polyethylene resin and / or crystalline polyester resin and ethylene-vinyl acetate The copolymer is mixed in the resin fine particles. As a result, the polar group of the modified polyethylene resin and / or crystalline polyester resin enhances the dispersion stability of the emulsion, so that the particle size distribution of the toner can be easily controlled.
Specifically, an ethylene-vinyl acetate copolymer, a modified polyethylene resin and / or a crystalline polyester resin are dissolved by heating in an organic solvent, and a basic compound and, if necessary, a surfactant are added to the resulting solution. To prepare a mixture. Subsequently, a co-emulsion liquid (resin fine particle dispersion) containing a resin is prepared by slowly adding an aqueous medium while applying a shearing force with a homogenizer or the like. Alternatively, a co-emulsion liquid containing a resin is prepared by applying a shearing force with a homogenizer or the like after the addition of the aqueous medium.
Thereafter, the organic solvent is removed by heating or decompressing to prepare a resin fine particle co-emulsion (resin fine particle dispersion).
The concentration of the resin component dissolved in the organic solvent is preferably 10% by mass or more and 50% by mass or less, and more preferably 30% by mass or more and 50% by mass or less with respect to the organic solvent.
Any organic solvent can be used as long as it can dissolve the resin. Solvents having high solubility in ethylene-vinyl acetate copolymers such as toluene, xylene, and ethyl acetate are preferred.
The surfactant is not particularly limited, but anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap; amine salt type, And cationic surfactants such as quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols.
Moreover, it is preferable to use together two types, a sulfonate type and a carboxylate type, from a viewpoint of controllability of a particle diameter in the process of obtaining the aggregate mentioned later.
Examples of the basic compound include inorganic substances such as sodium hydroxide and potassium hydroxide, and organic substances such as triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more.
The volume-based median diameter of the resin fine particles is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.1 μm or more and 0.6 μm or less. When the median diameter is within the above range, toner particles having a desired particle diameter can be easily obtained.
The volume-based median diameter may be measured using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso).

<Step of obtaining an aggregate>
In the step of obtaining an agglomerate, a dispersion of the emulsified particles of the polysiloxane derivative and a dispersion of the resin fine particles, and a dispersion of the colorant fine particles and a dispersion of the aliphatic hydrocarbon compound fine particles as necessary are mixed. Prepare a mixture. And each particle contained in the prepared liquid mixture is aggregated, and an aggregate is formed.
As a method for forming an aggregate, a method in which a flocculant is added and mixed in the above-mentioned mixed solution, and a temperature is increased or mechanical power is appropriately added can be suitably exemplified.
The dispersion of the colorant fine particles is prepared by dispersing the colorant in an aqueous medium or the like.
The dispersion liquid of the aliphatic hydrocarbon compound fine particles is prepared by dispersing the aliphatic hydrocarbon compound in an aqueous medium or the like.
The colorant fine particles or the aliphatic hydrocarbon compound fine particles are dispersed by a known method. For example, a media-type disperser such as a rotary shear type homogenizer, a ball mill, a sand mill, and an attritor, a high-pressure counter-collision disperser, etc. Preferably used. In addition, a surfactant or a polymer dispersant that imparts dispersion stability can be added as necessary.
Examples of the flocculant include metal salts of monovalent metals such as sodium and potassium; metal salts of divalent metals such as calcium and magnesium; metal salts of trivalent metals such as iron and aluminum; Examples thereof include polyvalent metal salts such as aluminum.
From the viewpoint of controllability of the particle diameter in the step, it is preferable to use a divalent metal salt such as calcium chloride or magnesium sulfate and a polyvalent metal salt such as polyaluminum chloride in combination.
The addition and mixing of the flocculant is preferably performed in a temperature range from room temperature to 65 ° C. When mixing is performed under this temperature condition, aggregation proceeds in a stable state. The mixing can be performed using a known mixing device, homogenizer, mixer, or the like.
The volume-based median diameter of the aggregate formed in this step is not particularly limited, but is usually 4.0 μm or more and 7.7 so as to be the same as the volume-based median diameter of the toner particles to be obtained. It may be controlled to 0 μm or less. This control can be easily performed, for example, by appropriately setting or changing the temperature at the time of addition and mixing of the flocculant and the like and the stirring and mixing conditions.
The volume-based median diameter of the aggregates may be measured using a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter) by the Coulter method.

<Fusion process>
In the fusing step, the aggregate is heated to the melting point or higher of the ethylene-vinyl acetate copolymer to fuse the aggregate. In this step, resin particles having a smooth aggregate surface are obtained.
In addition, when this aggregate contains a modified polyethylene resin and / or a crystalline polyester resin, it is preferable to heat above the melting point of these resins.
Before entering the fusion step, a chelating agent, a pH adjusting agent, a surfactant or the like can be appropriately added to prevent fusion between the aggregates.
Chelating agents include alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium citrate and sodium citrate, nitrotriacetate (NTA) salts, functionalities of both COOH and OH. And many water-soluble polymers (polymer electrolytes) including the property.
The heating temperature can be arbitrarily set as long as it is between the melting point of the ethylene-vinyl acetate copolymer and the temperature at which the ethylene-vinyl acetate copolymer is thermally decomposed.
As for the heat fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the time of heat fusion depends on the temperature of heating and cannot be defined unconditionally, but is generally 10 minutes or more and 10 hours or less.

After the fusing step, it is preferable to cool the resin particles obtained in the fusing step to a temperature lower than the crystallization temperature of the ethylene-vinyl acetate copolymer (hereinafter also referred to as a cooling step).
Generation of coarse particles can be prevented by cooling to a temperature lower than the crystallization temperature of the ethylene-vinyl acetate copolymer. The cooling rate is preferably about 0.1 ° C./min to 50 ° C./min.
Further, during cooling or after cooling, annealing may be performed to keep the ethylene-vinyl acetate copolymer at a temperature at which the crystallization speed is high and promote crystallization. That is, by holding at a temperature of 30 ° C. or higher and 70 ° C. or lower during or after cooling, crystallization is promoted and blocking resistance during storage of the toner is improved.

  The resin particles produced through the above steps can remove impurities in the resin particles by repeating washing and filtration. Specifically, the resin particles are washed with pure water or alcohol such as methanol or ethanol, and the filtration is repeated a plurality of times to remove metal salts, surfactants, and the like in the resin particles. The number of times of filtration is preferably 3 to 20 times from the viewpoint of production efficiency, and more preferably 3 to 10 times.

The washed resin particles may be dried to obtain toner particles.
In addition, the toner particles may include inorganic particles such as silica fine particles, alumina fine particles, titania fine particles, and calcium carbonate fine particles, and resin particles such as vinyl resin, polyester resin, and silicone resin in a dry state, if necessary. You may add by applying a shearing force.
These inorganic fine particles and resin particles function as external additives such as fluidity aids and cleaning aids.

<Method for measuring acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize an acid component such as free fatty acid or resin acid contained in 1 g of a sample. The acid value is measured according to JIS K 0070-1992. Specifically, the acid value is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95% by volume) is added to make 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 mL of 0.1 mol / L hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the pulverized sample is precisely weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: Mass (g) of the sample.

<Measurement method of molecular weight distribution of resin, etc.>
The molecular weight distribution [number average molecular weight (Mn), weight average molecular weight (Mw) and peak molecular weight (Mp)] of the resin or the like is measured using gel permeation chromatography (GPC) as follows.
Special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added to o-dichlorobenzene for gel chromatography so that the concentration becomes 0.10% by mass, and dissolved at room temperature. The sample and the o-dichlorobenzene added with the BHT are put into a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the sample.
Once the sample has melted, place it in a preheated filter unit and place it on the body. The sample that has passed through the filter unit is used as a GPC sample.
The sample solution is adjusted so that the concentration is about 0.15% by mass.
Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography (addition of 0.10% by mass of BHT)
Flow rate: 1.0 mL / min
Injection volume: 0.4mL
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “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.

<Method for measuring crystallinity of crystalline resin>
The crystallinity of the crystalline resin is measured using the wide angle X-ray diffraction method under the following conditions.
X-ray diffractometer: D8 ADVANCE made by Bruker AXS
X-ray source: Cu-Kα ray (single color with graphite monochromator)
Output: 40kV, 40mA
Slit system: slit DS, SS = 1 °, RS = 0.2 mm,
Measurement range: 2θ = 5 ° -60 °
Step interval: 0.02 °
Scan speed: 1 ° / min
After the crystalline resin was pulverized in a mortar, a wide-angle X-ray diffraction profile was obtained under the above conditions. The obtained wide-angle X-ray diffraction profile is separated into a crystal peak and amorphous scattering, and the crystallinity is calculated from the area using the following formula.
Crystallinity (%) = Ic / (Ic + Ia) × 100
Ic: Total area of crystal peaks detected in the range of 5 ° ≦ 2θ ≦ 60 ° Ia: Total area of amorphous scattering detected in the range of 5 ° ≦ 2θ ≦ 60 °

<Measuring method of kinematic viscosity of polysiloxane derivative>
The kinematic viscosity of the polysiloxane derivative is measured at 25 ° C. using a fully automatic microkinematic viscometer (manufactured by Viscotec Corporation).

<Method of measuring elongation at break of ethylene-vinyl acetate copolymer>
The breaking elongation of the ethylene-vinyl acetate copolymer is measured under conditions based on JIS K 7162.

<Ethylene-vinyl acetate copolymer structure determination>
The structure of the ethylene-vinyl acetate copolymer can be measured using a general analytical technique, and for example, techniques such as nuclear magnetic resonance (NMR) and pyrolysis gas chromatography can be applied.
For example, the content ratio of each monomer unit in an ethylene-vinyl acetate copolymer (monomer unit ratio derived from vinyl acetate: 15% by mass) by ¹ H-NMR is calculated by the following method.
A solution of 5 mg of ethylene-vinyl acetate copolymer dissolved in 0.5 mL of heavy acetone containing tetramethylsilane as an internal standard of 0.00 ppm is put in a sample tube, the repetition time is 2.7 seconds, and the number of integrations is 16 times. The ¹ H-NMR spectrum is measured under the following conditions.
The peak of 1.14 to 1.36 ppm corresponds to CH ₂ —CH ₂ of the monomer unit derived from ethylene, and the peak near 2.04 ppm corresponds to CH ₃ of the monomer unit derived from vinyl acetate. The ratio of the integrated values of those peaks is calculated to calculate the content ratio of each monomer unit.
<Structure determination of polysiloxane derivative>
The polysiloxane derivative contained in the toner can be separated from the toner as a hexane-dissolved material by dispersing the toner in hexane, heating it at 50 ° C. for 10 minutes, and then filtering off and collecting the filtrate.
From the mixture of the polysiloxane derivatives A and B contained in hexane, for example, the polysiloxane derivative B is isolated by using a recrystallization method or the like, and an existing analytical method such as infrared spectroscopy or nuclear magnetic resonance (NMR) is used. Can be used to determine the structure.
Similarly, the polysiloxane derivative A can be analyzed by analyzing the mixture of the polysiloxane derivatives A and B by NMR or the like and removing the detection data derived from the polysiloxane derivative B.
As a specific analysis means, ²⁹ Si-NMR is used.
For example, when a ²⁹ Si-NMR spectrum of dimethylpolysiloxane was measured, a peak derived from Si—O (CH ₃ ) ₃ was observed in the vicinity of 6-8 ppm, and —O—Si (CH ₃ ) ₂ — was observed in the vicinity of 20-23 ppm. O-derived peaks can be observed.

  Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, the aspect of this invention is not limited to these. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Example of production of resin fine particle 1 dispersion>
-Toluene (manufactured by Wako Pure Chemical Industries) 300 parts-Ethylene-vinyl acetate copolymer (A) 100 parts (content of monomer units derived from vinyl acetate: 15 mass%, weight average molecular weight (Mw): 110,000, Melt flow rate: 12 g / 10 min, melting point: 86 ° C., elongation at break = 700%)
Crystalline polyester resin (B) 25 parts [composition (molar ratio) [1,9-nonanediol: sebacic acid = 100: 100], number average molecular weight (Mn): 5,500, weight average molecular weight (Mw): 15,500, peak molecular weight (Mp): 11,400, melting point: 72 ° C., acid value: 13 mgKOH / g]
The above formulations were mixed and dissolved at 90 ° C.
Separately, 1.2 parts of sodium dodecylbenzenesulfonate, 0.6 parts of sodium laurate, and 1.6 parts of N, N-dimethylaminoethanol were added to 700 parts of ion-exchanged water and dissolved by heating at 90 ° C.
Next, the above toluene solution and aqueous solution were mixed together, K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics).
Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.).
Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (resin fine particle 1 dispersion) having a resin fine particle 1 concentration of 20%.
The volume-based median diameter of the resin fine particles 1 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.65 μm.

<Example of production of resin fine particle 2 dispersion>
Crystalline polyester resin (B) is ethylene-methacrylic acid copolymer (C) [content of monomer unit derived from methacrylic acid: 15% by mass, melt flow rate: 60 g / 10 min, melting point: 90 ° C., acid value : 90 mg KOH / g) A resin fine particle 2 dispersion was obtained in the same manner as in the production example of the resin fine particle 1 dispersion, except that 25 parts were changed. The obtained resin fine particles 2 had a volume-based median diameter of 0.55 μm.

<Example of production of resin fine particle 3 dispersion>
The amount of ethylene-vinyl acetate copolymer (A) used is 50 parts, the amount of crystalline polyester resin (B) used is 37.5 parts, the amount of N, N-dimethylaminoethanol used is 4.8 parts, Further, a resin fine particle 3 dispersion was obtained in the same manner as in the production example of the resin fine particle 1 dispersion, except that 37.5 parts of ethylene-methacrylic acid copolymer (C) was used. The volume-based median diameter of the obtained resin fine particles 3 was 0.45 μm.

<Example of production of resin fine particle 4 dispersion>
Tetrahydrofuran (Wako Pure Chemical Industries) 250 parts Crystalline polyester resin (B) 25 parts Polyester resin (D) 100 parts [Composition (mol%) [Polyoxypropylene (2.2) -2,2-bis ( 4-hydroxyphenyl) propane: isophthalic acid: terephthalic acid = 100: 50: 50], number average molecular weight (Mn): 4,600, weight average molecular weight (Mw): 16,500, peak molecular weight (Mp): 10, 400, Mw / Mn: 3.6, softening point (Tm): 122 ° C., glass transition temperature (Tg): 70 ° C., acid value: 10 mgKOH / g]
Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 0.6 parts The above formulation was mixed and dissolved at 50 ° C.
Next, 2.7 parts of N, N-dimethylaminoethanol was added, and an ultra-high speed stirring device T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primemics).
Furthermore, 400 parts of ion-exchanged water was added at a rate of 1 part / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (resin fine particle 4 dispersion) having a concentration of resin fine particles 4 of 20%. The obtained resin fine particles 4 had a volume-based median diameter of 0.20 μm.

<Production example of polysiloxane derivative A1 emulsion>
Polysiloxane derivative A1 20.0 parts (dimethyl silicone oil, Shin-Etsu Chemical Co., Ltd .: KF96-50CS, kinematic viscosity at 25 ° C. 50 mm ² / s)
・ 1.0 part of anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) ・ 79.0 parts of ion-exchanged water Mix for about 1 hour using a high-pressure impact disperser Nanomizer (Yoshida Kikai Kogyo Co., Ltd.) An emulsified liquid having a concentration of 20% of polysiloxane derivative A1 obtained by dispersing and dispersing polysiloxane derivative A1 was prepared. When the volume-based median diameter of the polysiloxane derivative A1 emulsion particles in the obtained emulsion of the polysiloxane derivative A1 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), 0.09 μm Met.

<Production example of polysiloxane derivative A2 emulsion>
Polysiloxane derivative A1 is converted to polysiloxane derivative A2 (dimethylsilicone oil).
A polysiloxane derivative A2 emulsion was produced in the same manner as in the production example of the polysiloxane derivative A1 emulsion, except that it was changed to Shin-Etsu Chemical Co., Ltd .: KF96-1000CS, kinematic viscosity at 25 ° C. 1000 mm ² / s). The volume-based median diameter of the polysiloxane derivative A2 emulsified particles in the obtained emulsion of the polysiloxane derivative A2 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: Nikkiso Co., Ltd.). Met.

<Production Example of Polysiloxane Derivative A3 Emulsion>
The same method as in the production example of the polysiloxane derivative A1 emulsion except that the polysiloxane derivative A1 was changed to polysiloxane derivative A3 (dimethylsilicone oil manufactured by Shin-Etsu Chemical Co., Ltd .: KF96-3000CS, kinematic viscosity at 25 ° C. 3000 mm ² / s). To produce a polysiloxane derivative A3 emulsion. When the volume-based median diameter of the polysiloxane derivative A3 emulsion particles in the obtained emulsion of the polysiloxane derivative A3 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: Nikkiso Co., Ltd.), it was 0.22 μm. Met.

<Production example of polysiloxane derivative A4 emulsion>
The same as the production example of the polysiloxane derivative A1 emulsion, except that the polysiloxane derivative A1 was changed to polysiloxane derivative A4 (methyl phenyl silicone oil, Shin-Etsu Chemical Co., Ltd .: KF50-100CS, kinematic viscosity at 25 ° C. 100 mm ² / S). The polysiloxane derivative A4 emulsion was manufactured by the method. When the volume-based median diameter of the polysiloxane derivative A4 emulsion particles in the obtained emulsion of the polysiloxane derivative A4 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), 0.27 μm Met.

<Production Example of Polysiloxane Derivative B1 Emulsion>
・ 20.0 parts of polysiloxane derivative B1 (stearoxymethicone / dimethylpolysiloxane copolymer manufactured by Shin-Etsu Chemical Co., Ltd .: KF-7002, melting point: 45 ° C.)
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part-Ion-exchanged water 79.0 parts The above was mixed, and the mixture was heated to 60 ° C. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, an emulsified liquid of polysiloxane derivative B1 was obtained by emulsifying at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). When the volume-based median diameter of the polysiloxane derivative B1 emulsion particles in the obtained emulsion of the polysiloxane derivative B1 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: Nikkiso Co., Ltd.), it was 0.35 μm. Met.

<Production example of polysiloxane derivative B2 emulsion>
A method similar to the production example of the polysiloxane derivative B1 emulsion except that the polysiloxane derivative B1 is changed to a polysiloxane derivative B2 (acrylic polymer / dimethylpolysiloxane copolymer, Shin-Etsu Chemical Co., Ltd .: KP-562P, melting point 50 ° C.). To produce a polysiloxane derivative B2 emulsion. The volume-based median diameter of the polysiloxane derivative B2 emulsion particles in the obtained polysiloxane derivative B2 emulsion was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: Nikkiso Co., Ltd.). Met.

<Production example of polysiloxane derivative B3 emulsion>
The same as the production example of the polysiloxane derivative B1 emulsion except that the polysiloxane derivative B1 was changed to a polysiloxane derivative B3 (carboxyl-modified silicone oil, Shin-Etsu Chemical Co., Ltd .: X22-162C, kinematic viscosity at 25 ° C. 220 mm ² / s). A polysiloxane derivative B3 emulsion was prepared by this method. The volume-based median diameter of the polysiloxane derivative B3 emulsion particles in the obtained emulsion of the polysiloxane derivative B3 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.). Met.

<Production Example of Polysiloxane Derivative A1 + B1 Co-Emulsion>
Polysiloxane derivative A1 20.0 parts (dimethyl silicone oil, Shin-Etsu Chemical Co., Ltd .: KF96-50CS, kinematic viscosity at 25 ° C. 50 mm ² / s)
・ 2.0 parts of polysiloxane derivative B1 (stearoxymethicone / dimethylpolysiloxane copolymer manufactured by Shin-Etsu Chemical Co., Ltd .: KF-7002, melting point 45 ° C.)
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.1 parts-Ion-exchanged water 86.9 parts K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primemics). Furthermore, co-emulsified liquid of polysiloxane derivative A1 and polysiloxane derivative B1 was obtained by emulsifying at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). The volume-based median diameter of the emulsified particles of the polysiloxane derivative A1 and polysiloxane derivative B1 in the obtained co-emulsified liquid was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso). .32 μm.

<Example of Production of Aliphatic Hydrocarbon Compound Fine Particle Dispersion>
Aliphatic hydrocarbon compound (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa) 20.0 parts Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.0 parts Ion-exchanged water 79. After putting 0 parts or more into a mixing vessel equipped with a stirrer, the mixture was heated to 90 ° C. and circulated to Claremix W-Motion (M Technique) for 60 minutes. The conditions for distributed processing were as follows.
・ Rotor outer diameter 3cm
・ Clearance 0.3mm
・ Rotor speed 19000r / min
・ Screen rotation speed 19000r / min
After the dispersion treatment, the system is cooled to 40 ° C. under the cooling treatment conditions of a rotor rotational speed of 1000 r / min, a screen rotational speed of 0 r / min, and a cooling rate of 10 ° C./min. A dispersion (aliphatic hydrocarbon compound fine particle dispersion) was obtained.
The volume-based median diameter of the aliphatic hydrocarbon compound fine particles in the obtained dispersion was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.15 μm.

<Production Example of Colorant Fine Particle Dispersion>
Colorant 10.0 parts (Cyan pigment, manufactured by Dainichi Seika: Pigment Blue 15: 3)
・ Anionic surfactant (Daiichi Kogyo Seiyaku: Neogen RK) 1.5 parts ・ Ion-exchanged water 88.5 parts Mix and dissolve the above. An aqueous dispersion (colorant fine particle dispersion) having a concentration of 10% of colorant fine particles obtained by dispersing the colorant for about 1 hour was prepared. The volume-based median diameter of the colorant fine particles in the obtained dispersion was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.20 μm.

<Production Example of Toner 1>
-Resin fine particle 1 dispersion 100 parts-Polysiloxane derivative A1 emulsion 10 parts-Polysiloxane derivative B1 emulsion 4.5 parts-Aliphatic hydrocarbon compound fine particle dispersion 30 parts-Colorant fine particle dispersion 10 parts-Ion exchange 20 parts of water Each of the above materials was placed in a round stainless steel flask and mixed, and then 6 parts of a 2% polyaluminum chloride aqueous solution and 60 parts of a 2% magnesium sulfate aqueous solution were added.
Subsequently, the mixture was dispersed for 10 minutes at 5000 r / min using a homogenizer (manufactured by IKA: Ultra Tarrax T50).
Then, it heated to 60 degreeC, using the stirring blade in the heating water bath, adjusting suitably the rotation speed that a liquid mixture is stirred. After holding at 60 ° C. for 20 minutes, the volume-based median diameter of the formed aggregated particles was measured using Coulter Multisizer III, and it was confirmed that aggregated particles of about 6.0 μm were formed.
After adding 240 parts of 5% ethylenediamine tetraacetate aqueous solution to the above dispersion of aggregated particles, 4000 parts of ion-exchanged water was added, and the mixture was heated to 95 ° C. while stirring was continued. And the aggregated particle was united by hold | maintaining at 95 degreeC for 1 hour.
Then, it cooled to 50 degreeC and accelerated | stimulated crystallization of the ethylene-vinyl acetate copolymer by hold | maintaining for 3 hours. Then, after cooling to 25 degreeC and filtering and solid-liquid separation, the residue was fully wash | cleaned with ethanol, and also it wash | cleaned with ion-exchange water.
After the washing, toner particles 1 were obtained by drying using a vacuum dryer.
For 100 parts of toner particles 1, 1.5 parts of silica fine particles hydrophobized with primary particle number average diameter of 10 nm and silica fine particles hydrophobized with primary particle number average diameter of 100 nm Toner 1 was obtained by dry-mixing 2.5 parts with a Henschel mixer (Mitsui Mine). The obtained toner 1 had a volume-based median diameter of 5.2 μm.

<Production Example of Toner 2>
Toner 2 was obtained in the same manner as in the production example of toner 1 except that the amount of the polysiloxane derivative A1 emulsion was 25 parts and the amount of the polysiloxane derivative B1 emulsion was 11.25 parts. The volume-based median diameter of the obtained toner 2 was 5.3 μm.

<Production Example of Toner 3>
A toner 3 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle 1 dispersion was changed to the resin fine particle 2 dispersion. The obtained toner 3 had a volume-based median diameter of 5.1 μm.

<Production Example of Toner 4>
A toner 4 was obtained in the same manner as in the production example of the toner 1 except that the amount of the polysiloxane derivative B1 emulsion was 1 part. The obtained toner 4 had a volume-based median diameter of 4.9 μm.

<Production Example of Toner 5>
Toner 5 was obtained in the same manner as in the production example of toner 1, except that 11 parts of polysiloxane derivative A1 + B1 co-emulsified liquid was used instead of polysiloxane derivative A1 emulsion and polysiloxane derivative B1 emulsion. The resulting toner 5 had a volume-based median diameter of 4.9 μm.

<Production Example of Toner 6>
A toner 6 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative A1 emulsion was changed to the polysiloxane derivative A2 emulsion. The resulting toner 6 had a volume-based median diameter of 5.6 μm.

<Production Example of Toner 7>
A toner 7 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative B1 emulsion was changed to the polysiloxane derivative B2 emulsion. The obtained toner 7 had a volume-based median diameter of 4.9 μm.

<Production Example of Toner 8>
A toner 8 was obtained in the same manner as in the production example of the toner 1 except that the resin fine particle 1 dispersion was changed to the resin fine particle 3 dispersion. The obtained toner 8 had a volume-based median diameter of 5.1 μm.

<Production Example of Toner 9>
A toner 9 was obtained in the same manner as in the production example of the toner 1 except that the amount of the polysiloxane derivative A1 emulsion was 3 parts and the amount of the polysiloxane derivative B1 emulsion was 1.35 parts. The obtained toner 9 had a volume-based median diameter of 5.3 μm.

<Production Example of Toner 10>
A toner 10 was obtained in the same manner as in the production example of the toner 1 except that the amount of the polysiloxane derivative A1 emulsion was 40 parts and the amount of the polysiloxane derivative B1 emulsion was 18 parts. The toner 10 thus obtained had a volume-based median diameter of 5.6 μm.

<Production Example of Toner 11>
Toner 11 was obtained in the same manner as in the production example of toner 1 except that the amount of the polysiloxane derivative B1 emulsion was 0.3 parts. The toner 11 thus obtained had a volume-based median diameter of 5.4 μm.

<Production Example of Toner 12>
A toner 12 was obtained in the same manner as in the production example of the toner 1 except that the amount of the polysiloxane derivative B1 emulsion was 10 parts. The toner 12 thus obtained had a volume-based median diameter of 5.3 μm.

<Production Example of Toner 13>
A toner 13 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative A1 emulsion was changed to a polysiloxane derivative A3 emulsion. The volume-based median diameter of the obtained toner 13 was 5.8 μm.

<Production Example of Toner 14>
A toner 14 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative A1 emulsion was changed to a polysiloxane derivative A4 emulsion. The toner 14 thus obtained had a volume-based median diameter of 5.2 μm.

<Production Example of Toner 15>
A toner 15 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative B1 emulsion was changed to the polysiloxane derivative B3 emulsion. The obtained toner 15 had a volume-based median diameter of 5.1 μm.

<Production Example of Toner 16>
A toner 16 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative A1 emulsion and the polysiloxane derivative B1 emulsion were not used. The resulting toner 16 had a volume-based median diameter of 5.8 μm.

<Production Example of Toner 17>
A toner 17 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative B1 emulsion was not used. The obtained toner 17 had a volume-based median diameter of 5.4 μm.

<Production Example of Toner 18>
A toner 18 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative A1 emulsion was not used. The toner 18 thus obtained had a volume-based median diameter of 5.4 μm.

<Production Example of Toner 19>
A toner 19 was obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative B1 emulsion was not used, the amount of the polysiloxane derivative A1 emulsion was 5 parts, and further 5 parts of the polysiloxane derivative A2 emulsion was used. It was. The obtained toner 19 had a volume-based median diameter of 5.2 μm.

<Production Example of Toner 20>
A toner 20 is obtained in the same manner as in the production example of the toner 1 except that the polysiloxane derivative B1 emulsion is not used, the amount of the polysiloxane derivative B1 emulsion is 5 parts, and the polysiloxane derivative B2 emulsion is 5 parts. It was. The volume-based median diameter of the obtained toner 20 was 5.1 μm.

<Production Example of Toner 21>
-Resin fine particle 4 dispersion 100 parts-Polysiloxane derivative A1 emulsion 10 parts-Aliphatic hydrocarbon compound fine particle dispersion 30 parts-Colorant fine particle dispersion 10 parts-Ion-exchanged water 60 parts After putting into a flask and mixing, 20 parts of 2% magnesium sulfate aqueous solution was added.
Subsequently, the mixture was dispersed for 10 minutes at 5000 r / min using a homogenizer (manufactured by IKA: Ultra Tarrax T50).
Thereafter, the mixture was heated to 65 ° C. using a stirring blade in a heating water bath while appropriately adjusting the rotation speed so that the mixed solution was stirred. After maintaining at 65 ° C. for 30 minutes, the volume-based median diameter of the formed aggregated particles was measured using Coulter Multisizer III, and it was confirmed that aggregated particles of about 5.7 μm were formed.
After adding 100 parts of 5% ethylenediamine tetraacetate aqueous solution to the above dispersion of aggregated particles, 200 parts of ion-exchanged water was added, and the mixture was heated to 95 ° C. while stirring was continued. And the aggregated particle was united by hold | maintaining at 95 degreeC for 5 hours.
Thereafter, the mixture was cooled to 25 ° C., filtered and solid-liquid separated, and then washed with ion exchange water. After cleaning, toner particles 21 were obtained by drying using a vacuum dryer.
For 100 parts of toner particles 21, 1.5 parts of silica fine particles hydrophobized with primary particle number average diameter of 10 nm and silica fine particles hydrophobized with primary particle number average diameter of 100 nm 2.5 parts of the mixture was dry-mixed with a Henschel mixer (manufactured by Mitsui Mining) to obtain toner 21. The obtained toner 21 had a volume-based median diameter of 5.0 μm.

<Production Example of Toner 22>
A toner 22 was obtained in the same manner as in the production example of the toner 21 except that 10 parts of the polysiloxane derivative B1 emulsion was used without using the polysiloxane derivative A1 emulsion. The volume-based median diameter of the obtained toner 22 was 5.1 μm.

<Production example of toner 23>
80 parts of ethylene-vinyl acetate copolymer (E) (content of monomer unit derived from vinyl acetate: 20% by mass, melt flow rate: 200 g / 10 min, melting point: 75 ° C., elongation at break = 210%)
・ Crystalline polyester resin (B) 20 parts ・ Polysiloxane derivative A1 10 parts ・ Aliphatic hydrocarbon compound (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa) 30 parts ・ Colorant 5 parts (Cyan Pigment Dainichi Seika) (Made by Pigment Blue 15: 3)
The above materials were premixed with a Henschel mixer and then melt kneaded for 1 hour using a twin-screw kneading extruder (PCM-30: manufactured by Ikegai Iron Works Co., Ltd.) set at 130 ° C. and 200 rpm.
The obtained kneaded product is cooled and coarsely pulverized with a cutter mill, and then the obtained coarsely pulverized product is finely pulverized using a turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.), and a multi-division classifier utilizing the Coanda effect. Was used to classify toner particles 23.
For 100 parts of toner particles 23, 1.5 parts of hydrophobized silica fine particles with a primary particle number average diameter of 10 nm and hydrophobized silica fine particles with a primary particle number average diameter of 100 nm 2.5 parts of the mixture was dry mixed with a Henschel mixer (manufactured by Mitsui Mining) to obtain toner 23. The toner 23 thus obtained had a volume-based median diameter of 6.4 μm.

<Examples 1-15 and Comparative Examples 1-8>
The following evaluation tests were performed using toners 1 to 23. The evaluation results are shown in Table 2.

<Evaluation of low-temperature fixability>
Toner and a ferrite carrier surface-coated with a silicone resin (average particle size 42 μm) were mixed so that the toner concentration was 8% by mass to prepare a two-component developer.
A commercially available full color digital copying machine (CLC1100, manufactured by Canon Inc.) was used to form an unfixed toner image (0.6 mg / cm ² ) on image receiving paper (64 g / m ² ).
A fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed toner image was performed using the fixing unit.
The process speed was set to 246 mm / second in a normal temperature and humidity environment, and the appearance when the unfixed toner image was fixed was visually evaluated.
A: Fixing is possible at a temperature of 120 ° C. or lower B: Fixing is possible at a temperature higher than 120 ° C. and 140 ° C. or lower C: Fixing is possible at a temperature higher than 140 ° C.

<Evaluation of hot offset resistance>
A fixing test was performed in the same manner as the evaluation of the low-temperature fixability, and the appearance when the image was fixed was visually evaluated.
A: Fixing is possible at a temperature of 180 ° C. or higher B: Fixing is possible at a temperature of 160 ° C. or higher, hot offset occurs at a temperature of 180 ° C. or higher C: Fixing is possible at a temperature of 160 ° C. or lower, Hot offset occurs at temperatures of 160 ° C or higher, or there is no temperature range that can be fixed

<Evaluation of fluidity after long-term storage>
The toner was allowed to stand in a constant temperature and humidity chamber at a temperature of 30 ° C. and a humidity of 50% RH for one month, and the degree of blocking was evaluated visually.
A: Blocking does not occur, or even if blocking occurs, it disperses easily by light vibration. B: Blocking occurs, but disperses if it continues to vibrate. C: Blocking occurs. Even if force is applied, it does not disperse.

<Evaluation of blocking resistance>
The toner was allowed to stand for 3 days in a constant temperature and humidity chamber under conditions of a temperature of 50 ° C. and a humidity of 50% RH, and the degree of blocking was evaluated visually.
A: Blocking does not occur, or even if blocking occurs, it disperses easily by light vibration. B: Blocking occurs, but disperses if it continues to vibrate. C: Blocking occurs. Even if force is applied, it does not disperse.

<Evaluation of introduction rate of polysiloxane derivative>
The amount of polysiloxane derivative introduced into the completed toner was evaluated by detecting elemental Si using fluorescent X-rays in preparation for toner preparation.
The method will be described below.
Binder resins, polysiloxane derivatives A and B, and a colorant were melt-kneaded so as to have the same composition ratio as that of toner particles 1 to 23, and kneaded materials 1 to 23 were obtained.
50 mg of the obtained kneaded material was hot-pressed to prepare kneaded material thin films 1 to 23 having a size that can be accommodated in the inner frame 2 of a minute sample measuring container described later.
1 was prepared for each of toner particles 1 to 23 and kneaded material thin films 1 to 23.
The trace sample measuring container 10 is a container that can measure a very small amount of powder or thin film sample in a vacuum atmosphere and collect it as it is.
The manufacturing method of the trace sample measuring container 10 is as follows.
A microporous film 5 is placed on the inner frame 2 of the trace sample measuring container, and further 50 mg of toner or a kneaded material thin film (measurement sample 3) is placed thereon and covered with the cover film 4.
The cover film 4 is fixed by the minute sample measuring container outer frame 1.
The microporous film 5 is air permeable and allows air between sample particles to pass therethrough.
Moreover, the trace sample measuring container outer frame 1 and the trace sample measuring container inner frame 2 are made of polyethylene, the microporous film 5 is made of polypropylene, and the cover film 4 is made of prolene, and does not contain elemental Si.
The Kα peak angle of the element Si is 2θ = 109.05 (°). Then, the calibration curve sample is put into the fluorescent X-ray analyzer, and the sample chamber is depressurized and evacuated.
The X-ray intensity of each sample was determined under the following conditions.
<Measurement conditions>
Equipment ZSX100s (Rigaku Denki Kogyo Co., Ltd.)
Measurement potential, voltage 50kV-50mA
2θ angle 109.05 (°)
Crystal plate PET
Measurement time 60 seconds The X-ray intensity of each toner particle and the kneaded material thin film was determined, and the introduction rate of the polysiloxane derivative was determined according to the following formula.
(Formula) “Polysiloxane derivative introduction rate” = {(X-ray intensity of toner particles) / (X-ray intensity of kneaded material thin film)} × 100

In Table 1,
In the toner production method, “1” means an emulsion aggregation method, and “2” means a melt-kneading method.
In the polysiloxane derivative A, “X” means the ratio (parts by mass) of the polysiloxane derivative A to 100 parts by mass of the binder resin.
In the polysiloxane derivative B, “Y” means the ratio (parts by mass) of the polysiloxane derivative B to 100 parts by mass of the polysiloxane derivative A, and “Z” represents the polysiloxane derivative B with respect to 100 parts by mass of the binder resin. It means a ratio (part by mass).

1: Outer frame of trace sample measurement container, 2: Inner frame of trace sample measurement container, 3: Measurement sample, 4: Cover film, 5: Microporous film, 10: Trace sample measurement container

Claims (13)

A toner containing a binder resin containing an ethylene-vinyl acetate copolymer, a polysiloxane derivative A represented by the following structural formula 1, and a polysiloxane derivative B represented by the following structural formula 2.

(In Structural Formula 1, R _{1 to} R ₁₀ each independently represent a methyl group or a phenyl group, and l, m, and n each independently represent an integer of 1 or more.)

(In Structural Formula 2, at least one of R _{11 to} R ₂₀ has a C _4-30 alkyl group, a C _4-30 alkoxy group, an acrylic group, an amino group, a methacryl group, or a carboxy group. (It is an organic group, and the others independently represent a methyl group or a phenyl group, and p, q, and r each independently represent an integer of 1 or more.) The content of the polysiloxane derivative A is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.
The toner according to claim 1, wherein the content of the polysiloxane derivative B is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polysiloxane derivative A.   The toner according to claim 1, wherein the content of the ethylene-vinyl acetate copolymer in the binder resin is 50% by mass or more and 100% by mass or less. The toner according to claim 1, wherein the polysiloxane derivative A has a kinematic viscosity at 25 ° C. of 5 mm ² / s or more and 1000 mm ² / s or less.   The toner according to claim 1, wherein the polysiloxane derivative B has a melting point of 20 ° C. or higher and 70 ° C. or lower. The softening point of the binder resin is Tm ₀ (° C.)
The softening point of the mixture obtained by heating and kneading the binder resin and the polysiloxane derivative A at a mass ratio of 100: 10 is Tm ₁ (° C.),
When the softening point of the mixture obtained by heating and kneading the binder resin and the polysiloxane derivative B at a mass ratio of 100: 10 is Tm ₂ (° C.),
The toner according to claim 1, wherein the toner satisfies the relationship of the following formulas 1 and 2.
(Formula 1) 0.0 ≦ [Tm ₀ −Tm ₁ ] ≦ 3.0
(Formula 2) 5.0 ≦ [Tm ₀ −Tm ₂ ] ≦ 12.0 A step of emulsifying a polysiloxane derivative A represented by the following structural formula 1 and a polysiloxane derivative B represented by the following structural formula 2 to obtain emulsified particles of the polysiloxane derivative A and the polysiloxane derivative B;
A step of micronizing a binder resin containing an ethylene-vinyl acetate copolymer to obtain resin microparticles;
A step of agglomerating the emulsified particles and the resin fine particles to obtain an aggregate; and
A fusion step of fusing the aggregates;
A method for producing a toner comprising:

(In Structural Formula 1, R _{1 to} R ₁₀ each independently represent a methyl group or a phenyl group, and l, m, and n each independently represent an integer of 1 or more.)

(In Structural Formula 2, at least one of R _{11 to} R ₂₀ has a C _4-30 alkyl group, a C _4-30 alkoxy group, an acrylic group, an amino group, a methacryl group, or a carboxy group. (It is an organic group, and the others independently represent a methyl group or a phenyl group, and p, q, and r each independently represent an integer of 1 or more.) The step of obtaining the emulsified particles comprises:
A step of mixing the polysiloxane derivative A represented by the structural formula 1 and the polysiloxane derivative B represented by the structural formula 2 before the emulsification,
The method for producing a toner according to claim 7. The content of the polysiloxane derivative A is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.
The method for producing a toner according to claim 7 or 8, wherein the content of the polysiloxane derivative B is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polysiloxane derivative A.   10. The toner production method according to claim 7, wherein the content of the ethylene-vinyl acetate copolymer in the binder resin is 50% by mass or more and 100% by mass or less. The method for producing a toner according to claim 7, wherein the polysiloxane derivative A has a kinematic viscosity at 25 ° C. of 5 mm ² / s or more and 1000 mm ² / s or less.   The toner production method according to claim 7, wherein the polysiloxane derivative B has a melting point of 20 ° C. or higher and 70 ° C. or lower. The softening point of the binder resin is Tm ₀ (° C.)
The softening point of the mixture obtained by heating and kneading the binder resin and the polysiloxane derivative A at a mass ratio of 100: 10 is Tm ₁ (° C.),
When the softening point of the mixture obtained by heating and kneading the binder resin and the polysiloxane derivative B at a mass ratio of 100: 10 is Tm ₂ (° C.),
The method for producing a toner according to any one of claims 7 to 12, which satisfies a relationship of the following formulas 1 and 2.
(Formula 1) 0.0 ≦ [Tm ₀ −Tm ₁ ] ≦ 3.0
(Formula 2) 5.0 ≦ [Tm ₀ −Tm ₂ ] ≦ 12.0