JP2020060703A - toner - Google Patents

Abstract

To provide a toner that is excellent in low-temperature fixability and charge retentivity under a high-temperature and high-humidity environment.SOLUTION: A toner includes a core that contains an amorphous resin, and a shell that contains a urethane group-containing olefin copolymer and covers the core. The glass transition point Tg of the toner measured by a differential scanning calorimetry device (DSC) is 40°C or more and 55°C or less; the urethane group-containing olefin copolymer has monomer units Z1 and Z2 indicated by a specific structure; the urethane bond density of the urethane group-containing olefin copolymer is 2 mass% or more and 24 mass% or less.SELECTED DRAWING: None

Description

  The present invention relates to toner used in electrophotographic systems, electrostatic recording systems, electrostatic printing systems, and toner jet systems.

In recent years, as electrophotographic full-color copying machines have become widespread, higher speed, higher image quality, energy saving, longer life, etc. are required. At the same time, the printing market is required to support a wide range of media (paper types). For example, even if the paper type is changed from thick paper to thin paper, the constant speed of the media that enables continuous printing is required without changing the process speed according to the paper type or changing the heating set temperature of the fixing device. There is. In order to deal with the constant velocity of the medium, the toner is required to properly complete fixing in a wide fixing temperature range from low temperature to high temperature.
Various toners have been proposed in which a crystalline resin having a sharp melting property is added to a toner to improve the low-temperature fixing performance in order to complete the fixing at a wide range of fixable temperatures (Patent Document 1).
As another method, it has been proposed to lower the fixing temperature by using a resin having a low glass transition temperature. A toner containing an ethylene-based ester group-containing copolymer such as an ethylene-vinyl acetate copolymer or an ethylene-methyl acrylate-based copolymer has been proposed as a resin having a low glass transition temperature (Patent Documents 2 to 8). ).

JP, 2011-123352, A JP, 2011-107261, A Japanese Patent Laid-Open No. 11-202555 JP-A-8-184986 JP-A-4-21860 JP-A-3-150576 JP-A-59-18954 JP-A-58-95750

In Patent Document 1, by using the crystalline polyester resin, the plasticized amorphous polyester resin has a low viscosity, and a certain effect can be obtained on the low temperature fixing property. However, since the toner using the crystalline polyester resin has a low electric resistance of the crystalline polyester, the charge amount of the toner tends to fluctuate particularly during continuous printing for a long period under a high temperature and high humidity environment. As a result, there is a problem in that an image is disturbed due to fog and uneven density.
Further, it is difficult to satisfy the low-temperature fixability under high-speed conditions by only partially incorporating these olefinic ester group-containing copolymers into the toner as proposed in Patent Documents 2 to 6 above. there were.
On the other hand, as described in Patent Documents 7 and 8, when these olefinic ester group-containing copolymers are used as the main resin of the toner, the low temperature fixability is improved, but the charge retention in a high temperature and high humidity environment is reduced. A problem has occurred.
As described above, there is still room for study in order to have excellent low-temperature fixability and satisfy the charge retention in a high-temperature and high-humidity environment.
The present invention has been made in view of the above problems, and provides a toner excellent in low-temperature fixability and charge retention in a high-temperature and high-humidity environment.

As a result of intensive studies, the present inventors have made a toner having a core containing an amorphous resin, and a shell covering the core and containing a urethane group-containing olefin-based copolymer and covering the core. The present inventors have found that the use of a toner having particles makes it possible to obtain a toner excellent in charge retention in a high temperature and high humidity environment without impairing low temperature fixability.
That is, the present invention is a toner having toner particles having a core containing an amorphous resin and a shell containing a urethane group-containing olefin-based copolymer and coating the core,
The glass transition point Tg of the toner measured by a differential scanning calorimeter (DSC) is 40 ° C. or higher and 55 ° C. or lower,
The urethane group-containing olefin-based copolymer has a monomer unit Z1 represented by the following formula (1) and a monomer unit Z2 represented by the following formula (2) or (3),
The present invention relates to a toner, wherein the urethane group-containing olefin-based copolymer has a urethane bond concentration of 2% by mass or more and 24% by mass or less.

（前記式（１）、（２）、および（３）中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂はＨ又はＣＨ₃を示し、Ｒ₃は任意の有機基を示し、Ｒ₄はＨ又はＣＨ₃を示し、Ｒ₅は任意の有機基を示す。）

(In the formulas (1), (2), and (3), R ₁ represents H or CH ₃ , R ₂ represents H or CH ₃ , R ₃ represents any organic group, and R ₄ represents H or CH ₃ is shown, and R ₅ is an arbitrary organic group.)

  According to the present invention, it is possible to provide a toner excellent in low-temperature fixability and charge retention in a high temperature and high humidity environment.

  Hereinafter, modes for carrying out the present invention will be described in detail. The crystalline resin is a resin whose endothermic peak is observed in differential scanning calorimetry (DSC).

  The toner of the present invention is a toner having toner particles having a core containing an amorphous resin and a shell containing an olefin copolymer containing a urethane group and coating the core, and the toner is a differential scanning calorimetric analysis. The glass transition point Tg of the toner measured by a device (DSC) is 40 ° C. or higher and 55 ° C. or lower, and the urethane group-containing olefin-based copolymer is a monomer unit Z1 represented by the following formula (1): A toner having a monomer unit Z2 represented by the formula (2) or / and (3), wherein the urethane bond concentration of the urethane group-containing olefin-based copolymer is 2% by mass or more and 24% by mass or less. It has been found that when a toner having particles is obtained, a toner excellent in low-temperature fixability and charge retention in a high temperature and high humidity environment can be obtained.

（前記式（１）、（２）、および（３）中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂はＨ又はＣＨ₃を示し、Ｒ₃は任意の有機基を示し、Ｒ₄はＨ又はＣＨ₃を示し、Ｒ₅は任意の有機基を示す。）

(In the formulas (1), (2), and (3), R ₁ represents H or CH ₃ , R ₂ represents H or CH ₃ , R ₃ represents any organic group, and R ₄ represents H or CH ₃ is shown, and R ₅ is an arbitrary organic group.)

  The present inventors consider the action and effect of using the toner of the present invention having such a configuration as follows.

  It is important that the urethane group-containing olefin-based copolymer of the present invention is used as a toner by using it as a shell that covers a core containing an amorphous resin. In order to improve the low temperature fixability, it is effective to lower the glass transition temperature of the main binder used for the toner particles. As a means therefor, there is a method in which various plasticizers are added to a resin having a high glass transition temperature and a resin designed to have a low glass transition temperature is used as a main binder. However, the toner particles using the main binder having a low glass transition temperature have a low glass transition temperature on the surface thereof, and thus the molecules are likely to move at a high temperature. Further, in a high humidity environment, water is easily adsorbed on the surface of the toner particles, so that the molecular mobility is further promoted. As a result, the electrical resistivity of the surface of the toner particles is reduced, the charge amount of the toner is reduced when left in a high temperature and high humidity environment, and toner scattering and fog occur.

  In the toner of the present invention, the surface of the toner particles containing the amorphous resin has the coating layer containing the urethane group-containing olefin copolymer. Here, the coating layer is a layer in which a part or the entire surface of the toner particles is coated with resin fine particles. Since the olefin portion of the coating layer has a high electric resistance, the adsorption of water in a high humidity environment is suppressed, and the decrease in the charge amount of the toner is suppressed. Further, the urethane portion interacts with the paper at the time of fixing to improve the adhesiveness with the paper, thereby improving the fixability. From the above, the toner with the surface of the toner particles containing the amorphous resin has the coating layer containing the urethane group-containing olefin-based copolymer, the low temperature fixability and the charge retention in the high temperature and high humidity environment. It is thought that both sexes can be achieved.

  In the present invention, a preferable toner constitution for achieving the object will be described in detail below.

  The toner of the present invention has a glass transition point Tg measured by a differential scanning calorimeter (DSC) of 40 ° C. or higher and 55 ° C. or lower. When the glass transition point Tg of the toner is in the range of 40 ° C. or higher and 55 ° C. or lower, both low temperature fixability and storage stability can be achieved.

  In the present invention, the urethane group-containing olefin copolymer is a polymer in which a monomer unit having a urethane group is introduced into the polyolefin skeleton by means such as copolymerization. Specifically, it has a monomer unit Z1 represented by the above formula (1) and a monomer unit Z2 represented by the above formula (2) or / and (3).

  Hereinafter, the monomer unit Z1 represented by the formula (1) and the monomer unit Z2 represented by the formula (2) or / and (3) will be specifically described.

R _{3 and} R ₅ can have any organic group. Specifically, an alkyl group such as a methyl group, an ethyl group and a hexyl group, an alkenyl group such as a vinyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group and a naphthyl group, and a benzyl group. Examples thereof include, but are not limited to, an araalkyl group or a substituent in which a part of these hydrocarbon groups is substituted with halogen, alcohol, carboxylic acid, amine, sulfonic acid, or the like.

In the monomer unit Z1 represented by the formula (1) and the monomer unit Z2 represented by the formula (2) or / and (3), R ₁ is H, R ₂ is H, and R ₃ is a hydrocarbon group. An ethylene-urethane vinyl alcohol copolymer is preferable from the viewpoint of low-temperature fixability because it can be designed to have a low melting point.

  The urethane group-containing olefin-based copolymer may be contained in the toner in one or more kinds.

  The urethane bond concentration of the urethane group-containing olefin-based copolymer is 2% by mass or more and 24% by mass or less. When the urethane bond concentration was controlled to the above concentration, the urethane group-containing olefin-based copolymer of the present invention had high resistance and improved chargeability, despite having a highly polar urethane bond.

  If the urethane bond concentration is less than 2% by mass, the adhesiveness to the paper at the time of fixing may be deteriorated due to the interaction of the urethane group with the paper, and the low-temperature fixability may be deteriorated. On the other hand, when the urethane bond concentration exceeds 24% by mass, the melting point of the material is high, so that the low-temperature fixability is insufficient and the chargeability may be deteriorated due to the polarity of a large amount of urethane groups.

  Further, the total mass of the urethane group-containing olefin-based copolymer is X, the mass of the monomer unit Z1 represented by the formula (1) is a, and the mass of the monomer unit Z2 represented by the formula (2) or / and (3) is When the mass is b, the value of (a + b) / X in the olefinic hydroxyl group-containing copolymer contained in the resin component is 0.80 or more and 1.00 or less from the viewpoint of low-temperature fixability and charge maintainability. Preferably, it is 0.95 or more, more preferably 1.00 or less, and further preferably 1.00.

  The urethane group-containing olefin-based copolymer may contain a monomer unit other than the monomer unit Z1 and the monomer unit Z2. It is not particularly limited as long as the effects of the present invention are not impaired, but for example, a monomer unit represented by the following formula (4), a monomer unit represented by the following formula (5), or a monomer unit represented by the following formula (6). And so on. These are introduced by adding a corresponding monomer during the copolymerization reaction for producing the urethane group-containing olefin-based copolymer or by modifying the urethane group-containing olefin-based copolymer by a polymer reaction. You can

（前記式（６）中、Ｒ₆はＨ又はＣＨ₃を示し、Ｒ₇はＣＨ₃又はＣ₂Ｈ₅を示す。）

(In the formula (6), R ₆ represents H or CH ₃ , and R ₇ represents CH ₃ or C ₂ H _5. )

The mass of the monomer unit represented by each of the above formulas and the content of the monomer unit Z2 can be measured using a general analysis method. For example, techniques such as nuclear magnetic resonance method ( ¹ H-NMR) and thermal decomposition gas chromatography method can be applied.

  The melting point of the urethane group-containing olefin-based copolymer of the present invention is preferably 80 ° C or higher and 150 ° C or lower. From the viewpoint of toner durability, the melting point is 80 ° C. or higher, preferably 90 ° C. or higher. On the other hand, from the viewpoint of low-temperature fixability, the melting point is 150 ° C or lower, preferably 130 ° C or lower, and more preferably 110 ° C or lower.

  Further, the charge retention property was improved by setting the melting point to 150 ° C. or lower. The melting point of the urethane group-containing olefin copolymer can be controlled by, for example, the content of the urethane group-containing monomer unit (that is, the monomer unit Z2).

  The softening point (Tm) of the urethane group-containing olefin-based copolymer is preferably 100 ° C. or higher and 150 ° C. or lower from the viewpoint of withstanding impact and pressure when the toner is used. The softening point (Tm) can be controlled by changing the molecular weight of the urethane group-containing olefin-based copolymer, and the softening point can be increased by increasing the molecular weight.

  The content of the urethane group-containing olefin-based copolymer is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 10 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the toner particles. preferable. When the content is in the above range, it is possible to improve the adhesion to paper while suppressing the environmental change of the charging property.

  The method for producing the urethane group-containing olefin-based copolymer is not particularly limited, but from the viewpoint of ease of production, an ethylene-vinyl acetate copolymer is hydrolyzed to produce an ethylene-Povar copolymer, and then an isocyanate group is used. A production method of reacting with a compound containing An example of the manufacturing method is shown below. First, the ethylene-vinyl acetate copolymer was refluxed with sodium hydroxide in a mixed solvent of toluene and ethanol at 90 ° C. to hydrolyze the ester group of the ethylene-vinyl acetate copolymer. Thus, a hydroxyl group-containing olefin-based copolymer can be obtained. Next, the urethane group-containing olefin copolymer is obtained by mixing the obtained hydroxyl group-containing olefin copolymer and a compound having an isocyanate group and heating the mixture at 60 ° C.

  As the isocyanate compound, a blocked isocyanate compound protected by a blocker may be used. When a blocked isocyanate compound is used, it is necessary to raise it to a temperature at which the blocker is removed and the isocyanate group reacts, and it is necessary to select a solvent species having a high boiling point.

  Moreover, the following method is mentioned as another manufacturing method. By reacting the hydroxyl group-containing olefin-based copolymer with an excess amount of an isocyanate compound, the hydroxyl group of the hydroxyl group-containing olefin-based copolymer can be converted into an isocyanate group. By urethane-forming the obtained isocyanate group-containing olefin copolymer and a compound having a hydroxyl group, a urethane group-containing olefin copolymer can be prepared.

  The coating of the urethane group-containing olefin-based copolymer on the surface of the toner particles can be carried out by a known method such as an external addition method, an emulsion aggregation method, a mechanofusion method, a fluidized bed type, a wet coating method.

  According to the external addition method, it can be carried out by externally adding the urethane group-containing olefin-based copolymer to the surface of the toner particles by using a mixing device. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid.

  In the emulsion aggregation method, the coating layer can be formed by adding the urethane group-containing olefinic copolymer particle dispersion liquid to the toner particle dispersion liquid and adhering the resin particles to the toner particle surface. The obtained toner can be easily isolated from the reaction system by a general isolation and purification method such as filtration, washing with pure water, and vacuum drying.

  According to the mechanofusion method, for example, after the cyclic urethane group-containing olefin-based copolymer is electrostatically adsorbed on the surface of the toner particles, the surface of the toner particles is pressed by a mechanical shock to partially or entirely remove the cyclic polyolefin resin. Is melted to form a coating layer. To carry out the mechanofusion method, various commercially available mechanofusion devices can be used.

  Further, according to the fluidized bed coating method, a fluidized bed of toner particles is formed, and a solution of a urethane group-containing olefinic copolymer or urethane group-containing olefinic copolymer particles is spray-coated in the fluidized bed to obtain a solution. It is manufactured by drying the solvent contained in to form a coating layer. To implement the fluidized bed coating method, for example, a fluidized bed type coating device or the like can be used.

  The wet coating method includes, for example, a dipping method and a fluidized bed method. According to the fluidized bed method, the operation of raising the toner particles to an equilibrium height by an ascending pressurized gas flow and then spray-coating the urethane group-containing olefin-based copolymer solution until the toner particles fall The coating layer is formed by repeating. To carry out the wet coating method, for example, a spray coating device, a spray dryer or the like can be used.

  As the amorphous resin used in the present invention, a known polymer usually used for toner can be used. Specifically, the following polymers can be used, and two or more of them may be used in combination.

  Polystyrene, poly-p-chlorostyrene, homopolymers of styrene such as polyvinyltoluene and substitution products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrene-based copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic acid resins, acrylic resins , Methacrylic tree , Polyvinyl acetate, silicone resin, amorphous polyester, a crystalline polyester, polyurethane, polyamide, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, and petroleum resins. Among these, an amorphous polyester which is compatible with both low-temperature fixability and mechanical strength is preferable because it has excellent strength even with a low molecular weight.

  Examples of the monomer used in the polyester unit of the amorphous polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), and acid anhydrides thereof. Alternatively, a lower alkyl ester thereof is used. Here, in the case of producing a branched polymer, it is effective to partially crosslink within the molecule of the binder resin, and for that purpose, it is preferable to use a polyfunctional compound having a valence of 3 or more. Therefore, it is preferable that the raw material monomer of the polyester unit contains a carboxylic acid having a valence of 3 or more, an acid anhydride thereof or a lower alkyl ester thereof, and / or an alcohol having a valence of 3 or more.

  As the polyhydric alcohol monomer used for the polyester unit of the polyester resin, the following polyhydric alcohol monomers can be used.

  As the dihydric alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol represented by formula (A) and derivatives thereof;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 or more and 10 or less.)

  Diols represented by formula (B);

が挙げられる。

Is mentioned.

  Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned. Of these, glycerol, trimethylolpropane and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

  As the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.

  Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and These lower alkyl ester is mentioned. Of these, maleic acid, fumaric acid, terephthalic acid and n-dodecenylsuccinic acid are preferably used.

  Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Examples thereof include methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, enpol trimer acid, acid anhydrides thereof or lower alkyl esters thereof. Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof is particularly preferable because it is inexpensive and the reaction control is easy. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

  A hybrid resin containing other resin components may be used as long as it has a polyester resin as a main component. For example, a hybrid resin of polyester resin and vinyl resin may be mentioned. A method for obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, includes a vinyl resin or a vinyl copolymer unit and a monomer component capable of reacting with each of the polyester resins. Where the polymer is present, a method of carrying out a polymerization reaction of one or both resins is preferable.

  For example, among the monomers constituting the polyester resin component, those capable of reacting with the vinyl-based copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. To be Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  Further, the acid value of the binder resin of the present invention is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment. Further, the hydroxyl value of the binder resin of the present invention is preferably 2 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of low-temperature fixability and storability. Further, the glass transition temperature is preferably 30 ° C. or higher and 80 ° C. or lower. When the temperature is lower than 30 ° C., the preservability is deteriorated, and the resistance lowering due to the molecular motion of the resin is induced under the high temperature and high humidity environment to deteriorate the charging property. On the other hand, when the glass transition temperature is higher than 80 ° C, the fixability is poor. Further, the glass transition temperature is preferably 40 ° C. or higher from the viewpoint of storage stability. Further, the glass transition temperature is preferably 70 ° C. or lower from the viewpoint of fixability. The softening temperature (Tm) is preferably 70 ° C or higher and 150 ° C or lower, more preferably 80 ° C or higher and 140 ° C or lower, and further preferably 80 ° C or higher and 130 ° C or lower. When Tm is within the above temperature range, both blocking resistance and offset resistance are well achieved, and further, the toner melted component is absorbed into the paper at the time of fixing at a high temperature, which is good. Surface smoothness is obtained.

  Further, the binder resin of the present invention may be used as a mixture of a high molecular weight binder resin A and a low molecular weight binder resin B. The content ratio (A / B) of the binder resin A having a high molecular weight and the binder resin B having a low molecular weight is 10/90 or more and 60/40 or less on a mass basis. Is preferred.

  The peak molecular weight of the high molecular weight binder resin A is preferably 10,000 or more and 20,000 or less from the viewpoint of hot offset resistance. The acid value of the high molecular weight binder resin is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

  The number average molecular weight of the low molecular weight binder resin B is preferably 1500 or more and 3500 or less from the viewpoint of low temperature fixability. Further, the acid value of the low molecular weight binder resin is preferably 10 mgKOH / g or less from the viewpoint of charge stability in a high temperature and high humidity environment.

  In the present invention, a crystalline polyester compatible with the amorphous resin of the core can be used if necessary. The crystalline polyester used in the present invention is obtained by polycondensing an aliphatic diol having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. The content of the crystalline polyester used in the present invention is preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the amorphous polyester resin. When the content of the crystalline polyester is within the above range, the low temperature fixability is improved. When the content of the crystalline polyester is less than 1 part by mass, the low temperature fixability is not improved. On the other hand, if the content exceeds 30 parts by mass, the crystalline polyester cannot be finely dispersed in the toner, and the low temperature fixability may not be improved.

  Examples of the wax used in the toner of the present invention include the following. Hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymers thereof; Waxes containing fatty acid esters such as carnauba wax as a main component; deoxidized fatty acid esters such as carnauba wax, which are partially or entirely deoxidized. Further, the following may be mentioned. Saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, melyl alcohol Saturated alcohols such as silalcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, and melyl alcohol. Esters with alcohols such as sil alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid Saturated fatty acid bisamides such as amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N'-dioleyl adipic acid amide, N, N'dioleyl Unsaturated fatty acid amides such as sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide, N, N 'distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Such as aliphatic metal salts (generally referred to as metallic soap); waxes obtained by grafting aliphatic hydrocarbon wax with vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride Value Al Partial esters of Lumpur; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

  Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable because the hot offset resistance is further improved.

  In the present invention, the wax is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin.

  Further, in the endothermic curve at the time of temperature increase measured by a differential scanning calorimetry (DSC) device, the peak temperature of the maximum endothermic peak of the wax is preferably 45 ° C or higher and 140 ° C or lower. It is preferable that the peak temperature of the maximum endothermic peak of the wax is within the above range because both the storage stability and the hot offset resistance of the toner can be achieved.

<Colorant>
Examples of the coloring agent that can be contained in the toner include the following.

  Examples of the black colorant include carbon black; those obtained by toning black with a yellow colorant, a magenta colorant and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image.

  Examples of the magenta toner pigment include the following. 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, 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, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C.I. I. Butt 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; C.I. I. Disperse Red 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil soluble dyes such as Disper 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; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

  Examples of cyan toner pigments 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 in which 1 to 5 phthalimidomethyl groups are substituted in the phthalocyanine skeleton.

  Examples of dyes for cyan toner include C.I. I. There is Solvent Blue 70.

Examples of the pigment for yellow toner 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.
Examples of dyes for yellow toner include C.I. I. There is Solvent Yellow 162.

  The amount of the colorant used is preferably 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the binder resin.

<Charge control agent>
The toner may contain a charge control agent, if necessary. As the charge control agent contained in the toner, known charge control agents can be used, but in particular, a metal compound of an aromatic carboxylic acid which is colorless and has a high charging speed of the toner and which can stably maintain a constant charge amount is preferable.

  As the negative charge control agent, a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a polymer type compound having a sulfonic acid or a carboxylic acid in the side chain, and a sulfonate or a sulfonate ester compound in the side chain Examples thereof include a polymer type compound, a polymer type compound having a carboxylic acid salt or a carboxylic acid ester compound as a side chain, a boron compound, a urea compound, a silicon compound, and a calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer type compound having the quaternary ammonium salt in its side chain, a guanidine compound, and an imidazole compound. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Inorganic fine particles>
The toner of the present invention may contain inorganic fine particles, if necessary. The inorganic fine particles may be internally added to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powders such as silica, titanium oxide and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

As the external additive for improving the fluidity, an inorganic fine powder having a specific surface area of 50 m ² / g or more and 400 m ² / g or less is preferable, and a specific surface area of 10 m ² / g or more and 50 m or more for stabilizing durability. It is preferably an inorganic fine powder of ² / g or less. In order to achieve both improvement of fluidity and stabilization of durability, inorganic fine powder having a specific surface area in the above range may be used together.

  The external additive is preferably used in an amount of 0.1 part by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

<Developer>
The toner of the present invention can be used also as a one-component developer, but in order to further improve dot reproducibility, it can be mixed with a magnetic carrier and used as a two-component developer, and a stable image can be obtained for a long period of time. Is preferred in that

  As the magnetic carrier, for example, surface-oxidized iron powder, or unoxidized iron powder, iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, metal particles such as rare earth, those Magnetic particles such as alloy particles, oxide particles, ferrite, and other magnetic materials, and a magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state are generally known. You can use one.

  When the toner of the present invention is mixed with a magnetic carrier to be used as a two-component developer, the carrier mixing ratio in that case is 2% by mass or more and 15% by mass or less, preferably the toner concentration in the two-component developer. When 4% by mass or more and 13% by mass or less, good results are usually obtained.

<Manufacturing method>
The method for producing the toner of the present invention is not particularly limited as long as it is a conventionally known toner production method such as an emulsion aggregation method, a melt kneading method, and a dissolution suspension method.

  The melt-kneading method is characterized by melt-kneading a toner composition as a raw material of toner particles and pulverizing the obtained kneaded product. An example of the manufacturing method will be described.

  In the raw material mixing step, polyester resin A, polyester resin B, an organometallic compound, and if necessary, other components such as wax and colorant are weighed and mixed in a predetermined amount as materials for forming toner particles, and mixed. . Examples of the mixing device include a double mixer, a V type mixer, a drum type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.) and the like.

  Next, the mixed materials are melt-kneaded to disperse other raw materials in the binder resin. In the melt-kneading step, a batch-type kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used, and a single-screw or twin-screw extruder is mainly used because of its superiority of continuous production. There is. For example, KTK twin-screw extruder (Kobe Steel Co., Ltd.), TEM twin-screw extruder (Toshiba Machinery), PCM kneader (Ikegai Tekko), twin-screw extruder (KCK) ), Co-Kneader (manufactured by Buss), Needex (manufactured by Nippon Coke Industry Co., Ltd.) and the like. Further, the resin composition obtained by melt-kneading may be rolled with a two-roll mill or the like and cooled with water or the like in the cooling step.

  Then, the cooled product of the resin composition is crushed to a desired particle size in a crushing step. In the crushing process, for example, after roughly crushing with a crusher such as a crusher, a hammer mill, and a feather mill, further, for example, a Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill. (Turbo Kogyo Co., Ltd.) or finely pulverized with an air jet type fine pulverizer.

  Then, if necessary, classification such as an inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal force classification type turboplex (manufactured by Hosokawa Micron), a TSP separator (manufactured by Hosokawa Micron), and a faculty (manufactured by Hosokawa Micron) To obtain toner particles. Among them, Faculty (manufactured by Hosokawa Micron Co., Ltd.) is preferable from the viewpoint that the spheroidizing treatment of the toner particles can be performed simultaneously with the classification, and the transfer efficiency is improved.

  If necessary, after grinding, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechanofusion system (manufactured by Hosokawa Micron Co., Ltd.), a faculty (manufactured by Hosokawa Micron Co., Ltd.), and a Meteoleinbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) are used. Thus, surface treatment of toner particles such as spheroidization treatment can be performed.

  The average circularity of the toner is preferably 0.930 or more and 0.985 or less from the viewpoint of achieving both improved transferability and cleaning performance. When the toner is produced by a pulverization method, the toner having the above-mentioned average circularity can be produced by subjecting the toner particles to a surface treatment such as a spheroidizing treatment or a heat treatment.

  An emulsion aggregation method will be described as another manufacturing method.

  The emulsion aggregation method is a production method for preparing core particles by preparing in advance resin fine particles that are sufficiently small for the target particle size and aggregating the resin fine particles in an aqueous medium. In the emulsion aggregation method, toner particles are manufactured through an emulsification step, an aggregation step, a fusing step, a cooling step and a washing step of resin fine particles. If necessary, a shelling step may be added after the cooling step to obtain a core-shell toner.

<Emulsification process of resin particles>
The resin fine particles containing a polyester resin as a main component can be prepared by a known method. For example, the resin is dissolved in an organic solvent and added to an aqueous medium, and the particles are dispersed in the aqueous medium with a disperser such as a homogenizer together with a surfactant and a polyelectrolyte, and then the solvent is removed by heating or reducing the pressure. A resin particle dispersion can be prepared. As the organic solvent used for dissolving, any solvent can be used as long as it dissolves the resin, but tetrahydrofuran, ethyl acetate, chloroform and the like are preferable from the viewpoint of solubility.

  Further, the resin and the surfactant, a base and the like are added to the aqueous medium, and the mixture is subjected to high-speed shearing force such as Clearmix, homomixer, and homogenizer to be emulsified and dispersed in the aqueous medium containing substantially no organic solvent. Is preferable from the viewpoint of environmental load. In particular, the content of the organic solvent having a boiling point of 100 ° C. or lower is preferably 100 μg / g or lower. When the amount is out of the above range, a step of removing and recovering the organic solvent is newly required when manufacturing the toner, which imposes a burden on wastewater treatment measures. The organic solvent content in the aqueous medium can be measured using gas chromatography (GC).

  The surfactant used at the time of emulsification is not particularly limited, but examples thereof include anionic surfactants such as a sulfate ester type, a sulfonate type, a carboxylate type, a phosphate ester type, and a soap type anionic surfactant; Examples thereof include amine salt-type and quaternary ammonium salt-type cationic surfactants; polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based nonionic surfactants and the like. The surfactants may be used alone or in combination of two or more.

  The volume-based median diameter of the resin fine particles is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.05 μm or more and 0.4 μm or less. If it exceeds 1.0 μm, it becomes difficult to obtain toner particles having a volume-based median diameter of 4.0 μm or more and 7.0 μm or less, which is suitable as toner particles. The volume-based median diameter can be measured by using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).

<Coagulation process>
The aggregating step is to prepare a mixed solution by mixing the above-mentioned resin fine particles, coloring material fine particles, and release agent fine particles according to the required amount, and then agglomerate the particles contained in the prepared mixed solution to form an aggregate. Is a step of forming. As a method for forming the agglomerates, for example, a method in which a flocculant is added / mixed in the mixed liquid and temperature, mechanical power and the like are appropriately added can be suitably exemplified.

  Examples of the aggregating agent 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.

  The addition and mixing of the aggregating agent is preferably performed at a temperature not higher than the glass transition temperature (Tg) of the resin particles contained in the mixed liquid. When the above mixing is performed under this temperature condition, aggregation proceeds in a stable state. The above-mentioned mixing can be performed using a known mixing device, homogenizer, mixer or the like.

  The weight average particle diameter of the agglomerates formed here is not particularly limited, but is usually controlled to 4.0 μm or more and 7.0 μm or less so as to be approximately the same as the weight average particle diameter of the toner particles to be obtained. Good to do. The control can be easily performed, for example, by appropriately setting / changing the temperature at the time of adding / mixing the coagulant or the like and the conditions of the stirring / mixing. The particle size distribution of the toner particles can be measured with a particle size distribution analyzer by the Coulter method (Coulter Multisizer III: manufactured by Coulter).

<Fusion process>
The fusing step is a step of producing particles in which the surface of the agglomerate is smoothed by heating the agglomerate to a temperature not lower than the glass transition point (Tg) of the resin to fuse the particles. Before entering the primary fusing step, a chelating agent, a pH adjusting agent, a surfactant and the like can be added as appropriate in order to prevent fusion between the toner particles.

  Examples of chelating agents are alkali metal salts such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, sodium gluconate, sodium tartrate, potassium and sodium citrate, nitrotriacetate (NTA) salts, both COOH and OH. There are many water-soluble polymers (polyelectrolytes) containing the functionality of.

  The heating temperature may be between the glass transition temperature (Tg) of the resin contained in the aggregate and the temperature at which the resin thermally decomposes. As for the heating and fusing time, a shorter time is required if the heating temperature is higher, and a longer time is required if the heating temperature is lower. That is, the heating / fusing time cannot be unconditionally specified because it depends on the heating temperature, but it is generally 10 minutes to 10 hours.

<Cooling process>
The cooling step is a step of cooling the temperature of the aqueous medium containing the particles to a temperature lower than the glass transition point (Tg) of the core resin. Coarse particles are generated unless cooling is performed to a temperature lower than Tg. The specific cooling rate is 0.1 ° C./min or more and 50 ° C./min or less.

<Coating process>
Further, in the present invention, if necessary, a coating step can be inserted before the following washing and drying step. The coating step is a step in which resin particles are newly added to and adhered to the particles produced in the steps so far, and the particles are coated.

  The binder resin particles added here may have the same structure as the binder resin particles used for the core, or may have a different structure.

<Washing and drying process>
The particles produced through the above steps are washed and filtered with ion-exchanged water whose pH is adjusted with sodium hydroxide or potassium hydroxide, and subsequently washed with ion-exchanged water and filtered a plurality of times. Then, it can be dried to obtain emulsion aggregation toner particles.

  Next, methods for measuring each physical property relating to the present invention will be described.

  The methods for measuring various physical properties of the toner and raw materials will be described below.

<Measurement of Unit Mass Ratio of Urethane Group-Containing Olefin Copolymer>
Specifically, a urethane group-containing copolymer obtained by urethane-forming the hydroxyl group of ethylene-poval with phenyl isocyanate (containing a monomer unit (1) and a monomer unit (2), R ₁ = H, R ₂ = H, R ₃ Is a C ₆ H ₅ copolymer) and the monomer unit content ratio is calculated by the following method.

  The hydrogen atom of the alkylene group of the monomer unit represented by the formula (1) and the hydrogen integral ratio of the methine group to which the urethane group of the monomer unit represented by the formula (2) or / and (3) are bonded are compared with each other. Thus, the content ratio of each monomer unit can be calculated.

Hereinafter, the measuring method using ¹ H-NMR will be described.

About 5 mg of the sample is dissolved in 0.5 mL of heavy dimethyl sulfoxide (DMSO) containing 0.00 ppm of tetramethylsilane as an internal standard and tetrafluoroacetic acid (TFA) as an additive. The obtained solution is put into a sample tube, and a ¹ H-NMR spectrum is measured under the conditions of a repetition time of 2.7 seconds and an integration number of 16 times.

Peak of 1.1-1.4ppm corresponds to CH ₂ -CH ₂ monomer units derived from ethylene, the peak near 7.0-8.0ppm corresponds to C ₆ H ₅ phenyl groups. The ratio of the integrated values of those peaks is calculated to calculate the content ratio of each monomer unit.

  Hereinafter, the measuring method by the ATR method will be shown. The FT-IR spectrum by the ATR method was performed using a Spectrum One (Fourier transform infrared spectrophotometer) (PerkinElmer) equipped with a Universal ATR Sampling Accessory (universal ATR measurement accessory).

The incident angle of infrared light was set to 45 °. As the prism used for the ATR measurement, an ATR crystal of Ge (refractive index = 4.0) was used. Other conditions are as follows.
Range
Start: 4000 cm ^-1
End: 600 cm ^-1
Duration
Scan Number: 4
Resolution: 4.00 cm ^-1
Advanced: With CO ₂ / H ₂ O correction

The specific measurement procedure is as follows.
Calculation method of Pa (1) A Ge ATR crystal (refractive index = 4.0) is attached to the apparatus.
(2) Set Scan type to Background and Units to EGY, and measure the background.
(3) Set Scan type to Sample and Units to A.
(4) 0.01 g of the toner is precisely weighed on the ATR crystal.
(5) Pressurize the sample with the pressure arm. (Force Gauge is 100)
(6) Measure the sample.
(7) Baseline correction of 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 value of the absorption peak intensities at 1680 cm ^-1 and 1690 cm ^-1 (Pa2, carbonyl group of urethane).
(10) The urethane group concentration is calculated from Pa1 / Pa2.

<Measurement of glass transition temperature (Tg) of resin and toner particles>
The glass transition temperature of the resin and toner particles is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments).

  The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.

  Specifically, about 5 mg of a sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and a temperature rising rate is 10 ° C./min in a measurement range of 30 to 200 ° C. Measure with. The temperature is once raised to 180 ° C. and kept for 10 minutes, then lowered to 30 ° C., and then raised again. In the second heating process, a specific heat change is obtained in the temperature range of 30 to 100 ° C. The glass transition temperature (Tg) of the resin is defined as the intersection of the line at the midpoint of the baseline before and after the change in specific heat and the differential heat curve. Further, the amount of heat obtained from the area of the maximum endothermic peak of the temperature-endothermic amount curve in the temperature range of 60 to 90 ° C. is taken as the endothermic amount.

<Measurement of melting point of resin>
The melting point can be measured using an differential scanning calorimeter (DSC). Specifically, 0.01 to 0.02 g of the sample is weighed in an aluminum pan, and the calorific value is measured while increasing the temperature of the sample from room temperature at a temperature increase rate of 10 ° C./min. Then, from the obtained DSC curve, the peak temperature of the endothermic peak is taken as the melting point. The melting point of the crystalline olefinic hydroxyl group-containing copolymer present in the toner can also be measured by the same method. At that time, a melting point due to the release agent present in the toner may be observed. To determine the melting point of the releasing agent and the melting point of the crystalline olefinic hydroxyl group-containing copolymer, the releasing agent is extracted from the toner by Soxhlet extraction using a hexane solvent, and the scanning scanning calorimetry of the releasing agent alone is performed as described above. The melting point obtained is compared with the melting point of the toner.

<Measurement of DSC endothermic amount (ΔH) of wax and crystalline polyester>
The peak temperature (Tp) of the maximum endothermic peak of the wax and crystalline polyester in the present invention is measured using DSC Q1000 (TA Instruments) under the following conditions.
Temperature rising rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C

  The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.

  Specifically, about 5 mg of a sample is precisely weighed, placed in a silver pan, and measured once. An empty silver pan is used as a reference.

  When the toner is used as a sample and the maximum endothermic peak (maximum endothermic peak derived from the binder resin) does not overlap with the endothermic peaks of resins other than wax and crystalline polyester, the endothermic amount of the obtained maximum endothermic peak Is directly treated as the endothermic amount of the maximum endothermic peak derived from wax and crystalline polyester. On the other hand, when the toner is used as a sample, if the endothermic peak of the resin other than the wax and the binder resin overlaps with the maximum endothermic peak of the binder resin, the endothermic amount derived from the resin other than the wax and the binder resin is determined. , It is necessary to subtract from the obtained endothermic amount of the maximum endothermic peak.

  The maximum endothermic peak means the peak having the maximum endothermic amount when there are a plurality of peaks. Further, the endothermic amount (ΔH) of the maximum endothermic peak is calculated from the area of the peak by using the analysis software attached to the apparatus.

<Measurement of softening point of resin>
In the present invention, the softening temperature of the amorphous resin was measured using a constant load extrusion type capillary rheometer "Flow characteristic evaluation device Flow tester CFT-500D" (manufactured by Shimadzu Corporation). The CFT-500D melts while heating the temperature of the measurement sample filled in the cylinder while applying a constant load from the top with the piston, and pushes it out from the thin tube hole at the bottom of the cylinder. It is a device that can graph a flow curve from temperature (° C).

In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation apparatus Flow Tester CFT-500D" was defined as the softening temperature (Tm).
The melting temperature in the 1/2 method is calculated as follows.

  First, a half of the difference between the amount of lowering of the piston when the outflow ends (outflow end point, Smax) and the amount of lowering of the piston when the outflow starts (minimum point, Smin) is calculated. (This is designated as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of drop of the piston was the sum of X and Smin was taken as the melting temperature in the 1/2 method.

  The measurement sample is about 1.2 g of the binder resin at about 10 MPa in a 25 ° C. environment using a tablet molding compressor (for example, a standard manual Newton press NT-100H, manufactured by NPA System Co., Ltd.). A columnar product having a diameter of about 8 mm which is compression molded for about 60 seconds is used. The specific operation for 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
Ultimate temperature: 200 ℃
Measurement interval: 1.0 ° C
Temperature rising rate: 4.0 ° C / min
Cross-sectional area of piston: 1.000 cm ²
Test load (piston load): 5.0kgf (49N)
Preheat time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement of weight average molecular weight by GPC>
The column is stabilized in a heat chamber at 40 ° C., THF as a solvent is caused to flow at a flow rate of 1 ml / min, and about 100 μl of a THF sample solution is injected into the column at this temperature for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count value of the calibration curve prepared using several kinds of monodisperse polystyrene standard samples. As the standard polystyrene sample for preparing the calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh or Showa Denko is used, and it is suitable to use a standard polystyrene sample of at least about 10 points. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, a combination of Shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK and a product manufactured by Tosoh Corporation. The combination of TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgurd column is listed. be able to.

  The sample is prepared as follows.

  The sample is placed in THF, left at 25 ° C. for several hours, shaken well, mixed well with THF (until the coalescence of the sample disappears), and left still for 12 hours or more. At that time, the leaving time in THF is set to be 24 hours. After that, a sample that has passed through a sample processing filter (pore size 0.2 μm or more and 0.5 μm or less, for example, Mysholydisk H-25-2 (manufactured by Tosoh Corp.) can be used) is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 mg / ml or more and 5.0 mg / ml or less.

<Method of measuring weight average particle diameter (D4) of toner particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) by a pore electrical resistance method equipped with an aperture tube of 100 μm. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis, the measurement data is measured with 25,000 effective measurement channels. Is calculated and calculated.

  The electrolytic aqueous solution used for the measurement may be prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).

  Before the measurement and analysis, the dedicated software is set as follows.

  On the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained by using the product. The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the flash of the aperture tube after the measurement is checked.

  On the "pulse-to-particle size conversion setting screen" of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measuring method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution was placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution was placed in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder, pH7 precision measurement as a dispersant was added to this). Approximately 0.3 ml of a diluting solution prepared by diluting a 10 mass% aqueous solution of a neutral detergent for cleaning vessels with Wako Pure Chemical Industries, Ltd. with ion-exchanged water to 3 mass times is added.
(3) Two oscillators with an oscillating frequency of 50 kHz are built in with the phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios) with an electric output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker becomes maximum.
(5) About 10 mg of toner is added little by little to the electrolytic aqueous solution in a state where the electrolytic aqueous solution in the beaker of the above (4) is irradiated with ultrasonic waves and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C or higher and 40 ° C or lower.
(6) To the round-bottom beaker of (1) installed in the sample stand, drop the toner-dispersed aqueous electrolyte solution of (5) with a pipette and adjust so that the measured concentration is about 5%. . Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The “average diameter” on the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measurement of particle size of emulsified fine particles>
The particle size distribution of particles such as emulsified particles is measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) according to the operation manual of the device. Specifically, the volume distribution was measured by adjusting the measurement sample so that the transmittance was within the measurement range (70 to 95%) in the sample introduction part of the measurement device. The 50% particle size based on volume distribution is a particle size (median size) corresponding to cumulative 50%.

<Measurement of Shell Coverage on Toner Particle Surface>
Evaluation of the shell coverage of the toner particle surface by a scanning electron microscope (SEM) can be carried out as follows.

  By ruthenium dyeing the surface of the toner particles, a clear contrast can be obtained in the crystalline resin. It is considered that this is because there is a difference in density between the crystalline resin and the amorphous resin, so that the dyeing strength can be enhanced.

  The toner to be dyed is put in a petri dish, 20 μL of ruthenium chloride and 20 μL of 10 mass% sodium periodate are put therein, the lid is immediately closed and the mixture is left standing for 5 minutes. Then 100 μL of sodium thiosulfate is added and left to stand for another 5 minutes to quench. Finally, add 200 μL of hydrochloric acid.

  For the dyed toner, an SEM image of the dyed toner was obtained using a field emission scanning electron microscope (Hitachi High-Technologies Corp .: S-4800, applied voltage 2.0 kV).

  The obtained images of 20 randomly selected toner particles were binarized, and the coverage of the shell on the toner particle surface was calculated. The coverage in the present invention is preferably 90% or more.

<Measurement of shell thickness on toner particle surface>
The thickness of the shell on the surface of the toner particles can be determined as follows by observing a cross section with a transmission electron microscope (TEM).

  After applying an Os film (5 nm) and a naphthalene film (20 nm) to the toner as a protective film using an osmium plasma coater (FPC, OPC80T), and embedding the photocurable resin D800 (JEOL Ltd.) A toner cross section having a film thickness of 60 nm (or 70 nm) was prepared at a cutting speed of 1 mm / s using a sonic ultramicrotome (Leica, UC7).

The obtained cross section was dyed for 15 minutes in a RuO ₄ gas atmosphere of 500 Pa using a vacuum electron dyeing apparatus (VSC4R1H, manufactured by filgen), and STEM observation was performed using TEM (JEMOL, JEM2800).

  The STEM probe size was 1 nm, and the image size was 1024 × 1024 pixels.

  The obtained image is binarized (a threshold of 120/255) with image processing software [Image-Pro Plus (manufactured by Media Cybernetics)].

  The obtained image is binarized to extract the shell in the toner particles, and the thickness thereof is measured. With respect to one toner particle, the thicknesses at the four positions of the upper, lower, left and right are measured, and the average shell thickness per toner particle is calculated. The same measurement was performed on 20 randomly selected toner particles, the average value was calculated, and the average thickness of the shell on the toner particle surface was obtained. The average thickness in the present invention is preferably 0.1 μm or more and 1.0 μm or less.

<Measurement of average circularity of toner>
The average circularity of the toner is measured by a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration work.

  The specific measuring method is as follows. First, about 20 ml of ion-exchanged water from which impure solids and the like have been removed beforehand is placed in a glass container. In this, as a dispersant, "contaminone N" (a nonionic surfactant, anionic surfactant, a 10 mass% aqueous solution of a neutral detergent for washing precision measuring instruments of pH 7 comprising an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.2 ml of a diluted solution is added. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion liquid for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion becomes 10 ° C. or higher and 40 ° C. or lower. As the ultrasonic disperser, a tabletop type ultrasonic cleaner disperser having an oscillation frequency of 50 kHz and an electric output of 150 W (for example, “VS-150” (manufactured by Vervoclea)) was used, and a predetermined amount of water was stored in the water tank. Ion-exchanged water is added, and about 2 ml of the Contaminone N is added to the water tank.

  For the measurement, the flow-type particle image analyzer equipped with "UPlanApro" (magnification 10 times, numerical aperture 0.40) as an objective lens was used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as a sheath liquid. It was used. The dispersion prepared according to the above procedure is introduced into the flow-type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analyzed particle diameter is limited to the equivalent circle diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner is obtained.

  In the measurement, standard latex particles (for example, "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific Co., Ltd. are diluted with ion-exchanged water) to perform automatic focus adjustment before starting the measurement. After that, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In addition, in the present invention, a flow type particle image measuring device, which has been calibrated by Sysmex Corporation and has been issued a calibration certificate issued by Sysmex Corporation, is used. The measurement is carried out under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to the equivalent circle diameter of 1.985 μm or more and less than 39.69 μm.

  The measurement principle of the flow-type particle image measuring device “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles as a still image and perform image analysis. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent to the flat sheath flow is sandwiched by the sheath liquid and forms a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be captured as a still image. Further, since the flow is flat, the image is captured in a focused state. The particle image is captured by a CCD camera, and the captured image is image-processed with an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel), and the contour of each particle image is extracted to obtain the particle image. The projected area S, the perimeter L, and the like are measured.

Next, using the area S and the perimeter L, the equivalent circle diameter and circularity are obtained. The equivalent circle diameter is the diameter of a circle that has the same area as the projected area of the particle image.The circularity is the value obtained by dividing the circumference of the circle obtained from the equivalent diameter of the circle by the circumference of the projected particle image. It is defined and calculated by the following formula.
Circularity = 2 x (π x S) ^1/2 / L

  The circularity becomes 1.000 when the particle image is circular, and the circularity becomes smaller as the degree of unevenness on the outer periphery of the particle image increases. After calculating the circularity of each particle, the range of circularity 0.200 to 1.000 is divided into 800, an arithmetic mean value of the obtained circularities is calculated, and the value is defined as the average circularity.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these do not limit the present invention in any way. In the following examples, the number of parts is based on parts by mass.

<Production Example of Urethane Group-Containing Olefin Copolymer E1>
Ethylene-vinyl acetate copolymer A (content of monomer unit derived from vinyl acetate: 10% by mass, acid value: 0 mgKOH / g, weight average molecular weight: 110000, softening point (Tm): 135 ° C, melting point: 93 ° C ) 100 parts 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 reflux was performed for 6 hours. Then, by washing with ethanol, a copolymer EVOH-A (ethylene-Poval copolymer; that is, a hydroxy group-containing olefin copolymer) was obtained.

  100 parts of EVOH-A obtained by the above production method and 0.5 part of phenylisocyanate were added, dissolved in dimethylsulfoxide, and reacted at 60 ° C. to give a urethane group-containing olefin polymer E1. Obtained. Table 1 shows the physical properties of the obtained urethane group-containing olefin copolymer.

<Production Example of Urethane Group-Containing Olefin Copolymer E2>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate copolymer B (content of monomer unit derived from vinyl acetate: 15% by mass, acid value: 0 mgKOH / g, Tm: 128 ° C, melting point: 86 The urethane group-containing olefin-based copolymer E2 was produced in the same manner as in the production example of E1 except that (C) was used.

<Production Example of Urethane Group-Containing Olefin Copolymer E3>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate copolymer C (content of monomer unit derived from vinyl acetate: 25% by mass, acid value: 0 mgKOH / g, Tm: 115 ° C, melting point: 70 The urethane group-containing olefin-based copolymer E3 was produced in the same manner as in the production example of E1 except that (° C.) was used.

<Production Example of Urethane Group-Containing Olefin Copolymer E4>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate copolymer D (content of monomer unit derived from vinyl acetate: 5% by mass, acid value: 0 mgKOH / g, Tm: 140 ° C, melting point: 105 The urethane group-containing olefin-based copolymer E4 was produced in the same manner as in the production example of E1 except that (C) was used.

<Production Example of Urethane Group-Containing Olefin Copolymer E5>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate copolymer E (content of monomer unit derived from vinyl acetate: 33% by mass, acid value: 0 mgKOH / g, Tm: 104 ° C, melting point: 53 The urethane group-containing olefin copolymer E5 was produced in the same manner as in the production example of E1 except that (° C.) Was used.

<Production Example of Urethane Group-Containing Olefin Copolymer E6>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate-styrene copolymer F (content of monomer unit derived from vinyl acetate: 5% by mass, polymerization ratio of ethylene unit / vinyl acetate unit / styrene unit: A urethane group-containing olefin copolymer E6 was produced in the same manner as in the production example of E1 except that 73/7/20, hydroxyl value: 0 mgKOH / g, Tm: 121 ° C., melting point: 73 ° C.) were used.

<Production Example of Urethane Group-Containing Olefin Copolymer E7>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate-styrene copolymer G (content of monomer unit derived from vinyl acetate: 5% by mass, polymerization ratio of ethylene unit / vinyl acetate unit / styrene unit: 70/5/25, hydroxyl value: 0 mgKOH / g, Tm: 118 ° C., melting point: 71 ° C.) were used to produce a urethane group-containing olefin copolymer E7 in the same manner as in the production example of E1.

<Production Example of Urethane Group-Containing Olefin Copolymer E8>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate copolymer H (content of monomer unit derived from vinyl acetate: 1% by mass, acid value: 0 mgKOH / g, Tm: 138 ° C, melting point: 110 The urethane group-containing olefin-based copolymer E8 was produced in the same manner as in the production example of E1 except that (° C.) Was used.

<Production Example of Urethane Group-Containing Olefin Copolymer E9>
Instead of ethylene-vinyl acetate copolymer A, ethylene-vinyl acetate copolymer I (content of monomer unit derived from vinyl acetate: 37% by mass, acid value: 0 mgKOH / g, Tm: 100 ° C, melting point: 48 The urethane group-containing olefin-based copolymer E9 was produced in the same manner as in the production example of E1 except that (° C.) Was used.

<Production Example of Urethane Group-Containing Olefin Copolymer E10>
100 parts of EVOH-A and 2.0 parts of phenylisocyanate were added, dissolved in dimethylsulfoxide, and reacted at a temperature of 60 ° C., thereby reacting the hydroxyl groups of EVOH-A with an isocyanate group-containing ethylene-isocyanate group-containing copolymer. A polymer EIC was obtained.

  A urethane group-containing olefin copolymer E10 was produced in the same manner as in the production example of E1 except that 33 parts of EVOH-A was used and 67 parts of EIC was used instead of phenyl isocyanate.

<Production Example of Amorphous Resin A1>
After substituting a 5-liter four-necked flask equipped with a nitrogen introduction tube, a cooling tube, a stirrer, and a thermocouple with nitrogen, the raw material monomers and tin (II) octylate shown in Table 2 were charged, and the temperature was raised at 180 ° C. After warming, they were reacted for 10 hours. After reacting at 15 mmHg for 5 hours, trimellitic anhydride was added according to Table 2 in the second reaction step and reacted at 180 ° C. for 3 hours to obtain an amorphous resin A1. The resin properties are shown in Table 2.

<Production Example of Amorphous Resin B1>
In the production example of the amorphous polyester resin A1, it was confirmed that the raw materials shown in Table 2 were used and the softening point measured according to ASTM D36-86 reached the desired temperature shown in Table 2 in the second reaction step. Then, an amorphous resin B1 was synthesized in substantially the same manner as in the production example of the resin A1 except that the reaction was stopped. The resin properties are shown in Table 2.

<Production Example of Amorphous Resin C1>
After 50 parts of xylene was charged into the autoclave and purged with nitrogen, the temperature was raised to 160 ° C. in a sealed state with stirring. A mixed solution of 90 parts of styrene, 10 parts of n-butyl acrylate, 5 parts of di-t-butyl peroxide, and 20 parts of xylene was continuously added dropwise for 3 hours for polymerization while controlling the internal temperature of the autoclave at 160 ° C. It was Further, the temperature was kept at the same temperature for 1 hour to complete the polymerization, and the solvent was removed to obtain an amorphous resin C1. The obtained amorphous resin C1 had a number average molecular weight (Mn) of 3000, a glass transition temperature (Tg) of 60 ° C. and a softening point (Tm) of 90 ° C.

<Production Example of Crystalline Polyester D1>
* 1,6-hexanediol:
34.5 parts (0.29 mol; 100.0 mol% based on the total number of polyhydric alcohols)
・ Dodecanedioic acid:
65.5 parts (0.29 mol; 100.0 mol% based on the total number of polycarboxylic acid mols)
-Tin 2-ethylhexanoate: 0.5 part The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introducing tube, and a thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually raised with stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.

  Next, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was performed for 4 hours while maintaining the temperature at 200 ° C. Then, the pressure inside the reaction tank was reduced to 5 kPa or less again and the reaction was carried out at 200 ° C. for 3 hours to obtain a crystalline polyester D1. The crystalline polyester D1 thus obtained had a number average molecular weight (Mn) of 4000 and a softening point (Tm) of 70 ° C.

(Amorphous resin A1, B1, C1 dispersion)
Amorphous resins A1, B1 and C1 were adjusted to pH 8.5 with ammonia at a composition ratio of 80% ion-exchanged water and a concentration of amorphous resin of 20%, and heated with a Cavitron at 100 ° C. The operation was performed to obtain amorphous resin A1, B1, and C1 dispersions (solid content: 20%), respectively.

<Production Example of Resin Fine Particle 1 Dispersion>
-Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts-Urethane group-containing olefin-based copolymer E1 100 parts were mixed and dissolved at 90 ° C.

  Separately, to 700 parts of ion-exchanged water, 0.7 parts of sodium dodecylbenzenesulfonate, 1.5 parts of sodium laurate, and 0.8 parts of N, N-dimethylaminoethanol were added and dissolved by heating at 90 ° C.

  Then, the above-mentioned toluene solution and the aqueous solution are mixed, and the ultra-high-speed stirring apparatus T. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix Corporation).

  Further, it was emulsified at a pressure of 200 MPa using a high pressure impact disperser Nanomizer (made by Yoshida Kikai).

  Then, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion liquid (resin fine particle 1 dispersion liquid) having a resin fine particle 1 concentration of 20%.

  The volume-based median diameter of the resin fine particles 1 was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.), and was 0.50 μm.

<Production Example of Resin Fine Particles 2-10 Dispersion>
Resin fine particles 2 to 10 dispersion liquids were produced in the same manner as in the production example of the resin fine particle 1 dispersion liquid, except that the urethane group-containing olefinic copolymers E2 to E10 were used instead of the urethane group-containing olefinic copolymer E1.

<Production example of resin fine particle 11 dispersion>
A resin fine particle 11 dispersion liquid was produced in the same manner as in the production example of the resin fine particle 1 dispersion liquid except that a cyclic olefin copolymer (manufactured by Daicel Chemical Industries: 8007) was used instead of the urethane group-containing olefin copolymer.

(Crystalline polyester D1 dispersion)
80 parts of crystalline polyester D1 and 720 parts of ion-exchanged water were placed in a stainless beaker and heated to 100 ° C. When the crystalline polyester C1 was melted, it was stirred using a homogenizer. Next, 2.0 parts of an anionic surfactant (solid content: 20%) was added dropwise to carry out emulsion dispersion to obtain a crystalline polyester D1 dispersion (solid content: 10%).

(Colorant dispersion)
-C. I. Pigment Blue 15: 3 1000 parts / anionic surfactant 150 parts / ion-exchanged water 9000 parts The above components were mixed and dissolved, and then dispersed using a high-pressure impact disperser.

  The volume average particle diameter D50 of the colorant particles in the obtained colorant dispersion was 0.16 μm, and the colorant concentration was 23%.

(Wax dispersion)
・ Hydrocarbon wax (FNP0090 manufactured by Nippon Seiro Co., Ltd .; peak temperature of maximum endothermic peak 90 ° C.) 45 parts ・ Anionic surfactant 5 parts ・ Ion-exchanged water 150 parts Heat the above to 95 ° C. and use a homogenizer After being dispersed, a dispersion treatment was carried out with a pressure discharge type Gohlin homogenizer to prepare a wax dispersion liquid (wax concentration: 20%) in which a release agent having a volume average particle diameter of 210 nm was dispersed.

<Production Example of Toner 1>
・ Amorphous resin A1 dispersion 70 parts (resin equivalent)
・ Amorphous resin B1 dispersion 30 parts (resin equivalent)
・ Crystalline polyester D1 dispersion 10 parts (resin equivalent)
The above was mixed and dispersed in a round stainless steel flask with a homogenizer. To this, 0.15 parts of polyaluminum chloride was added, and the dispersion operation was continued with Ultra Turrax. afterwards,
・ Colorant dispersion 7 parts (equivalent to colorant)
・ Wax dispersion 5 parts (wax equivalent)
In addition to the above, 0.05 part of polyaluminum chloride was further added, and the dispersion operation was continued with Ultra Turrax.

A stirrer and a mantle heater are installed, and while adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred, the temperature is raised to 60 ° C. and kept at 60 ° C. for 15 minutes, then at 0.05 ° C./min. The particle diameter was measured with a Coulter Multisizer III (aperture diameter: 50 μm, manufactured by Beckman-Coulter) every 10 minutes while the temperature was raised, and when the volume average particle diameter was 5.0 μm,
・ Resin particle 1 dispersion 15 parts (resin equivalent)
Was added over 3 minutes. After being charged for 30 minutes, the pH was adjusted to 9.0 using a 5% aqueous sodium hydroxide solution. Then, while adjusting the pH to 9.0 at every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface property were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), when the circularity reached 0.960, the particles were cooled to 20 ° C at 1 ° C / minute. Was solidified.

  Thereafter, the reaction product was filtered, thoroughly washed with ion-exchanged water, and then dried using a vacuum dryer, to obtain toner particles 1.

The toner particles 1 100 parts of hydrophobic silica (BET: 200m ² /g)1.0 parts of titanium oxide fine particles surface-treated with isobutyl trimethoxysilane (BET: 80m ² / g) 1.0 parts of , Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.) at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min. And mixed to obtain Toner 1.

  In the DSC measurement of the obtained toner 1, an endothermic peak derived from crystalline polyester was observed.

<Production Example of Toner 2>
-Amorphous resin A1 70 parts-Amorphous resin B1 30 parts-Crystalline polyester D1 10 parts-Hydrocarbon wax (FNP0090 manufactured by Nippon Seiro Co., Ltd .; peak temperature of maximum endothermic peak 90 ° C) 5 parts-C.I. I. Pigment Blue 15: 3 7 parts, 3,5-di-t-butylsalicylic acid aluminum compound (CA agent) 0.3 parts Using the above materials, a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.) The rotation speed was 20 s ⁻¹ and the rotation time was 5 min, followed by kneading with a biaxial kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 150 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed material. The obtained coarsely pulverized product was finely pulverized by a mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.). Further, using a Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 2. The operating conditions were a classification rotor rotation speed of 130 s ⁻¹ and a dispersion rotor rotation speed of 120 s ⁻¹ .

15 parts of urethane group-containing olefin-based copolymer E1 fine particles were added to 100 parts of the obtained toner particles 2, and the rotation speed was 30 s ^-1 with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.). , And was mixed at a rotation time of 10 min.

To 100 parts of the obtained toner particles 1, 1.0 part by weight of hydrophobic silica (BET: 200 m ^{2 /} g) and 1.0 part by weight of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (BET: 80 m ^{2 /} g) were added. Was added, and the rotation speed was 30 s ⁻¹ and the rotation time was 10 min. With a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.). And mixed to obtain Toner 2.

  In the DSC measurement of the obtained toner 2, an endothermic peak derived from crystalline polyester was observed.

<Production Example of Toners 3 to 23>
Toners 3 to 23 were obtained in substantially the same manner as in the production example of Toner 1, except that the materials described in Table 3 were blended according to Table 3 in the production example of Toner 1.

<Production Example of Magnetic Carrier Particles 1>
・ Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.7 parts MnCO ₃ 29.5 parts Mg (OH) ₂ 6.8 parts SrCO ₃ 1.0 part The ferrite raw materials were weighed so that the above materials had the above composition ratio. Then, the mixture was pulverized and mixed for 5 hours by a dry vibration mill using stainless beads having a diameter of 1/8 inch.
-Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square with a roller compactor. Coarse powders were removed from the pellets by a vibrating screen having an opening of 3 mm, and then fine particles were removed by a vibrating screen having an opening of 0.5 mm. Then, the pellets were burned in a nitrogen atmosphere (oxygen concentration: 0. (01 vol%) at a temperature of 1000 ° C. for 4 hours to prepare a calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
・ Process 3 (crushing process):
After crushing to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and crushed with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours with a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (finely calcinated ferrite product).
・ Process 4 (granulation process):
To 100 parts of calcined ferrite, 1.0 part of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added to the ferrite slurry, and the particles were formed into spherical particles with a spray dryer (manufacturer: Okawara Kakoki). Granulated. After adjusting the particle size of the obtained particles, it was heated at 650 ° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and the binder.
・ Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300 ° C. in 2 hours in an electric furnace in a nitrogen atmosphere (oxygen concentration 1.00% by volume), and then firing was performed at 1150 ° C. for 4 hours. Then, the temperature was lowered to 60 ° C. over 4 hours, the nitrogen atmosphere was returned to the atmosphere, and the sample was taken out at a temperature of 40 ° C. or lower.
・ Process 6 (selection process):
After disintegrating the agglomerated particles, the low magnetic force product is cut by magnetic separation, and coarse particles are removed by sieving with a sieve having an opening of 250 μm to obtain a 50% particle diameter (D50) of 37.0 μm based on volume distribution. Magnetic carrier particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8 mass%
Methyl methacrylate monomer 0.2 mass%
Methyl methacrylate macromonomer 8.4 mass%
(Macromonomer having methacryloyl group at one end and having a weight average molecular weight of 5000)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0 mass%
Of the above materials, cyclohexylmethacrylate, methylmethacrylate, methylmethacrylate macromonomer, toluene, methylethylketone were added to a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen introduction tube and stirring device, and nitrogen gas was added. Was introduced into the autoclave to make it sufficiently nitrogen atmosphere, then heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was separated by filtration and vacuum dried to obtain a coating resin 1. The obtained coating resin 1 was dissolved in 30 parts, 40 parts of toluene, and 30 parts of methyl ethyl ketone to obtain a polymer solution 1 (solid content: 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3 mass%
Toluene 66.4% by mass
Carbon black 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption amount 75 ml / 100 g)
Was dispersed with a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Production Example of Magnetic Carrier 1>
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing type kneader maintained at room temperature such that the resin component was 2.5 parts with respect to 100 parts of the filled magnetic carrier particles 1. After charging, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, the solvent was volatilized at a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. The magnetic carrier thus obtained is separated into low-magnetism products by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier, and a magnetic carrier having a volume distribution-based 50% particle diameter (D50) of 38.2 μm. Got 1.

<Production example of two-component developer>
The toners 1 to 23 and the magnetic carrier 1 described above were mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) at 0.5 s ^{−1 at} a rotation time of 5 min so that the toner concentration was 8.0% by mass. By mixing, two-component developers 1 to 23 were obtained.

[Example 1]
Using the above two-component developer 1, the following low temperature fixability evaluation and charge retention evaluation were carried out.
Evaluation was carried out based on the following evaluation methods, and the results are shown in Table 4.

<Evaluation 1: Evaluation of low temperature fixability>
Paper: CF-C104 (104.0 g / m ² ).
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.90 mg / cm ²
Evaluation image: An image of 25 cm ² is arranged in the center of the A4 paper. Fixing test environment: low temperature and low humidity environment: temperature 15 ° C./humidity 10% RH (hereinafter “L / L”)
After adjusting the DC voltage V _DC of the developer carrying member, the charging voltage V _D of the electrostatic latent image carrying member, and the laser power so that the amount of toner deposited on the paper is as described above, the process speed is 300 mm / sec, The fixing temperature was set to 130 ° C. and the low temperature fixing property was evaluated. The value of the image density reduction rate was used as an evaluation index of low temperature fixability. As for the image density reduction rate, first, the image density of the central portion is measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g / cm ² ) is applied to the portion where the image density is measured, and the fixed image is rubbed (5 reciprocations) with the sillbon paper, and the image density is measured again. Then, the reduction rate (%) of the image density before and after the rubbing was measured.

The evaluation criteria are as follows.
A: Density reduction rate of less than 1.0% (very excellent)
B: Density reduction rate 1.0% or more and less than 5.0% (excellent)
C: Density reduction rate of 5.0% or more and less than 10.0% (prior art level)
D: Density reduction rate 10.0% or more (inferior to conventional)

<Evaluation 2: Evaluation of charge retention>
Images were output in a high-temperature and high-humidity environment (30 ° C./80% Rh) using a Canon full-color copying machine image RUNNER ADVANCE C9075PRO. The output image was a vertical strip image of 4 A horizontal and 10 cm wide in the monochrome mode, and was adjusted so that the reflection density of cyan on the paper was 1.35. As the evaluation paper, copy paper GF-C081 (A4, basis weight 81.4 g / m ² , sold by Canon Marketing Japan Co., Ltd.) was used. Then, the developing device was taken out and left for 150 hours, the main body was started up, the developing device was returned to the inside of the main body, and the same image was output again under the same developing conditions. The reflection density of the obtained output image was measured by using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite Co., Ltd.) at an average value of 9 positions, and compared with the reflection density before and after standing. Was evaluated according to the standard.

(Evaluation criteria: Reflection density difference between output images before and after leaving)
A: Less than Δ0.05 (very excellent)
B: Δ0.05 or more and less than Δ0.10 (excellent)
C: Δ0.10 or more and less than Δ0.20 (prior art level)
D: Δ0.20 or more (inferior to conventional)

[Examples 2 to 18, Comparative Examples 1 to 5]
Evaluations were performed in the same manner as in Example 1 using the developers 2 to 18 and Comparative Examples 1 to 5 shown in Table 4. The evaluation results are shown in Table 4.

Claims (6)

A toner having toner particles having a core containing an amorphous resin and a shell containing an urethane group-containing olefin-based copolymer and coating the core,
The glass transition point Tg of the toner measured by a differential scanning calorimeter (DSC) is 40 ° C. or higher and 55 ° C. or lower,
The urethane group-containing olefin-based copolymer has a monomer unit Z1 represented by the following formula (1) and a monomer unit Z2 represented by the following formula (2) or / and (3),
A toner having a urethane bond concentration of the urethane group-containing olefin-based copolymer of 2% by mass or more and 24% by mass or less.

(In the formulas (1), (2), and (3), R ₁ represents H or CH ₃ , R ₂ represents H or CH ₃ , R ₃ represents any organic group, and R ₄ represents H or CH ₃ is shown, and R ₅ is an arbitrary organic group.)   The total mass of the urethane group-containing olefin-based copolymer was X, the mass of the unit represented by the formula (1) was a, and the mass of the unit represented by the formula (2) or / and (3) was b. The toner according to claim 1, wherein the value of (a + b) / X is 0.80 or more and 1.00 or less.   The toner according to claim 1, wherein the average thickness of the shell is 0.1 μm or more and 1.0 μm or less, and the coverage of the shell with respect to the core is 90% or more.   The toner according to claim 1, wherein the content of the urethane group-containing olefin-based copolymer is 1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the toner particles.   The toner according to claim 1, wherein the amorphous resin is an amorphous polyester.   The toner according to claim 1, wherein the core further contains a crystalline polyester.