JP2019066711A - TONER AND METHOD FOR MANUFACTURING TONER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in low-temperature fixability, hot offset resistance and charge retention. A toner having toner particles containing a resin component, wherein the resin component contains a urethane group-containing olefin copolymer A, and the urethane group-containing olefin copolymer A has the following formula (1) And at least one structure Z2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3): A toner characterized in that the concentration of urethane groups of united A is 2% by mass or more and 24% by mass or less. 【Selection chart】 None

Description

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

  In recent years, in the image formation, as the demand for energy saving is increased, efforts are made to lower the fixing temperature of toner.

As one of methods for improving the low-temperature fixability of the toner, Patent Documents 1 to 3 propose a technique using a crystalline polyester resin having a sharp melt property, in which the viscosity is greatly reduced when the melting point is exceeded.
However, since crystalline polyester resin has high molecular mobility and polarity, there is a problem that the charge retention of the toner is lowered.
In Patent Documents 4 to 8, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer or ethylene, which is an olefin resin having a low glass transition temperature and melting point, in order to improve fixability. Proposals have also been made for toners containing an ester group-containing ethylene-based copolymer such as methyl methacrylate copolymer.
However, low temperature fixability was insufficient only by adding a part of these copolymers.
Thus, Patent Document 9 proposes a technique for improving low-temperature fixability and charge retention by using an ethylene-vinyl acetate copolymer or an ethylene-ethyl acrylate copolymer as a main binder.

Japanese Patent Publication No. 56-13943 Japanese Examined Patent Publication No. 62-39428 JP-A-4-120554 JP, 2011-107261, A JP-A-11-202555 JP-A-8-184986 JP-A-4-21860 JP-A-3-150576 JP, 2016-224422, A

However, when an ethylene-vinyl acetate copolymer, an ethylene-ethyl acrylate copolymer, or the like as described in Patent Document 9 is used as a main binder, the hot offset resistance of the low temperature fixability is improved. The problem of falling
The present inventors attempted to use a commonly known high molecular weight resin in combination in order to improve the hot offset resistance. However, it is believed that the ester group-containing olefin copolymer has low polarity and low intermolecular force, and therefore, the high offset resistance of the high molecular weight resin of the ester group-containing olefin copolymer is also possible. Could not improve.
The present invention provides a toner excellent in low-temperature fixability, hot offset resistance, and charge retention, and a method for producing the toner.

The present inventors include a urethane group in the olefin material to cope with the problem of the hot offset resistance of the toner using the olefin material, and increase the cohesion by the intramolecular hydrogen bond, and the hot offset resistance We tried to improve the sex.
As a result, it has been found that it is possible to obtain hot offset resistance by using an olefin copolymer having a urethane group.
Further, since the polarity difference between the urethane group and the olefin structure which is the main skeleton is large, the highly polar urethane group causes microphase separation in the low polarity olefin structure, and the charge retention is further improved. Furthermore, the low temperature fixability was also good due to the olefin resin having a low glass transition temperature (Tg).

That is, the present invention
A toner having toner particles containing a resin component,
The resin component contains a urethane group-containing olefin copolymer A;
The urethane group-containing olefin copolymer A is
A structure Z1 represented by the following formula (1), and at least one structure Z2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The toner is characterized in that the urethane group concentration of the urethane group-containing olefin copolymer A is 2% by mass or more and 24% by mass or less.

Also, the present invention is
A method for producing a toner having toner particles containing a resin component, comprising:
The resin component contains a urethane group-containing olefin copolymer A;
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium, or
Dispersing the resin composition in which the resin component is dissolved in an organic solvent in an aqueous medium to prepare particles of the resin composition,
The urethane group-containing olefin copolymer A is
A structure Z1 represented by the following formula (1), and at least one structure Z2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The method for producing a toner is characterized in that the urethane group concentration of the urethane group-containing olefin copolymer A is 2% by mass or more and 24% by mass or less.

（該式（１）〜（３）中、Ｒ^１はＨ又はＣＨ_３であり、Ｒ^２はＨ又はＣＨ_３であり、Ｒ^３は有機基であり、Ｒ^４はＨ又はＣＨ_３であり、Ｒ^５は有機基である。）

(In the formulas (1) to (3), R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is an organic group, R ⁴ is H or CH ₃ , R ⁵ is an organic group)

  According to the present invention, it is possible to provide a toner and a method for producing the toner, which are excellent in low-temperature fixability, hot offset resistance and charge retention.

In the present invention, the descriptions of “more than or equal to or less than xxx” and “o to xxx” indicating numerical ranges mean numerical ranges including the lower limit and the upper limit which are end points unless otherwise noted.
Moreover, a monomer unit means the reacted form of the monomer substance in a polymer or resin.
The crystalline resin is a resin in which an endothermic peak is observed in differential scanning calorimetry (DSC).
In the present invention, the resin component refers to a polymer component mainly contributing to the fixing performance.

The urethane group-containing olefin copolymer A is a polymer in which a structure having a urethane group is introduced into the polyolefin skeleton by means such as copolymerization.
Specifically, it has at least one structure Z2 selected from the group consisting of a structure Z1 represented by the following formula (1), a structure represented by the following formula (2), and a structure represented by the following formula (3) .

In the formulas (1) to (3), R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is an organic group, R ⁴ is H or CH ₃ , R ⁵ is an organic group.

Hereinafter, the structure shown by Formula (1), Formula (2), and Formula (3) is demonstrated concretely.
Arbitrary organic groups can be used for R ³ and R ⁵ .
It can be suitably illustrated that R ³ and R ⁵ are a hydrocarbon group.
Specific examples of the hydrocarbon group include C _1-12 alkyl groups such as methyl, ethyl and hexyl, C _2-12 alkenyl such as vinyl, and C _5-10 such as cyclohexyl. Examples thereof include a C _6-18 aryl group such as a cycloalkyl group, a phenyl group and a naphthyl group, and a C _7-12 araalkyl group such as a benzyl group.
In addition, R ³ and R ⁵ may be exemplified by those in which a part of hydrogen atoms of the hydrocarbon group is substituted with halogen, alcohol, carboxylic acid, amine, sulfonic acid etc., but is not limited thereto. is not.
Among these, a _C1-12 alkyl group and a phenyl group can be illustrated suitably.
For example, when R ³ is a phenyl group, low temperature fixability can be further improved because crystallinity is lower.
On the other hand, the urethane group-containing olefin copolymer A is produced, for example, by reacting an ethylene-pobar copolymer or an ethylene-vinyl acetate-pobar copolymer with a compound having an isocyanate group to form a urethane bond. You may

In addition, the urethane group-containing olefin copolymer A may have a crosslinked structure in the molecule or with another polymer via the organic group.
The case where urethane group containing olefin type copolymer A has the crosslinked structure by a urethane bond can be illustrated.
The urethane group-containing olefin copolymer B having a crosslinked structure can be produced by reacting an olefin copolymer having an isocyanate group with an olefin copolymer having a hydroxyl group to form a urethane. It is.
For example, it is mentioned that the said urethane group containing olefin type copolymer A is a structure where said Formula (2) is shown by following formula (a1). Moreover, it can be illustrated suitably that it is a structure shown by following formula (a2).
On the other hand, the urethane group-containing olefin copolymer A may be a structure in which the above formula (3) is represented by the following formula (a4).
When said Formula (2) or Formula (3) is this structure, it is preferable from a viewpoint of a hot offset resistance, and the viewpoint of low temperature fixability in order to be able to design low melting point.
Furthermore, when the urethane bond has a structure in which the urethane bond is crosslinked by a hexamethylene group (a structure represented by the following formula (a3)) in the crosslinked structure, the mobility of the crosslinking site is increased, Since the melting point of the copolymer does not become too high, the low temperature fixability can be further improved.
The urethane group-containing olefin copolymer A may be contained singly or in combination in the resin component.

In the formulas (a1) to (a4), p and q each independently represent an integer of 1 or more, r represents an integer of 4 to 8, and L ¹ and L ² are each independently. And a divalent substituent obtained by removing one more hydrogen from the above hydrocarbon group, a single bond, and the like. R ² and R ⁴ are as described above.

The urethane group concentration of the urethane group-containing olefin copolymer A is 2% by mass or more and 24% by mass or less. Moreover, it is preferable that this urethane group density | concentration is 5 to 15 mass%.
From the viewpoint of improving the hot offset resistance, the urethane group concentration is 2% by mass or more, and from the viewpoint of improving the charge retention, it is 24% by mass or less.

  Further, from the viewpoint of hot offset resistance and low temperature fixability, the content of the urethane group-containing olefin copolymer A in the resin component is preferably 50% by mass or more, and 70% by mass or more. More preferably, it is 80 mass% or more. The upper limit is not particularly limited, but is preferably 90% by mass or less.

Also, let M be the total mass of the urethane group-containing olefin copolymer A,
Let l be the mass of the structure shown in equation (1),
Let m be the mass of the structure shown in equation (2),
When the mass of the structure represented by the equation (3) is n,
The value of (l + m + n) / W in the urethane group-containing olefin copolymer A contained in the resin component is 0.80 or more from the viewpoint of low-temperature fixability, hot offset resistance and charge retention. Is preferably 0.95 or more, more preferably 1.00.

Furthermore, from the viewpoint of low-temperature fixability, hot offset resistance and charge retention, the content of the above-mentioned structure Z2 in the urethane group-containing olefin copolymer A is 2.0% by mass or more and 20.0% by mass or less Is preferable, and more preferably 2.0% by mass or more and 10.0% by mass or less.
When the content of the structure Z2 is 20.0% by mass or less, the melting point is lowered, and the low temperature fixability and the charge retention of the toner are further improved.
On the other hand, when the content of the structure Z2 is 2.0% by mass or more, the hot offset resistance is further improved by the interaction of the intermolecular hydrogen bond by the urethane group.

The urethane group-containing olefin copolymer A may contain a structure other than the structure Z1 and the structure Z2.
There is no particular limitation unless the effects of the present invention are impaired, but for example, a structure represented by the following formula (4), a structure represented by the following formula (5), a structure represented by the following formula (6), or The structure etc. which are shown by (7) are mentioned.
These are introduced by adding a corresponding monomer in the copolymerization reaction for producing the urethane group-containing olefin copolymer A, or modifying the urethane group-containing olefin copolymer by the polymer reaction. be able to.

（該式（４）〜（７）中、Ｒ^８はＨ又はＣＨ_３を示し、Ｒ^９はＨ又はＣＨ_３を示し、Ｒ^１０はＨ又はＣＨ_３を示し、Ｒ^１１はＨ又はＣＨ_３を示す。）

(In the formulas (4) to (7), R ⁸ represents H or CH ₃ , R ⁹ represents H or CH ₃ , R ¹⁰ represents H or CH ₃ , R ¹¹ represents H or CH ₃ Show)

The mass [l], [m], [n] of the structure represented by each of the above formulas, and the urethane group concentration can be measured using a general analysis method.
For example, methods such as ¹ H-NMR method, ATR method (infrared spectroscopy), thermal decomposition gas chromatography method and the like can be applied.
For example, a urethane group-containing olefin copolymer A (formula (1)) obtained by urethanizing hydroxyl groups of an ethylene-poval copolymer with phenyl isocyanate, and a structure represented by formula (2), R ^{1 = H, R 2 = H} , the content ratio of each structure of the copolymer) which is a R _{3 =} C 6 _{H 5} is measured by the following method.
^The measuring method using < ¹ > H-NMR is shown.
Containing each structure by comparing the integral ratio of the hydrogen atom of the alkylene in the structure represented by the formula (1) and the hydrogen atom of the phenyl group (R ³ is a phenyl group) in the structure represented by the formula (2) The ratio can be calculated.
Device: JNM-ECZR series FT NMR (manufactured by JEOL Nippon Denshi Co., Ltd.)
A solution of about 5 mg of the sample in 0.5 mL of heavy dimethyl sulfoxide (DMSO) containing tetramethylsilane as an internal standard of 0.00 ppm is placed in a sample tube, and the repetition time is 2.7 seconds, and the number of integrations is 16 The ¹ H-NMR spectrum is measured under the conditions of ^each cycle.
The peak at 1.1 to 1.4 ppm corresponds to CH ₂ -CH ₂ of the structure derived from ethylene,
Since the peaks around 7.0-8.0 pm correspond to C ₆ H ₅ of the phenyl group, the ratio of the integral value of those peaks is calculated, and the content ratio is calculated.
The ester group concentration is calculated by the following method.
Ester group concentration (unit: mass%) = [(N × 44) / number average molecular weight] × 100
Here, N is the average of the number of ester groups per molecule of the ester group-containing olefin copolymer, and 44 is the formula weight of the ester group [-C (= O) O-].
Further, the hydroxyl group concentration is calculated by the following method.
Hydroxyl group concentration (unit: mass%) = [(N × 17) / number average molecular weight] × 100
Here, N is the average of the number of hydroxyl groups per molecule of the hydroxyl group-containing olefin copolymer, and 17 is the formula weight of the ester group [-OH].
The separation of the urethane group-containing olefin copolymer A, the acid group-containing olefin copolymer B, the ester group-containing olefin copolymer, etc. from the toner is the solubility in methyl ethyl ketone (MEK), toluene, tetrahydrofuran, etc. It is good to carry out using the difference.

On the other hand, a measurement method using the ATR method will be shown below.
The FT-IR spectrum by the ATR method is performed using Spectrum One (Fourier transform infrared spectrometer) manufactured by PerkinElmer, which is equipped with Universal ATR Sampling Accessory (Universal ATR measurement accessory).
The incident angle of infrared light is set to 45 °.
As a prism used for ATR measurement, an ATR crystal of Ge (refractive index = 4.0) is used.
Other conditions are as follows.
<Range>
Start: 4000 cm ^-1
End: 600 cm ^-1 (Ge ATR crystal)
<Duration>
Scan number: 4
Resolution: 4.00 cm ^-1
Advanced: CO ₂ / H ₂ O corrected The specific measurement procedure is as follows.
Calculation Method of Pa (1) An ATR crystal (refractive index = 4.0) of Ge is attached to the apparatus.
(2) Set the Scan type to Background and Units to EGY, and measure the background.
(3) Set Scan type to Sample and Units to A.
(4) Precisely weigh 0.01 g of the sample on the ATR crystal.
(5) Pressurize the sample with a pressure arm. (Force Gauge is 100)
(6) Measure the sample.
(7) Baseline correction is performed on the obtained FT-IR spectrum by Automatic Correction.
(8) calculates the maximum value of the absorption peak intensity of 1730 cm ^-1 or 1740 cm ^-1 or less. (Pa1, alkylene group)
(9) Calculate the average of the absorption peak intensities at 1680 cm ⁻¹ and 1690 cm ⁻¹ . (Pa2, carbonyl group of urethane structure)
(10) The proportion (unit: mol%) of the structure having a urethane group is calculated by Pa1 / Pa2.
(11) The ester group concentration (unit: mass%) is calculated by the following method.
Ester group concentration (unit: mass%) = [(N × 59) / number average molecular weight] × 100
Here, N is the average of the number of ester groups per molecule of the ester group-containing olefin copolymer, and 59 is the formula weight of the ester group [-NH-C (= O) O-].

The softening point (Tm) of the urethane group-containing olefin copolymer A is preferably 80 ° C. or more and 160 ° C. or less, and is 100 ° C. or more and 150 ° C. or less from the viewpoint of enduring impact and pressure when using the toner. Is preferred.
The softening point can be controlled by changing the molecular weight of the urethane group-containing olefin copolymer A, and the softening point can be increased by increasing the molecular weight.
The weight average molecular weight (Mw) of the urethane group-containing olefin copolymer A is preferably 50000 or more and 500000 or less, and more preferably 300000 or less from the viewpoint of achieving both low temperature fixability and hot offset resistance. .

Although the manufacturing method of this urethane group containing olefin type copolymer A is not specifically limited, An example of a manufacturing method is shown below.
It can be produced by reacting an ethylene-pobar copolymer or an ethylene-vinyl acetate-pobar copolymer with a compound having an isocyanate group to form a urethane bond.
When this method is used, in the step of preparing the particles of the resin composition described later,
A step of reacting the ethylene-pobar copolymer or the ethylene-vinyl acetate-pobar copolymer with a compound having an isocyanate group to form the urethane group-containing olefin copolymer A may be included.
On the other hand, the ethylene-vinyl acetate copolymer may be hydrolyzed to obtain a hydroxyl group-containing olefin copolymer and then the hydroxyl group-containing olefin copolymer may be reacted with a compound having an isocyanate group for production.
Specifically, an ethylene-vinyl acetate copolymer having an ester group concentration of about 2% by mass to 18% by mass is refluxed at 90 ° C. using sodium hydroxide in a mixed solvent of toluene and ethanol. By the reaction, it is possible to obtain a hydroxyl group-containing olefin copolymer in which the ester group of the ethylene-vinyl acetate copolymer is hydrolyzed.
Next, the obtained hydroxyl group-containing olefin copolymer and the compound having an isocyanate group are mixed, and heated at 60 ° C. to obtain a urethane group-containing olefin copolymer A.
The isocyanate compound may be a blocked isocyanate compound protected by a blocker. In the case of using a blocked isocyanate compound, it is necessary to raise the temperature to a temperature at which the blocker is released and the isocyanate group is reacted, and it is preferable to select a solvent type having a high boiling point.
On the other hand, in the method for producing a urethane group-containing olefin copolymer A, a urethane group-containing olefin copolymer A having a crosslinked structure is produced by using an isocyanate compound having two or more isocyanate groups. Can.
Moreover, the following method is mentioned as another manufacturing method.
The hydroxyl group of the hydroxyl group-containing olefin copolymer can be converted to an isocyanate group by reacting the hydroxyl group-containing olefin copolymer with an excess of the isocyanate compound.
A urethane group-containing olefin copolymer can be produced by urethanizing the obtained isocyanate group-containing olefin copolymer and the compound containing a hydroxyl group.
At this time, if a hydroxyl group-containing olefin copolymer is used as the hydroxyl group-containing compound, a crosslinked urethane group-containing olefin copolymer can be produced.
It is preferable to use an isocyanate compound having one isocyanate group from the viewpoint of designing a low melting point in order to improve low-temperature fixability. Moreover, when the network structure of resin is formed and it is set as the urethane-group containing olefin type copolymer which has a crosslinked structure, hot offset resistance can be improved more.

The resin component may further contain an acid group-containing olefin copolymer B.
Examples of the acid group-containing olefin-based copolymer B include resins in which a polyolefin such as polyethylene or polypropylene is used as a main component, and a monomer having an acid group is further subjected to random copolymerization, block copolymerization or graft copolymerization. It also contains the resin modified by polymer reaction.
As a monomer having an acid group, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, vinyl sulfonate and the like can be mentioned.
Moreover, components other than polyolefin and the monomer derived from the above-mentioned acid group may be included as long as the physical properties are not affected.
From the viewpoint of storage stability of the toner, the content of components other than the polyolefin and the monomer having the acid group in the acid group-containing olefin copolymer B is preferably 20% by mass or less, and 10% by mass. % Or less is more preferable, 5% by mass or less is even more preferable, and substantially 0% by mass is particularly preferable.
In addition, from the viewpoint of low-temperature fixability, a copolymer of ethylene and a monomer having an acid group is preferable. From the viewpoint of adhesion to paper, the monomer having an acid group is preferably acrylic acid or methacrylic acid. That is, the acid group-containing olefin copolymer B is preferably an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, or a mixture thereof.
The acid value of the acid group-containing olefin copolymer B is preferably 50 mg KOH / g or more and 300 mg KOH / g or less, and more preferably 80 mg KOH / g or more and 200 mg KOH / g or less. When the acid value is 50 mg KOH / g or more, adhesion to paper can be improved. When the acid value is 300 mg KOH / g or less, the charge retention can be improved.
When the resin component contains the acid group-containing olefin copolymer B, the carboxy group of the acid group-containing olefin copolymer B forms a hydrogen bond with the hydroxyl group of the paper surface, and the adhesion between the toner and the paper And the erase resistance of the fixed material by the eraser etc. is improved.
Furthermore, when toner particles are produced by the emulsion aggregation method described later, if the acid group-containing olefin copolymer B is contained, the aggregation is easily controlled by the acidic groups of the acid group-containing olefin copolymer B. As a result, the particle size distribution of the toner particles is improved.
The content of the acid group-containing olefin copolymer B in the resin component is preferably 10% by mass or more and less than 50% by mass, and preferably 10% by mass or more, from the viewpoint of adhesion to paper and charge retention. It is more preferable that it is 30 mass% or less.

The softening point (Tm) of the acid group-containing olefin copolymer B is 100 ° C. or more and 140 ° C. or less from the viewpoint of storage stability, adhesion to paper, and compatibility with the urethane group-containing olefin copolymer A. Is preferred.
The melting point of the acid group-containing olefin copolymer B is preferably 50 ° C. or more and 100 ° C. or less, and more preferably 50 ° C. or more and 90 ° C. or less from the viewpoint of low temperature fixability and storage stability. .

In the present invention, the melting point of a resin or a polymer can be measured using a differential scanning calorimeter (DSC).
Specifically, a sample of 0.01 to 0.02 g 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 taken as the melting point.

The breaking elongation of the acid group-containing olefin copolymer B is preferably 300% or more, and more preferably 500% or more. By setting the breaking elongation to 300% or more, the bending resistance of the fixed material is improved. The upper limit of the breaking elongation is about 1000% or less. The breaking elongation is measured under the conditions based on JIS K 7162.
When a plurality of the acid group-containing olefin copolymers B are contained in the resin component, the measurement is carried out under the above conditions after melt mixing.

The resin component may contain an ester group-containing olefin copolymer C.
As the ester group-containing olefin copolymer C, an ethylene (propylene) -vinyl ester copolymer such as ethylene-vinyl acetate copolymer, or ethylene (propylene) -acrylic such as ethylene-methyl acrylate copolymer Examples include ethylene (propylene) -methacrylic acid ester copolymers such as acid ester-based copolymers and ethylene-methyl methacrylate copolymers.
The content of the ester group-containing olefin copolymer C in the resin component is preferably 0% by mass or more and less than 50% by mass, and more preferably 20% by mass or more and 50% by mass or less. When the content of the ester group-containing olefin copolymer C is in the above range, the low temperature fixability is further improved.

The resin component is a polymer other than the urethane group-containing olefin copolymer A, the acid group-containing olefin copolymer B and the ester group-containing olefin copolymer C, to the extent that the effects of the present invention are not impaired. It may contain a resin.
Specifically, homopolymers of styrene and its substitution products such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene, etc .; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinyl naphthalene Copolymers, styrene copolymers such as styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer; polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, acrylic Resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin, polypropylene resin, etc. may be mentioned.

The toner particles may contain at least one compound selected from the group consisting of aliphatic hydrocarbons, aliphatic alcohols and aliphatic carboxylic acids (hereinafter also referred to as aliphatic hydrocarbon compounds).
The melting point of the aliphatic hydrocarbon compound is preferably 50 ° C. or more and 100 ° C. or less, and more preferably 70 ° C. or more and 100 ° C. or less.
Specific examples thereof include aliphatic hydrocarbons having 20 to 60 carbon atoms such as hexacosane, triacontane, and hexatriacontane; aliphatic alcohols such as docosanol; and aliphatic carboxylic acids such as stearic acid.
Among the aliphatic hydrocarbon compounds, aliphatic alcohol or aliphatic carboxylic acid is preferable from the viewpoint of low temperature fixability and good compatibility with the urethane group-containing olefin copolymer A. On the other hand, aliphatic hydrocarbons are preferred from the viewpoint of charge retention.
By using the aliphatic hydrocarbon compound, the urethane group-containing olefin copolymer forming the matrix can be plasticized at the time of heat fixing of the toner, and the low temperature fixing property can be enhanced. The aliphatic hydrocarbon compound having a melting point of 50 ° C. or more and 100 ° C. or less can also function as a crystal nucleating agent of the urethane group-containing olefin copolymer A. Therefore, micro mobility of the urethane group-containing olefin copolymer A is suppressed, and charge retention is improved.
The content of the aliphatic hydrocarbon compound is preferably 1 to 40 parts by mass, and more preferably 10 to 35 parts by mass with respect to 100 parts by mass of the resin component. More preferably, it is 10 parts by mass or more and 30 parts by mass or less.

The toner particles may contain silicone oil as a release agent.
The releasing agent generally used for toners such as alkyl wax is easily compatible with the urethane group-containing olefin copolymer A, and the releasing effect is hardly obtained.
When the toner particles contain a colorant, the dispersibility of the colorant is improved by the addition of the silicone oil, and a high density image can be easily obtained.
As silicone oil, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, amino modified silicone oil, carboxy modified silicone oil, alkyl modified silicone oil, fluorine modified silicone oil and the like can be exemplified.
The kinematic viscosity of the silicone oil is preferably 5 mm ² / S or more and 1000 mm ² / S or less, more preferably 20 mm ² / S or more and 1000 mm ² / S or less.
The content of the silicone oil is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component from the viewpoint of obtaining good separability while suppressing the decrease in fluidity. It is more preferable that it is a mass part or more and 20 mass parts or less.

The toner particles may contain a colorant. Examples of the colorant include the following.
Examples of the black colorant include those black-colored by using carbon black; magnetic material; yellow colorant, magenta colorant and cyan colorant.
Among these colorants, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full color image to improve the sharpness by using a dye and a pigment in combination.
As pigments for magenta toners, the following may be mentioned. C. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following. C. I. Solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disperse thread 9; C.I. I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disperse Violet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of pigments for cyan toner include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with one or more and five or less phthalimidomethyl groups.
As dyes for cyan toner, C.I. I. Solvent Blue 70 is mentioned.
Examples of pigments for yellow toners include the following. C. I. Pigment yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat Yellow 1, 3, 20.
As dyes for yellow toner, C.I. I. Solvent Yellow 162 can be mentioned.
These colorants can be used alone or in combination, or in the form of a solid solution.
The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the coloring agent is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component.

  The toner particles preferably have 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 particles may be measured using a particle size distribution analyzer (Coulter Multisizer III manufactured by Coulter) by the Coulter method.

The method for producing the toner of the present invention is
A method for producing a toner having toner particles containing a resin component, comprising:
The resin component contains a urethane group-containing olefin copolymer A;
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium, or
Dispersing the resin composition in which the resin component is dissolved in an organic solvent in an aqueous medium to prepare particles of the resin composition,
The urethane group-containing olefin copolymer A is
A structure Z1 represented by the following formula (1), and at least one structure Z2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The urethane group concentration of the urethane group-containing olefin copolymer A is 2% by mass or more and 24% by mass or less.

By preparing resin fine particles or resin composition particles in an aqueous medium, the highly hydrophilic urethane group-containing olefin copolymer A tends to be unevenly distributed to the surface layer of the toner particles.
As a result, the effect of the urethane group-containing olefin copolymer A is more easily exhibited.
From the viewpoint of controllability of particle size distribution, an emulsion aggregation method is preferable which includes a step of dispersing resin fine particles for producing a resin component in an aqueous medium.
In the emulsion aggregation method, a toner particle is produced by preparing a resin fine particle dispersion sufficiently small with respect to a target particle diameter, and aggregating the resin fine particle in an aqueous medium.

In the emulsion aggregation method, after the step of preparing the resin fine particle dispersion,
Aggregating the resin fine particles to form aggregate particles, and
Preferably, the method further comprises the step of heating and coalescing the aggregate particles.
In addition to the above steps, a cooling step, a washing step, a drying step, and the like may be performed.

Hereinafter, the method for producing a toner using the emulsion aggregation method will be specifically described, but it is not limited thereto.
<Step of Preparing Resin Fine Particle Dispersion (Preparation Step)>
The fine resin particle dispersion can be prepared by a known method, but the following method can be suitably exemplified.
For example, the resin component is dissolved in an organic solvent to form a uniform solution. After that, a basic compound and a surfactant are added as needed. Further, an aqueous medium is added to the solution to form fine particles. Finally, the organic solvent is removed to prepare a resin fine particle dispersion in which the resin fine particles are dispersed.
In the preparation step, the urethane group-containing olefin copolymer A and, if necessary, other components may be separately dispersed. Alternatively, two or more types of resin components may be converted to resin fine particles by a co-emulsification method.
For example, there is a co-emulsification method in which an acid group-containing olefin copolymer B is added to a urethane group-containing olefin copolymer A and simultaneously dissolved and emulsified.
When resin fine particles are formed by the co-emulsification method with the acid group-containing olefin copolymer B, the urethane group-containing olefin copolymer A, the acid group-containing olefin copolymer B, and the like in the organic phase. Mix together. As a result, the compatibility between the two in the toner particles is enhanced, and the adhesion between the toner and the paper is further enhanced.
More specifically, the urethane group-containing olefin copolymer A and the acid group-containing olefin copolymer B are heated and dissolved in an organic solvent, and a surfactant and a basic compound are added. Subsequently, a co-emulsion (resin fine particle dispersion) containing a resin component is produced by slowly adding the aqueous medium while applying shear force with a homogenizer or the like.
Alternatively, after addition of the aqueous medium, a shear force is applied by a homogenizer or the like to prepare a co-emulsion containing the resin component.
Thereafter, the resin fine particle dispersion is prepared by heating or depressurizing to remove the organic solvent.

The amount of the resin component to be dissolved in the organic solvent when preparing the resin fine particle dispersion is preferably 10 parts by mass to 50 parts by mass and 30 parts by mass to 50 parts by mass with respect to 100 parts by mass of the organic solvent. More preferable.
Any organic solvent can be used as long as it can dissolve the resin component, but a solvent having high solubility in an olefin resin such as toluene, xylene, ethyl acetate and the like is preferable.
The surfactant is not particularly limited. For example, anionic surfactants of sulfate ester type, sulfonate type, carboxylate type, phosphate type, soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type, Examples thereof include alkylphenol ethylene oxide adduct type surfactants and polyhydric alcohol type nonionic surfactants.
Examples of the basic compound include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as triethylamine, trimethylamine, dimethylaminoethanol and diethylaminoethanol. The basic compounds 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 1.00 μm or less, and more preferably 0.10 μm or more and 0.60 μm or less. When the median diameter is in 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 analyzer (Nanotrac UPA-EX 150: manufactured by Nikkiso Co., Ltd.).

<Flocculation process>
In the aggregation step, for example, the colorant fine particle dispersion, the aliphatic hydrocarbon compound fine particle dispersion, and the silicone oil emulsion are mixed with the above-mentioned resin fine particle dispersion, if necessary, to prepare a mixed liquid, The step of aggregating fine particles contained in the prepared mixture liquid to form aggregate particles.
As a method of forming the aggregate particles, a method of adding and mixing an aggregating agent into the above mixed solution, raising the temperature, and appropriately adding mechanical power and the like can be suitably exemplified.
The colorant fine particle dispersion is prepared by dispersing the above-mentioned colorant. The colorant fine particles are dispersed by a known method, but for example, a media type disperser such as a rotary shear type homogenizer, a ball mill, a sand mill, an attritor, a high pressure counter collision type disperser, etc. are preferably used. In addition, surfactants and polymer dispersants that impart dispersion stability can be added as necessary.
The aliphatic hydrocarbon compound fine particle dispersion and the silicone oil emulsion are prepared by dispersing each material in an aqueous medium. Each material is dispersed by a known method, but for example, a media type dispersing machine such as a rotary shear type homogenizer, a ball mill, a sand mill, an attritor, a high pressure counter collision type dispersing machine, etc. are preferably used. In addition, surfactants and polymer dispersants that impart dispersion stability can be added as necessary.
Examples of the coagulant 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; polyaluminum chloride And polyvalent metal salts such as From the viewpoint of particle diameter controllability of the aggregation step, metal salts of divalent metals such as calcium chloride and magnesium sulfate are preferable.
The addition and mixing of the flocculant is preferably performed in a temperature range from room temperature to 75 ° C. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The above mixing can be carried out using a known mixing device, homogenizer, mixer or the like.
The volume-based median diameter of the aggregate particles formed in the aggregation step is not particularly limited, but usually about 4.0 μm or more and 7.0 μm or less so as to be about the same as the median diameter of toner particles to be obtained. It is good to control it. The control can be easily performed, for example, by appropriately setting and changing the temperature at the time of addition and mixing of the coagulant and the like and the conditions of the stirring and mixing.
The volume-based median diameter of the aggregate particles may be measured using a particle size distribution analyzer (Coulter Multisizer III manufactured by Coulter) by the Coulter method.

<Fusion process>
The fusion step is a step of producing particles in which the surface of the aggregate particle is smoothed by heating and coalescing the aggregate particle, preferably to a temperature higher than the melting point of the olefin resin.
Before entering the fusion step, in order to prevent fusion between the obtained resin particles, a chelating agent, a pH adjuster, a surfactant and the like can be appropriately added.
Examples of chelating agents are alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium citrate and sodium citrate, nitrilotriacetate (NTA) salts, both COOH and OH Water-soluble polymers (polyelectrolytes) that contain the functionality of
The heating temperature may be equal to or higher than the melting point of the urethane group-containing olefin copolymer A contained in the aggregate particles and not higher than the temperature at which the urethane group-containing olefin copolymer A thermally decomposes. The heating and fusion time is short if the heating temperature is high and long if the heating temperature is low. That is, the time of heat fusion depends on the temperature of heating and can not be generally defined, but is generally about 10 minutes to 10 hours.

<Cooling process>
In the cooling step, it is preferable to cool the temperature of the aqueous medium containing the resin particles obtained in the fusion step to a temperature lower than the crystallization temperature of the urethane group-containing olefin copolymer A.
By performing cooling to a temperature lower than the crystallization temperature, generation of coarse particles can be suppressed. The specific cooling rate is about 0.1 to 50 ° C./minute.
Moreover, it is preferable to hold | maintain at the temperature whose crystallization rate of urethane group containing olefin type copolymer A is quick during cooling, or after cooling, and to perform the annealing which promotes crystallization. By maintaining the temperature at about 30 to 70 ° C., crystallization is promoted, and the blocking resistance of the toner is improved.

<Washing process>
Impurities in the resin particles can be removed by repeating washing and filtration of the resin particles produced through the above steps.
Specifically, it is preferable to wash the resin particles using an aqueous solution containing a chelating agent such as ethylenediaminetetraacetic acid (EDTA) and its Na salt and further washing with pure water.
By repeating washing with pure water and filtration a plurality of times, metal salts and surfactants in resin particles can be removed. The number of times of filtration is preferably 3 to 20 times in view of production efficiency, and more preferably 3 to 10 times.

<Drying process>
The washed resin particles can be dried to obtain toner particles.
The toner particles may be used as toner as they are. In addition, if necessary, a toner fine particle such as silica fine particle, alumina fine particle, titania fine particle, calcium carbonate fine particle or the like, or resin fine particle such as vinyl resin, polyester resin, silicone resin etc. It may be added to particles to obtain a toner. These inorganic fine particles and resin fine particles function as external additives such as a flowability aid and a cleaning aid.

On the other hand, a solution suspension method may be used in which a resin composition in which a resin component is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium.
In the dissolution suspension method, a resin composition obtained by dissolving a resin component in an organic solvent is dispersed in an aqueous medium to granulate particles of the resin composition, and the particles of the resin composition are contained in the particles of the resin composition. By removing the organic solvent, toner particles are produced.
The dissolution and suspension method is adaptable to any resin component that is soluble in an organic solvent, and shape control is easy depending on the conditions at the time of solvent removal.

Hereinafter, the method for producing a toner using the dissolution suspension method will be specifically described, but it is not limited thereto.
The lysis suspension method may include the following steps.
A step of dissolving or dispersing other components such as a resin component and, if necessary, a colorant, an aliphatic hydrocarbon compound and a silicone oil in an organic solvent to prepare a resin composition (resin component dissolving step).
A step of dispersing the obtained resin composition in an aqueous medium to the size of toner particles to prepare particles of the resin composition (granulation step).
Process of removing the organic solvent contained in the particles of the obtained resin composition (solvent removal process).
After the solvent removal step, the toner particles may be produced by washing and drying (washing and drying step).

<Resin component dissolution process>
In the resin component dissolving step, the urethane group-containing olefin copolymer A and, if necessary, other components such as a colorant, an aliphatic hydrocarbon compound and a silicone oil are dissolved or dispersed in an organic solvent to obtain a resin The composition is prepared.
The organic solvent to be used may be any solvent as long as it can dissolve the resin component. Specific examples include toluene, xylene, chloroform, methylene chloride and ethyl acetate. In addition, it is preferable to use toluene and ethyl acetate from the crystallization acceleration | stimulation property of crystalline resin, and the ease of solvent removal.
The amount of the organic solvent used is not limited, but it may be an amount that allows the resin composition to be dispersed in a poor medium such as water and granulated. Specifically, the mass ratio of the resin component and, if necessary, other components such as the colorant, the aliphatic hydrocarbon compound and the silicone oil and the organic solvent is 10/90 to 50/50, which will be described later. It is preferable from the viewpoint of the graininess and the production efficiency of toner particles.
On the other hand, the coloring agent, the aliphatic hydrocarbon compound and the silicone oil do not need to be dissolved in the organic solvent, and may be dispersed. In the case of using the colorant, the aliphatic hydrocarbon compound and the silicone oil in a dispersed state, it is preferable to disperse using a disperser such as a bead mill.

Granulation process
The granulating step is a step of dispersing the obtained resin composition in an aqueous medium using a dispersant so as to obtain a predetermined toner particle diameter to prepare particles of the resin composition.
Water is mainly used as the aqueous medium.
The aqueous medium preferably contains a monovalent metal salt in an amount of 1% by mass to 30% by mass. By containing a monovalent metal salt, diffusion of the organic solvent in the resin composition into the aqueous medium is suppressed, and the crystallinity of the resin component contained in the obtained toner particles is enhanced.
As a result, the blocking resistance of the toner tends to be good, and the particle size distribution of the toner tends to be good.
Examples of the monovalent metal salt include sodium chloride, potassium chloride, lithium chloride and potassium bromide. Among these, sodium chloride and potassium chloride are preferable.
The mixing ratio (mass ratio) of the aqueous medium to the resin composition is preferably 90/10 to 50/50.
The dispersant is not particularly limited, but surfactants of cationic type, anionic type and nonionic type are used as the organic dispersant, and anionic type is preferable.
For example, sodium alkylbenzene sulfonate, sodium α-olefin sulfonate, sodium alkyl sulfonate, sodium alkyl diphenyl ether disulfonate and the like can be mentioned. On the other hand, examples of the inorganic dispersant include tricalcium phosphate, hydroxyapatite, calcium carbonate fine particles, titanium oxide fine particles and silica fine particles.
Among these, tricalcium phosphate as an inorganic dispersant is preferable. The reason for this is that there is very little adverse effect on the granulation and its stability and also on the properties of the toner obtained.
The addition amount of the dispersant is determined according to the particle size of the granulated material, and the particle size decreases as the addition amount of the dispersant increases. Therefore, although the addition amount of a dispersing agent changes with desired particle diameters, it is preferable to be used in 0.1-15 mass% with respect to a resin composition.
Moreover, when preparing the particle | grains of a resin composition in an aqueous medium, it is preferable to be performed under high speed shear. The particles of the resin composition dispersed in the aqueous medium preferably have a weight average particle diameter of 10 μm or less, and more preferably 4 to 9 μm.
As a device for applying high speed shearing, various high speed dispersing machines and ultrasonic dispersing machines may be mentioned.
On the other hand, the weight average particle diameter of the particles of the resin composition may be measured using a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter, Inc.) by the Coulter method.

Solvent removal process
In the solvent removal step, the organic solvent contained in the particles of the obtained resin composition is removed to produce toner particles.
The removal of the organic solvent may be carried out with stirring. Moreover, the removal rate of the organic solvent can also be controlled by heating and depressurizing as necessary.
The removal rate of the organic solvent preferably satisfies the following.
From (X / 12) / h to (X / 36) / h
X: Charge of organic solvent h: Hour

<Washing and drying process>
After the solvent removal step, a washing and drying step of washing with water etc. multiple times, filtering and drying toner particles may be carried out. When a dispersant that dissolves under acidic conditions such as tricalcium phosphate is used as the dispersant, washing with hydrochloric acid or the like is preferable followed by washing with water. By washing, the dispersant used for granulation can be removed to improve the toner properties. After washing, toner particles can be obtained by filtering and drying.
The toner particles may be used as toner as they are. In addition, toner particles such as silica particles, alumina particles, titania particles, inorganic particles such as titania particles, calcium carbonate particles, and resin particles such as vinyl resin, polyester resin, silicone resin, etc. are applied in a dry state, as necessary, as a toner. It may be added to particles to obtain a toner. These inorganic fine particles and resin particles function as external additives such as a flowability aid and a cleaning aid.

Hereinafter, methods of measuring various physical properties of the toner and the raw material will be described.
<Method of measuring acid number>
The acid value is the number of mg of potassium hydroxide required to neutralize an acid component such as free fatty acid and resin acid contained in 1 g of a sample. Although a measuring method is measured according to JISK 0070-1992, it specifically measures according to the following procedures.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), ion-exchanged water is added to make it 100 mL, and a phenolphthalein solution is obtained.
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 liter. The solution is placed in an alkali resistant container and left for 3 days so as not to touch carbon dioxide gas, etc., and then filtered to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali resistant container. Factor of potassium hydroxide solution Take 25 mL of 0.1 mol / L hydrochloric acid into an Erlenmeyer flask, add a few drops of phenolphthalein solution, titrate with potassium hydroxide solution, amount of potassium hydroxide solution required for neutralization Ask from As 0.1 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.
(2) Operation (A) This Test Precisely weigh 2.0 g of the ground sample in a 200 mL Erlenmeyer flask, add 100 mL of a mixed solution of toluene / ethanol (2: 1), and dissolve over 5 hours. Then, add a few drops of phenolphthalein solution as an indicator and titrate with potassium hydroxide solution. The end point of titration is assumed to be when the pale pink color of the indicator continues for about 30 seconds.
(B) Blank test The same titration as in the above operation is performed except that no sample is used (ie, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The obtained result is substituted into the following equation to calculate the acid value.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mg KOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: mass of sample (g).

<Method of measuring softening point (Tm)>
The softening point (Tm) is measured according to a manual attached to the apparatus, using a load extrusion type capillary rheometer "flow characteristic evaluation apparatus flow tester CFT-500D" (manufactured by Shimadzu Corporation).
In this apparatus, while applying a constant load from the top of the measurement sample by the piston, the measurement sample filled in the cylinder is melted while raising its temperature, and the melted measurement sample is extruded from the die at the bottom of the cylinder. The flow curve can be graphed from the amount (mm) and the temperature (° C).
In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "Flow Characteristic Evaluation Device Flow Tester CFT-500D" is taken as the softening point.
The melting temperature in the 1⁄2 method is calculated as follows.
First, a half of the difference between the amount of descent of the piston at the end of the outflow (the end point of the outflow, Smax) and the amount of descent of the piston at the start of the outflow (the minimum point, Smin) (This is assumed to be X. X = (Smax-Smin) / 2). Then, in the flow curve, the temperature at which the amount of descent of the piston is the sum of X and Smin is taken as the melting temperature in the 1/2 method.
For the measurement sample, 1.2 g of the sample was compression molded at 10 MPa for 60 seconds under an environment of 25 ° C. using a tablet molding and compression machine (standard manual type Newton press NT-100H, manufactured by NPA system). Use a cylindrical shape with a diameter of 8 mm.
The specific operation in measurement is performed according to the manual attached to the device.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising method start temperature: 60 ° C
Reaching temperature: 200 ° C
Measurement interval: 1.0 ° C
Heating rate: 4.0 ° C / min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 5.0 kgf
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

<Measuring method of molecular weight of each olefin copolymer>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of each olefin copolymer are measured as follows using gel permeation chromatography (GPC).
First, each olefin copolymer is dissolved in toluene at 135 ° C. for 6 hours. Then, the resulting solution is filtered through a solvent-resistant membrane filter "Maechoridisc" (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 toluene is about 0.1% by mass. It measures on condition of the following using this sample solution.
Device: HLC-8121GPC / HT (made by Tosoh Corporation)
Column: TSKgel GMHHR-H HT (7.8 cm ID × 30 cm) 2 series (made by Tosoh Corporation)
Detector: RI for high temperature
Temperature: 135 ° C
Solvent: Toluene flow rate: 1.0 mL / min
Sample: 0.4 mL injection of a 0.1% by mass sample In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a monodispersed polystyrene standard sample is used. Furthermore, it calculates by converting into polyethylene by the conversion equation derived from the Mark-Houwink viscosity equation.

  Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto. In the examples and comparative examples, the numbers of parts are all based on mass unless otherwise noted.

<Production of Ethylene-Poval Copolymer EVOH-A>
100 parts of ethylene-vinyl acetate copolymer 1 (ester group concentration: 8% by mass, acid value: 0 mg KOH / g, Tm: 120 ° C.) was dissolved at 90 ° C. in a mixed solvent of 500 mL of toluene and 500 mL of ethanol. Subsequently, 10 parts of sodium hydroxide was added and refluxing was performed for 6 hours. Then, the ethylene-poval copolymer EVOH-A was obtained by washing with ethanol.

<Production of Ethylene-Poval Copolymer EVOH-B>
Except using ethylene-vinyl acetate copolymer 2 (ester group concentration: 14 mass%, acid value: 0 mg KOH / g, Tm: 120 ° C.) instead of ethylene-vinyl acetate copolymer 1, it is EVOH-A EVOH-B was obtained as in the preparation.

<Production of Ethylene-Poval Copolymer EVOH-C>
Except using ethylene-vinyl acetate copolymer 3 (ester group concentration: 3 mass%, acid value: 0 mg KOH / g, Tm: 120 ° C.) instead of ethylene-vinyl acetate copolymer 1, it is EVOH-A EVOH-C was obtained in the same manner as production.

<Production of Ethylene-Poval Copolymer EVOH-D>
Example of EVOH-A except using ethylene-vinyl acetate copolymer 4 (ester group concentration: 3 mass%, acid value: 0 mg KOH / g, Tm: 95 ° C.) instead of ethylene-vinyl acetate copolymer 1 EVOH-D was obtained as in production.

<Production of Ethylene-Poval Copolymer EVOH-E>
Except using ethylene-vinyl acetate copolymer 6 (ester group concentration: 21 mass%, acid value: 0 mg KOH / g, Tm: 45 ° C.) instead of ethylene-vinyl acetate copolymer 1, it is EVOH-A EVOH-E was obtained in the same manner as production.

<Production of Ethylene-Poval Copolymer EVOH-F>
Except using ethylene-vinyl acetate copolymer 7 (ester group concentration: 1% by mass, acid value: 0 mg KOH / g, Tm: 69 ° C.) instead of ethylene-vinyl acetate copolymer 1, it is EVOH-A EVOH-F was obtained in the same manner as production.

<Production of Ethylene-Isocyanate Group-Containing Copolymer EIC>
100 parts of EVOH-A and 2.0 parts of phenyl isocyanate are added, dissolved in dimethyl sulfoxide, reacted under conditions of 60 ° C., ethylene-isocyanate group-containing co-having the hydroxyl group of the above EVOH-A substituted with isocyanate group Polymer EIC was obtained.

<Production of Urethane Group-Containing Olefin Copolymer EUR-A>
100 parts of EVOH-A and 0.5 parts of phenyl isocyanate were added, dissolved in dimethyl sulfoxide and reacted under the condition of 60 ° C. to obtain EUR-A (urethane group-containing olefin copolymer A) .

<Production of Urethane Group-Containing Olefin Copolymer EUR-B>
EUR-B was prepared as for EUR-A except that n-hexyl isocyanate was substituted for phenyl isocyanate.

<Production of Urethane Group-Containing Olefin Copolymer EUR-C>
EUR-C was prepared in the same manner as EUR-A except that 0.6 parts of hexamethylene diisocyanate was substituted for 0.5 parts of phenylisocyanate.

<Production of Urethane Group-Containing Olefin Copolymer EUR-D>
EUR-D was prepared the same as EUR-A except using EVOH-B instead of EVOH-A.

<Production of Urethane Group-Containing Olefin Copolymer EUR-E>
EUR-E was prepared the same as EUR-A except using EVOH-C instead of EVOH-A.

<Production of Urethane Group-Containing Olefin Copolymer EUR-F>
EUR-F was prepared the same as EUR-A except using EVOH-D instead of EVOH-A.

<Production of Urethane Group-Containing Olefin-Based Copolymer EUR-G>
EUR-G was prepared in the same manner as EUR-A except using 33 parts of EVOH-A and using 67 parts of EIC instead of phenylisocyanate.

<Production of Urethane Group-Containing Olefin Copolymer EUR-H>
EUR-H was prepared in the same manner as EUR-A except that 0.5 part of phenylisocyanate was changed to 0.3 part of phenylisocyanate.

<Production of Urethane Group-Containing Olefin Copolymer EUR-I>
In place of EVOH-A, it is EUR- except that ethylene-vinyl acetate-vinyl alcohol copolymer 5 (ester group concentration: 8 mass%, acid value: 0 mg KOH / g, Tm: 120 ° C., melting point: 106 ° C.) is used. Similar to the preparation of A, EUR-I was prepared.

<Production of Urethane Group-Containing Olefin Copolymer EUR-J>
EUR-J was prepared the same as EUR-A except using EVOH-E instead of EVOH-A.

<Production of Urethane Group-Containing Olefin-Based Copolymer EUR-K>
EUR-K was produced as for EUR-A except using EVOH-F instead of EVOH-A.

<Production of Urethane Modified Polyester PUR>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 343 parts of bisphenol A ethylene oxide adduct, 166 parts of isophthalic acid and 2 parts of dibutyltin oxide are added and reacted for 8 hours at 230 ° C. under normal pressure did.
Furthermore, after reacting for 5 hours under reduced pressure of 0.001 to 0.002 MPa, it cooled to 110 degreeC. In toluene, 13 parts of hexamethylene diisocyanate was added to the obtained reaction product, and reaction was carried out at 110 ° C. for 5 hours.
Subsequently, the solvent was removed to prepare a urethane-modified polyester PUR having a weight-average molecular weight of 50,700 and a urethane group concentration of 3% by mass.

<Production of Resin Fine Particle A-1 Dispersion>
Toluene (Wako Pure Chemical Industries, Ltd.) 300 parts Urethane group-containing olefin copolymer EUR-A 100 parts ^{(R 1 = H, R 2} = H, R 3 = C 6 H 5, urethane group concentration: 10 wt% , Tm: 115 ° C., weight average molecular weight: 110000)
・ Acid group-containing olefin copolymer EMA-A 25 parts (ethylene-methacrylic acid copolymer, Tm: 123 ° C., melting point: 90 ° C., acid value: 90 mg KOH / g)
The above formulations were mixed and dissolved at 90 ° C.
Separately, 0.7 part of sodium dodecylbenzene sulfonate, 1.5 parts of sodium laurate and 0.8 parts of N, N-dimethylaminoethanol were added to 700 parts of ion-exchanged water, and the mixture was heated and dissolved at 90 ° C. Then, the above-mentioned toluene solution and aqueous solution are mixed, and an ultra high speed stirring device T.I. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix Co., Ltd.).
Further, the mixture was emulsified at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai 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 A-1 dispersion) having a concentration of 20% by mass of the resin fine particle A-1.
The volume-based median diameter of the resin fine particles A-1 was measured using a dynamic light scattering particle size distribution diameter (Nanotrac: manufactured by Nikkiso Co., Ltd.) and was 0.40 μm.

<Production of Resin Fine Particle A-2 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-B (R 1 = H} , R 2 = H, R 3 = C 6 H 13, urethane group concentration: 10 wt%, Tm: 115 ℃, weight average molecular weight A resin fine particle A-2 dispersion liquid was obtained in the same manner as in the production of the resin fine particle A-1 dispersion liquid except that it was changed to 110000). The volume-based median diameter of the obtained resin fine particles A-2 was 0.42 μm.

<Production of Resin Fine Particle A-3 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-C (R 1 = H} , R 2 = H, R 3 = C6H12-NH-C (= O) -O-Q, Q is an olefin-based copolymer Resin fine particle A-1 dispersion except that the structure represented by the formula (2) is changed to the structure (a3), urethane group concentration: 10% by mass, Tm: 143 ° C., weight average molecular weight: 250000). Resin fine particle A-3 dispersion liquid was obtained in the same manner as in the production of. The volume-based median diameter of the obtained resin fine particles A-3 was 0.44 μm.

<Production of Resin Fine Particle A-4 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-D (R 1 = H} , R 2 = H, R 3 = C 6 H 5, urethane group concentration: 18 wt%, Tm: 121 ℃, weight average molecular weight A resin fine particle A-4 dispersion liquid was obtained in the same manner as in the production of the resin fine particle A-1 dispersion liquid except that it was changed to 110000). The volume-based median diameter of the obtained resin fine particles A-4 was 0.42 μm.

<Production of Resin Fine Particle A-5 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-E (R 1 = H} , R 2 = H, R 3 = C 6 H 5, urethane group concentration: 4 wt%, Tm: 110 ℃, weight average molecular weight A resin fine particle A-5 dispersion liquid was obtained in the same manner as in the production of the resin fine particle A-1 dispersion liquid except that it was changed to 110000). The volume-based median diameter of the obtained resin fine particles A-5 was 0.46 μm.

<Production of Resin Fine Particle A-6 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-F (R 1 = H} , R 2 = H, R 3 = C 6 H 5, urethane group concentration: 4 wt%, Tm: 86 ℃, weight average molecular weight A resin fine particle A-6 dispersion liquid was obtained in the same manner as in the production of the resin fine particle A-1 dispersion liquid except that it was changed to 110000). The volume-based median diameter of the obtained resin fine particles A-6 was 0.51 μm.

<Production of Resin Fine Particle A-7 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-G (R 1 = H} , R 4 = H, R 5 = O-Q, Q denotes an olefin copolymer, represented by the formula (3) Resin fine particle A-1 dispersed except that the structure is the structure of the above (a4) and L ² is a single bond, urethane group concentration: 10 mass%, Tm: 133 ° C., weight average molecular weight: 300000) A resin fine particle A-7 dispersion was obtained in the same manner as in the production of the solution. The volume-based median diameter of the obtained resin fine particles A-7 was 0.49 μm.

<Production of Resin Fine Particle A-8 Dispersion>
A resin fine particle A-8 dispersion was obtained in the same manner as in the production of the resin fine particle A-1 dispersion except that the acid group-containing olefin copolymer EMA-A was not used. The volume-based median diameter of the obtained resin fine particles A-8 was 1.25 μm.

<Production of Resin Fine Particle A-9 Dispersion>
Resin fine particles A- except that EMA-A is changed to an acid group-containing olefin copolymer EMA-B (ethylene-methacrylic acid copolymer, Tm: 130 ° C., melting point: 95 ° C., acid value: 33 mg KOH / g) Resin fine particle A-9 dispersion liquid was obtained in the same manner as in the production of the dispersion liquid 1. The volume-based median diameter of the obtained resin fine particles A-9 was 0.52 μm.

<Production of Resin Fine Particle A-10 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-H (R 1 = H} , R 2 = H, R 3 = C 6 H 5, urethane group concentration: 8 wt%, hydroxyl group concentration: 2 wt%, Tm Resin fine particle A-10 dispersion liquid was obtained in the same manner as production of resin fine particle A-1 dispersion liquid except changing to 117 ° C., weight average molecular weight: 110,000). The volume-based median diameter of the obtained resin fine particles A-10 was 0.49 μm.

<Production of Resin Fine Particle A-11 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-I (R 1 = H} , R 2 = H, R 3 = C 6 H 5, urethane group concentration: 8 mass%, the ester group concentration: 2% by mass, A resin fine particle A-11 dispersion was obtained in the same manner as in the production of the resin fine particle A-1 dispersion except that the Tm was changed to 113 ° C., and the weight average molecular weight: 110000). The volume-based median diameter of the obtained resin fine particles A-11 was 0.49 μm.

<Production of Resin Fine Particle A-12 Dispersion>
Resin except that 100 parts of EUR-A was changed to 125 parts of urethane-modified polyester PUR (urethane group concentration: 3% by mass, Tm: 110 ° C.) and the acid group-containing olefin copolymer EMA-A was not used A resin fine particle A-12 dispersion was obtained in the same manner as in the production of the fine particle A-1 dispersion. The volume-based median diameter of the obtained resin fine particles A-12 was 0.99 μm.

<Production of Resin Fine Particle A-13 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-J (R 1 = H} , R 2 = H, R 3 = C 6 H 5, urethane group concentration: 26 wt%, Tm: 148 ℃, weight average molecular weight A resin fine particle A-13 dispersion liquid was obtained in the same manner as in the production of the resin fine particle A-1 dispersion liquid except that it was changed to 80000). The volume-based median diameter of the obtained resin fine particles A-13 was 0.49 μm.

<Production of Resin Fine Particle A-14 Dispersion>
EUR-A urethane group-containing olefin copolymer ^{EUR-K (R 1 = H} , R 2 = H, R 3 = C 6 H 5, urethane group concentration: 1 wt%, Tm: 126 ℃, weight average molecular weight A resin fine particle A-14 dispersion liquid was obtained in the same manner as in the production of the resin fine particle A-1 dispersion liquid except that it was changed to 150000). The volume-based median diameter of the obtained resin fine particles A-14 was 0.49 μm.

<Production of Resin Fine Particle B-1 Dispersion>
100 parts of EUR-A is ethylene-vinyl acetate copolymer EVA-A (vinyl acetate-derived monomer unit content: 15% by mass, ester group concentration: 8% by mass, hydroxyl value: 0 mg KOH / g, weight average molecular weight Resin fine particles except that 110000, melting point: 86 ° C., softening point (Tm): 128 ° C., elongation at break: 700%, changed to 125 parts and acid group-containing olefin copolymer EMA-A was not used A resin fine particle B-1 dispersion was obtained in the same manner as in the production of the A-1 dispersion. The volume-based median diameter of the obtained resin fine particles B-1 was 0.40 μm.

<Production of Resin Fine Particle B-2 Dispersion>
Ethylene-vinyl acetate copolymer EVA-A (content of monomer unit derived from vinyl acetate: 15% by mass, ester group concentration: 8% by mass, hydroxyl value: 0 mg KOH / g, weight average molecular weight: 110000, EUR-A) Melting point: 86 ° C, softening point (Tm): 128 ° C, elongation at break: 700%), EMA-A is a crystalline polyester resin [composition (mol%) [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: 78 ° C, acid value: 13 mg KOH / g] Resin fine particle B-2 dispersion liquid was obtained like manufacture of resin fine particle A-1 dispersion liquid except having carried out. The volume-based median diameter of the obtained resin fine particles B-2 was 0.66 μm.

<Manufacture of colorant fine particle dispersion>
-Coloring agent 10.0 parts (Cyan pigment made by Dainichiseika: Pigment Blue 15: 3)
・ Anionic surfactant (Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts ・ ion-exchanged water 88.5 parts Mix the above and use high pressure impact type dispersing machine Nanomizer (Yoshida Kako Kogyo) The mixture was time-dispersed to prepare an aqueous dispersion (colorant particle dispersion liquid) having a concentration of 10% by mass of the colorant particles formed by dispersing the colorant. The volume-based median diameter of the obtained colorant fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrac: manufactured by Nikkiso Co., Ltd.), and was 0.20 μm.

<Production of aliphatic hydrocarbon compound fine particle dispersion>
Aliphatic hydrocarbon compound (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa Co., Ltd.) 20.0 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part After 0 parts or more were charged into a mixing vessel equipped with a stirrer, the mixture was heated to 90 ° C. and circulated to Clearmix W Motion (manufactured by M. Technique) to carry out dispersion treatment for 60 minutes. The conditions of the distributed processing were as follows.
・ Rotor outer diameter 3 cm
・ Clearance 0.3 mm
・ Rotor rotation speed 19000 r / min
・ Screen rotation speed 19000 r / min
After dispersion treatment, the concentration is 20% by mass of aliphatic hydrocarbon compound fine particles by cooling to 40 ° C. under cooling processing conditions of a rotor rotation speed of 1000 r / min, a screen rotation number of 0 r / min and a cooling rate of 10 ° C./min. The aqueous dispersion (aliphatic hydrocarbon compound fine particle dispersion) of The volume-based median diameter of the aliphatic hydrocarbon compound fine particles was measured using a dynamic light scattering particle size distribution diameter (Nanotrac: manufactured by Nikkiso Co., Ltd.) and was 0.15 μm.

<Manufacture of silicone oil emulsion>
-20.0 parts of silicone oil (Dimethyl silicone oil Shin-Etsu Chemical Co., Ltd .: KF 96-50 CS)
An anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part An aqueous emulsion having a concentration of 20% by mass of silicone oil dispersed by dispersing the silicone oil was prepared. The volume-based median diameter of silicone oil particles in the obtained silicone oil emulsion was measured using a dynamic light scattering particle size distribution diameter (Nanotrac: manufactured by Nikkiso Co., Ltd.) and was 0.09 μm.

Example 1 Production of Toner 1
Resin fine particle A-1 dispersion 500 parts Colorant fine particle dispersion 80 parts Aliphatic hydrocarbon compound fine particle dispersion 150 parts Silicone oil emulsion 50 parts Ion-exchanged water 160 parts After charging the mixture into a flask and mixing, 60 parts of a 10% aqueous solution of magnesium sulfate was added. Subsequently, the homogenizer (manufactured by IKA: Ultra-Talux T)
It disperse | distributed for 10 minutes at 5000 r / min using 50). Thereafter, using a stirring blade in a heating water bath, the mixture was heated to 73 ° C. while appropriately adjusting the number of revolutions such that the mixture was stirred. After holding at 73 ° C. for 20 minutes, it was confirmed that the volume-based median diameter of the formed aggregate particles was about 6.0 μm.
After 330 parts of a 5% aqueous solution of ethylenediaminetetraacetic acid in water was added to the dispersion containing the above-mentioned aggregate particles, the mixture was heated to 98 ° C. while continuing the stirring. Then, the aggregate particles were fused by holding at 98 ° C. for 1 hour.
After that, cooling to 50 ° C. and holding for 3 hours promoted crystallization of the urethane group-containing olefin copolymer. Then, after cooling to 25 ° C., and filtering and solid-liquid separation, the filtrate was washed with a 0.5% aqueous solution of ethylenediaminetetraacetic acid sodium acetate, and further washed with ion exchanged water. After washing, the resultant was dried using a vacuum drier to obtain toner particles having a volume-based median diameter of 5.5 μm.
With respect to 100 parts of the obtained toner particles, 1.5 parts of hydrophobized silica fine particles having a number average particle diameter of 10 nm of primary particles, and a hydrophobized treatment of having a number average particle diameter of 100 nm of primary particles Toner 1 was obtained by dry-mixing 2.5 parts of the fine silica particles with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The constitution conditions of the obtained toner 1 are shown in Table 1.

Example 2
In a beaker set in a water bath, 11.7 parts of trisodium phosphate dodecahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1200 parts of ion exchange water were added to dissolve trisodium phosphate dodecahydrate. Subsequently, the temperature of the water bath was raised to 60.degree. After reaching 60 ° C., an aqueous solution in which 5.15 parts of calcium chloride (manufactured by Kishida Chemical Co., Ltd.) was dissolved in 100 parts of ion-exchanged water was added. Stirring was performed for 30 minutes after the addition to obtain an aqueous medium containing a dispersant (tricalcium phosphate).
next,
Urethane group-containing olefin copolymer EUR-A 80 parts Acid group-containing olefin copolymer EMA-A 20 parts Colorant 8 parts (Cyan pigment made by Dainichiseika: Pigment Blue 15: 3)
Aliphatic hydrocarbon compound (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa) 30 parts Silicone oil 10 parts (Dimethyl silicone oil Shin-Etsu Chemical Co., Ltd .: KF 96-50 CS)
Toluene 400 parts The above materials were mixed, and the temperature was raised to 80 ° C. with stirring to dissolve and disperse the materials, thereby producing a resin composition. On the other hand, 600 parts of the aqueous medium containing the above-mentioned tricalcium phosphate was heated to 80 ° C. while being stirred by Clearmix (manufactured by M. Technique).
The resin composition was added to the aqueous medium containing the tricalcium phosphate, and the dispersion was obtained by stirring for 10 minutes at a rotation number of 10000 rpm.
The resulting dispersion was cooled from 80 ° C. to 50 ° C. over 10 minutes while being stirred using a stirring blade, and stirring was continued at a temperature of 50 ° C. for 5 hours to remove toluene.
The particle diameter of the obtained resin particles was measured by a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter, Inc.) according to Coulter method, and the volume-based median diameter was 5.5 μm.
Then, it wash | cleaned and filtered with hydrochloric acid aqueous solution, and also wash | cleaned and filtered with ion-exchange water, and solid-liquid separation was carried out. Next, the obtained solid content was dried to obtain toner particles 2. The volume-based median diameter of the obtained toner particles 2 was 5.9 μm.
With respect to 100 parts of the obtained toner particles, 1.5 parts of hydrophobized silica fine particles having a number average particle diameter of 10 nm of primary particles, and a hydrophobized treatment of having a number average particle diameter of 100 nm of primary particles Toner 2 was obtained by dry-mixing 2.5 parts of the fine silica particles with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The constitution conditions of the obtained toner 2 are shown in Table 1.

Example 3
Toner 3 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-2 dispersion. The volume-based median diameter of the obtained toner particles 3 was 5.3 μm.

Example 4
Toner 4 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-3 dispersion. The volume-based median diameter of the obtained toner particles 4 was 5.5 μm.

Example 5
A urethane group-containing olefin copolymer EUR-A is prepared in the same manner as Example 2 except that 25 parts of ethylene-pobar copolymer EVOH-A and 55 parts of ethylene-isocyanate group-containing copolymer EIC are used. , Toner 5 was obtained. The volume-based median diameter of the obtained toner particles 5 was 5.5 μm.

Example 6
Toner 6 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-4 dispersion. The volume-based median diameter of the obtained toner particles 6 was 5.5 μm.

Example 7
Toner 7 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-5 dispersion. The volume-based median diameter of the obtained toner particles 7 was 5.4 μm.

Example 8
A toner 8 was obtained in the same manner as in Example 1, except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-6 dispersion. The volume-based median diameter of the obtained toner particles 8 was 5.4 μm.

Example 9
Toner 9 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-7 dispersion. The volume-based median diameter of the obtained toner particles 9 was 5.5 μm.

Example 10
A toner 10 was obtained in the same manner as Example 1, except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-8 dispersion. The volume-based median diameter of the obtained toner particles 10 was 7.7 μm.

Example 11
Toner 11 was obtained in the same manner as in Example 1 except that the dispersion of aliphatic hydrocarbon compound fine particles was not used. The volume-based median diameter of the obtained toner particles 11 was 5.4 μm.

Example 12
Toner 12 was obtained in the same manner as in Example 1 except that the aliphatic hydrocarbon compound fine particle dispersion and the silicone oil emulsion were not used. The volume-based median diameter of the obtained toner particles 12 was 5.5 μm.

Example 13
A toner 13 was obtained in the same manner as Example 1, except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-9 dispersion. The volume-based median diameter of the obtained toner particles 13 was 5.4 μm.

Example 14
A toner 14 was obtained in the same manner as in Example 1, except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-10 dispersion. The volume-based median diameter of the obtained toner particles 14 was 5.4 μm.

Example 15
A toner 15 was obtained in the same manner as in Example 1, except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-11 dispersion. The volume-based median diameter of the obtained toner particles 15 was 5.5 μm.

Example 16
A toner 16 was obtained in the same manner as in Example 1, except that the amount of the resin fine particle A-1 dispersed solution was 312.5 parts and 187.5 parts of the resin fine particle B-1 was added. The median diameter of the obtained toner particles 16 was 5.3 μm.

Comparative Example 1
A toner 17 was obtained in the same manner as in Example 1, except that the resin fine particle A-1 dispersion was changed to a resin fine particle B-1 dispersion. The volume-based median diameter of the obtained toner particles 17 was 10.3 μm.

Comparative Example 2
A toner 18 was obtained in the same manner as Example 1, except that the resin fine particle A-1 dispersion liquid was changed to the resin fine particle B-2. The volume-based median diameter of the obtained toner particles 18 was 6.6 μm.

Comparative Example 3
A toner 19 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-12 dispersion. The volume-based median diameter of the obtained toner particles 19 was 7.8 μm.

Comparative Example 4
A toner 20 was obtained in the same manner as in Example 1, except that the resin fine particle A-1 dispersion was changed to 400 parts of the resin fine particle B-1 dispersion and 100 parts of the resin fine particle A-12 dispersion. . The volume-based median diameter of the obtained toner particles 20 was 7.4 μm.

Comparative Example 5
A toner 21 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-13 dispersion. The volume-based median diameter of the obtained toner particles 21 was 7.8 μm.

Comparative Example 6
A toner 22 was obtained in the same manner as in Example 1 except that the resin fine particle A-1 dispersion was changed to a resin fine particle A-14 dispersion. The volume-based median diameter of the obtained toner particles 22 is 7.8 μm
Met.

The following evaluation tests were conducted using Toners 1 to 22. The evaluation results are shown in Table 2.
<Evaluation of low temperature fixability>
A toner and a ferrite carrier (average particle diameter 42 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 8% by mass, to prepare a two-component developer.
An unfixed toner image (0.75 mg / cm ² ) was formed on an image receiving paper (64 g / m ² ) using a commercially available full color digital copying machine (CLC 1100, manufactured by Canon Inc.).
The fixing unit removed from a commercially available full color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon Inc.) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed toner image was performed using this.
The process speed was set to 357 mm / sec under an environment of a room temperature of 15 ° C. and a humidity of 10% RH, and the appearance when the above-mentioned unfixed toner image was fixed was visually evaluated.
A: Fixing is possible at a temperature of 140 ° C. or less.
B: Fixing is possible at temperatures higher than 140 ° C. and lower than 150 ° C.
C: Fixing is possible at a temperature higher than 150 ° C., or there is no temperature range that can be fixed.

<Evaluation of hot offset resistance>
The two-component developer prepared in "Evaluation of low temperature fixability" was used.
A commercially available full color digital copier (CLC1100, manufactured by Canon Inc.) was used for evaluation, and an unfixed toner image (0.1 mg / cm ² ) was formed on an image receiving paper (64 g / m ² ).
The fixing unit removed from a commercially available full color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon Inc.) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed toner image was performed using this.
The process speed was set to 357 mm / sec under an environment of room temperature 23 ° C. and humidity 5% RH, and the appearance when the above-mentioned unfixed toner image was fixed was visually evaluated.
A: Hot offset does not occur at temperatures higher than 160 ° C., or hot offset does not occur up to 200 ° C.
B: Hot offset occurs at temperatures higher than 140 ° C. and lower than 160 ° C.
C: Hot offset occurs at a temperature higher than 130 ° C. and lower than 140 ° C.
D: Hot offset occurs at a temperature of 130 ° C. or less.

<Evaluation of charge retention>
0.01 g of toner was weighed in an aluminum pan and charged to -600 V using a scorotron charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface voltmeter (model 347 manufactured by Trek Japan) under an atmosphere of temperature 30 ° C. and humidity 80% RH.
From the measured results, the charge retention rate was calculated by the following equation. The charge retention was evaluated based on the charge retention.
Charge retention after 30 minutes (%) = (surface potential after 30 minutes / initial surface potential) × 100
A: charge retention rate is 90% or more B: charge retention rate is 50% or more and less than 90% C: charge retention rate is less than 50%

表中、
含有量（１）は、樹脂成分中のウレタン基含有オレフィン系共重合体Ａの含有量（質量％）を表す。
含有量（２）は、樹脂成分中の酸基含有オレフィン系共重合体Ｂの含有量（質量％）を表す。
含有量（３）は、樹脂成分中のエステル基含有オレフィン系共重合体Ｃの含有量（質量％）を表す。
含有量（４）は、樹脂成分１００質量部に対する、脂肪族炭化水素系化合物の含有量（質量部）を表す。
含有量（５）は、樹脂成分１００質量部に対する、シリコーンオイルの含有量（質量部）を表す。
ウレタン基濃度の単位は、“質量％”である。
酸価の単位は、“ｍｇＫＯＨ／ｇ”である。

In the table,
Content (1) represents the content (mass%) of the urethane group-containing olefin copolymer A in the resin component.
The content (2) represents the content (% by mass) of the acid group-containing olefin copolymer B in the resin component.
The content (3) represents the content (% by mass) of the ester group-containing olefin copolymer C in the resin component.
The content (4) represents the content (parts by mass) of the aliphatic hydrocarbon compound with respect to 100 parts by mass of the resin component.
Content (5) represents the content (parts by mass) of silicone oil with respect to 100 parts by mass of the resin component.
The unit of urethane group concentration is "mass%".
The unit of the acid value is "mg KOH / g".

Claims (19)

A toner having toner particles containing a resin component,
The resin component contains a urethane group-containing olefin copolymer A;
The urethane group-containing olefin copolymer A is
A structure Z1 represented by the following formula (1), and at least one structure Z2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
A toner, wherein the urethane group concentration of the urethane group-containing olefin copolymer A is 2% by mass or more and 24% by mass or less.

(In the formulas (1) to (3), R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is an organic group, R ⁴ is H or CH ₃ , R ⁵ is an organic group)   The toner according to claim 1, wherein a content of the urethane group-containing olefin copolymer A in the resin component is 50% by mass or more. The total mass of the urethane group-containing olefin copolymer A is represented by W,
Let l be the mass of the structure represented by the formula (1),
Let m be the mass of the structure represented by the formula (2),
When the mass of the structure represented by the formula (3) is n,
The toner according to claim 1, wherein a value of (l + m + n) / W in the urethane group-containing olefin copolymer A contained in the resin component is 0.80 or more. The urethane group-containing olefin copolymer A has a structure Z1 represented by the formula (1) and a structure Z2 represented by the formula (2),
The toner according to any one of claims 1 to 3, wherein R ¹ is H, R ² is H, and R ³ is a hydrocarbon group. The urethane group-containing olefin copolymer A has a structure Z1 represented by the formula (1) and a structure Z2 represented by the formula (2),
The toner according to any one of claims 1 to 3, wherein R ¹ is H, R ² is H, and R ³ is a phenyl group.   The toner according to any one of claims 1 to 3, wherein the urethane group-containing olefin copolymer A has a crosslinked structure by a urethane bond. The urethane group-containing olefin copolymer A has a structure Z1 represented by the formula (1) and a structure Z2 represented by the formula (2),
The toner according to claim 6, wherein the structure Z2 is the following formula (a3).

The toner according to any one of claims 1 to 7, wherein the urethane group-containing olefin copolymer A has a structure represented by the following formula (6).

(In the formula (6), R ¹⁰ is H or CH _3. ) The toner according to any one of claims 1 to 8, wherein the urethane group-containing olefin copolymer A has a structure represented by the following formula (7).

(In the formula (7), R ¹¹ is H or CH _3. )   The toner according to any one of claims 1 to 9, wherein the softening point of the urethane group-containing olefin copolymer A is 100 ° C or more and 150 ° C or less. The resin component further contains an acid group-containing olefin copolymer B,
The toner according to any one of claims 1 to 10, wherein the acid value of the acid group-containing olefin copolymer B is 50 mgKOH / g or more and 300 mgKOH / g or less. The toner particles contain at least one compound selected from the group consisting of aliphatic hydrocarbons, aliphatic alcohols and aliphatic carboxylic acids,
The toner according to any one of claims 1 to 11, wherein the melting point of the compound is 50 ° C to 100 ° C.   The toner according to any one of claims 1 to 12, wherein the toner particles contain silicone oil. A method for producing a toner having toner particles containing a resin component, comprising:
The resin component contains a urethane group-containing olefin copolymer A;
Preparing a fine resin particle dispersion, wherein fine resin particles for producing the resin component are dispersed in an aqueous medium, or
Dispersing the resin composition in which the resin component is dissolved in an organic solvent in an aqueous medium to prepare particles of the resin composition,
The urethane group-containing olefin copolymer A is
A structure Z1 represented by the following formula (1), and at least one structure Z2 selected from the group consisting of a structure represented by the following formula (2) and a structure represented by the following formula (3),
The method for producing a toner, wherein the urethane group concentration of the urethane group-containing olefin copolymer A is 2% by mass or more and 24% by mass or less.

(In the formulas (1) to (3), R ¹ is H or CH ₃ , R ² is H or CH ₃ , R ³ is an organic group, R ⁴ is H or CH ₃ , R ⁵ is an organic group)   The toner according to claim 14, wherein a content of the urethane group-containing olefin copolymer A in the resin component is 50% by mass or more.   The urethane group-containing olefin copolymer A is produced by reacting an ethylene-poval copolymer or an ethylene-vinyl acetate-poval copolymer with a compound having an isocyanate group to form a urethane bond. A method of producing a toner according to claim 14 or 15. After the step of preparing the resin fine particle dispersion,
Aggregating the resin fine particles to form aggregate particles,
Heating and fusing the aggregate particles;
The method for producing a toner according to any one of claims 14 to 16, further comprising After the step of preparing the particles of the resin composition,
Distilling off the organic solvent contained in the particles of the resin composition,
The method for producing a toner according to any one of claims 14 to 16, further comprising In the step of preparing particles of the resin composition,
A process comprising reacting the ethylene-pobar copolymer or the ethylene-vinyl acetate-pobar copolymer with a compound having an isocyanate group to form the urethane group-containing olefin copolymer B. 16. A method of producing a toner according to any one of 16.