JP2019003083A - toner - Google Patents

Abstract

To provide a toner simultaneously realizing low temperature fixability and hot offset durability, without deteriorating shelf stability of the toner.SOLUTION: A toner includes a binder resin and a toner particle containing a fatty acid metal salt. The binder resin includes a hybrid resin having a polyester portion and a styrene-acrylic copolymer portion. The fatty acid metal salt is a fatty acid calcium salt. In the fatty acid calcium salt, fatty acid has 8-28 carbon atoms. A content of the fatty acid calcium salt is 0.5-10 pts.mass with regard to the binder resin 100 pts.mass. In a cross section of the toner particle observed by a transmission electron microscope, a number average dispersion diameter of the fatty acid calcium salt is 50-500 nm. A content of the styrene-acrylic copolymer portion is 5-50 mass% in the binder resin. An acid value is 5-30 mgKOH/g in the binder resin.SELECTED DRAWING: None

Description

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

In recent years, with the development of image forming apparatuses such as copiers and printers, there is a demand for toners that can cope with higher speed, higher image quality, longer life, and energy saving than ever before.
In order to achieve energy saving in a copying machine or the like, it is effective to lower the toner fixing temperature. In order to prevent the toner from adhering to the fixing device at the time of fixing, it is effective to add wax for the purpose of giving the toner releasability.

Therefore, it is known that low temperature fixability and hot offset resistance can be improved by using a hybrid resin in which a polyester resin excellent in low temperature fixability and a styrene acrylic resin excellent in wax dispersibility are chemically bonded. (Patent Document 1).
However, even when such a resin is used, when aiming at a toner that can cope with higher speed, higher image quality, longer life, and energy saving than conventional ones, low-temperature fixability and hot offset resistance can be obtained. It was insufficient.
Therefore, in order to improve the hot offset resistance, a technique for crosslinking the binder resin composition of the toner has been proposed as means for increasing the viscosity of the toner at a high temperature (Patent Document 2).
On the other hand, in order to improve low-temperature fixability, a technique using crystalline polyester in the toner (Patent Document 3) and a technique using a higher fatty acid salt to lower the melt viscosity of the binder resin have been proposed (Patent Document 4). ).

JP 2007-293327 A JP 2012-173322 A Japanese Patent Laid-Open No. 4-120554 JP 2006-126529 A

It is possible to improve the viscosity of the toner by cross-linking molecular chains to a hybrid resin in which a polyester resin and a styrene acrylic resin are chemically bonded, as proposed in Patent Document 2. However, in this case, there is a problem that the low-temperature fixability is also lowered.
On the other hand, in order to improve the low-temperature fixability, when using a material having a plastic effect such as crystalline polyester and higher fatty acid salt as proposed in Patent Documents 3 to 4, hot offset resistance and toner storage There was a problem with sex.
Accordingly, the present invention provides a toner that achieves both low-temperature fixability and hot offset resistance without deteriorating the storage stability of the toner.

As a result of intensive studies by the present inventors, the storage stability of the toner can be improved by including a hybrid resin having a polyester moiety and a styrene acrylic copolymer moiety and a specific fatty acid metal salt as constituents of the toner particles. It has been found that both low temperature fixability and hot offset resistance can be achieved without lowering.
That is, the present invention
A toner having toner particles containing a binder resin and a fatty acid metal salt,
The binder resin contains a hybrid resin having a polyester moiety and a styrene acrylic copolymer moiety,
The fatty acid metal salt is a fatty acid calcium salt;
The number of carbon atoms of the fatty acid in the fatty acid calcium salt is from 8 to 28;
The fatty acid calcium salt content is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.
In the cross section of the toner particles observed with a transmission electron microscope,
The number average dispersion diameter of the fatty acid calcium salt is 50 nm or more and 500 nm or less,
The content of the styrene acrylic copolymer site in the binder resin is 5% by mass or more and 50% by mass or less,
The present invention relates to a toner wherein the acid value of the binder resin is 5 mgKOH / g or more and 30 mgKOH / g or less.

  According to the present invention, it is possible to provide a toner excellent in low-temperature fixability and hot offset resistance without deteriorating storage stability.

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
Moreover, a monomer unit means the form which the monomeric substance in the polymer or copolymer reacted.
The toner of the present invention is
A toner having toner particles containing a binder resin and a fatty acid metal salt,
The binder resin contains a hybrid resin having a polyester moiety and a styrene acrylic copolymer moiety,
The fatty acid metal salt is a fatty acid calcium salt;
The number of carbon atoms of the fatty acid in the fatty acid calcium salt is from 8 to 28;
The fatty acid calcium salt content is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.
In the cross section of the toner particles observed with a transmission electron microscope,
The number average dispersion diameter of the fatty acid calcium salt is 50 nm or more and 500 nm or less,
The content of the styrene acrylic copolymer site in the binder resin is 5% by mass or more and 50% by mass or less,
The acid value of the binder resin is 5 mgKOH / g or more and 30 mgKOH / g or less.

By incorporating the hybrid resin having a polyester moiety and a styrene acrylic copolymer moiety and a fatty acid calcium salt in toner particles under special conditions, the following effects are exhibited.
(1) The carboxyl group and calcium in the hybrid resin are metal-crosslinked, the toner particles have a high viscosity, and the hot offset resistance of the toner is improved.
(2) The long-chain alkyl part of the fatty acid in the fatty acid calcium salt effectively plasticizes the hybrid resin, thereby improving the low-temperature fixability of the toner.
Here, when a metal salt other than calcium, for example, a fatty acid metal salt such as zinc or aluminum and a hybrid resin is combined, hot offset resistance is not improved as in the case of using a fatty acid calcium salt.

That is, only the fatty acid calcium salt shows such a unique effect.
The reason is presumed as follows.
The fatty acid calcium salt has higher hydrophilicity than other fatty acid metal salts, and has a high affinity with the carboxy group in the hybrid resin. Therefore, it is considered that the entire binder resin can be effectively cross-linked through the metal cross-linking of calcium in the carboxy group and the fatty acid calcium salt.
On the other hand, in the case of a fatty acid metal salt such as zinc or aluminum, the fatty acid metal salt is segregated at the styrene acrylic copolymer site in the hybrid resin, so that it is considered that the effect as the fatty acid calcium salt does not appear.

The number of carbon atoms of the fatty acid in the fatty acid calcium salt is 8 or more and 28 or less.
When the number of carbon atoms of the fatty acid is less than 8, it is difficult to disperse the fatty acid calcium salt in the binder resin, and it is difficult to develop a crosslinking effect.
On the other hand, when the number of carbon atoms of the fatty acid is greater than 28, the plastic effect of the long-chain alkyl moiety on the binder resin exceeds the cross-linking effect of calcium, making it difficult to improve hot offset resistance.
The fatty acid has preferably 8 or more and 18 or less carbon atoms, more preferably 8 or more and 12 or less.
Examples of fatty acids having 8 to 28 carbon atoms include caprylic acid (octanoic acid), pelargonic acid (nonanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), pentadecanoic acid, palmitic acid Examples include acid (hexadecanoic acid), 9-hexadecenoic acid, heptadecanoic acid, stearic acid (octadecanoic acid), 11-octadecenoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, and octacosanoic acid.
These fatty acid calcium salts can be used alone or in combination of two or more.
The fatty acid calcium salt preferably contains at least one fatty acid calcium salt selected from the group consisting of calcium laurate, calcium myristate, calcium palmitate, and calcium stearate.
The fatty acid calcium salt can replace the hydrogen atom of the fatty acid having the same valence as calcium with a calcium ion, and these can also be exemplified as the fatty acid calcium salt.
For example, calcium dilaurate, calcium dimyristate, calcium dipalmitate, and calcium distearate.

The content of the fatty acid calcium salt is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.
When the content of the fatty acid calcium salt is less than 0.5 parts by mass, the effect of hot offset resistance is hardly exhibited. On the other hand, when the content is more than 10 parts by mass, the fatty acid calcium salt tends to ooze out from the toner particles, and the image quality is likely to deteriorate.
The content of the fatty acid calcium salt is preferably 0.5 parts by mass or more and 5 parts by mass or less, and 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferred.

In the cross section of the toner particles observed with a transmission electron microscope,
The number average dispersion diameter of the fatty acid calcium salt is 50 nm or more and 500 nm or less.
When the number average dispersion diameter of the fatty acid calcium salt is smaller than 50 nm, the effect of hot offset resistance is hardly exhibited. On the other hand, even when the number average dispersion diameter is larger than 500 nm, the effect of hot offset resistance is hardly exhibited.
The number average dispersion diameter of the fatty acid calcium salt is preferably 50 nm or more and 300 nm or less, and more preferably 50 nm or more and 200 nm or less.
In addition, as a method for controlling the number average dispersion diameter of the fatty acid calcium salt within the above range,
For example, it may be controlled depending on the toner production conditions. For example, when a pulverization method is used, the shear rate and temperature conditions during melt kneading of the raw materials may be controlled.

The amount of free fatty acid contained in the fatty acid calcium salt is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less.
When the amount of the free fatty acid is within the above range, crosslinking with the resin tends to proceed effectively.
A method for adjusting the amount of the free fatty acid within the above range includes adjusting the raw material concentration and the reaction temperature in the production conditions of the fatty acid calcium salt.

The binder resin contains a hybrid resin having a polyester component and a styrene acrylic copolymer site.
The binder resin may be composed only of the hybrid resin, but may contain a resin other than the hybrid resin. Examples of the resin other than the hybrid resin include known resins used for toner.
The content of the hybrid resin in the binder resin is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, and 80% by mass or more and 100% by mass or less. More preferably, it is as follows.

The polyester moiety is not particularly limited, and examples thereof include a condensate of an alcohol component and an acid component.
Specifically, the polyester moiety preferably contains a monomer unit derived from the following alcohol component and a monomer unit derived from the following acid component.
Examples of the alcohol component include the following dihydric or higher alcohols.
Examples of the divalent alcohol component include 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 bisfer A, bisphenol represented by the following formula (I) and derivatives thereof, and represented by the following formula (II) Examples include diols.
Examples of the trihydric or higher polyhydric alcohol include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol and the like.

（式中、Ｒはエチレン基又はプロピレン基を示し、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 represents an ethylene group or a 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.)

Examples of the acid component include the following divalent or higher carboxylic acids.
Examples of divalent carboxylic acids include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or the like. Anhydrides; succinic acid substituted with an alkyl group having 6 to 18 carbon atoms or an alkenyl group having 6 to 18 carbon atoms; or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid An acid or its anhydride is mentioned.
Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, and These acid anhydrides or lower alkyl esters are mentioned.
Among these, it is preferable that a polyester site | part contains the monomer unit derived from a terephthalic acid, a fumaric acid, and trimellitic acid.

The styrene-acrylic copolymer site is not particularly limited, and examples thereof include a copolymer of a styrene-based component and an acrylic acid-based and / or methacrylic acid-based component.
The following are mentioned as a monomer for obtaining a styrene acrylic copolymer.
Styrene; styrene derivatives such as o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, Α-methylene aliphatic monocarboxylic such as isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate Acid esters; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate , Stearyl acrylate, 2-chloroethyl, and acrylic acid esters such as phenyl acrylate

Although it does not specifically limit as a manufacturing method of this hybrid resin, The following are mentioned.
(I) A method for producing a polymer by carrying out a transesterification reaction between a polyester component and a polymer containing a monomer component having an ester group such as an acrylic ester or a methacrylic ester.
(Ii) A method for producing an esterification reaction between a polymer containing a monomer component having a carboxylic acid group such as acrylic acid or methacrylic acid and a polyester component.
(Iii) A method for producing a polymer by polymerizing a monomer component constituting a styrene acrylic copolymer site in the presence of a polyester site containing a monomer component having an unsaturated bond such as fumaric acid.
As described above, the hybrid resin contains a monomer capable of reacting with both sites in the monomer component constituting the styrene acrylic copolymer site and / or the monomer component constituting the polyester site. A method of producing them by reacting them can be suitably exemplified.
Moreover, the mass ratio of the polyester moiety to the styrene acrylic copolymer moiety in the hybrid resin is preferably 100: 10 to 100: 50, and more preferably 100: 15 to 100: 30.

The content of the styrene acrylic copolymer moiety in the binder resin is 5% by mass or more and 50% by mass or less.
When the content of the styrene-acrylic copolymer site is less than 5% by mass, the dispersibility of the release agent or the like tends to be lowered, and the hot offset resistance is hardly improved. On the other hand, when the content of the styrene acrylic copolymer site is more than 50% by mass, the low-temperature fixability is lowered.
The content of the styrene acrylic copolymer moiety in the binder resin is preferably 10% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 30% by mass or less.

The acid value of the binder resin is 5 mgKOH / g or more and 30 mgKOH / g or less.
When the acid value of the binder resin is smaller than 5 mgKOH / g, the crosslinking effect by calcium is small, and the hot offset resistance is hardly improved. On the other hand, when the acid value is larger than 30 mgKOH / g, the dispersibility of the release agent or the like tends to be lowered, and the hot offset resistance is hardly improved.
The acid value of the binder resin is preferably 5 mgKOH / g or more and 25 mgKOH / g or less, and more preferably 10 mgKOH / g or more and 20 mgKOH / g or less.
In addition, as a technique for controlling the acid value of the binder resin within the above range, the molecular weight is controlled, the terminal of the binder resin has two or more carboxy groups, or does not have a carboxy group. And modification with other monomers.

The toner particles may contain a release agent. The release agent is not particularly limited, and a known wax can be used.
Examples of the wax include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof Products: Waxes mainly composed of fatty acid esters such as carnauba wax; Deoxidized part or all of fatty acid esters such as deoxidized carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol , Saturated alcohols such as merisyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnauvir alcohol , Esters with alcohols such as ceryl alcohol, melyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylenebisstearic acid amide, ethylene Saturated fatty acid bisamides such as scapric amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N 'Unsaturated fatty acid amides such as dioleyl sebacic acid amide; m-xylene bis stearic acid amide, N, N' aromatic bisamides such as distearyl isophthalic acid amide; obtained by hydrogenation of vegetable oils and fats A methyl ester compound having a hydroxy group.
Among these, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low-temperature fixability and hot offset resistance.
The content of the release agent is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.
Moreover, in the endothermic curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus, the peak temperature of the maximum endothermic peak of the release agent is preferably 45 ° C. or higher and 140 ° C. or lower.
When the peak temperature of the maximum endothermic peak of the release agent is within the above range, it is easy to achieve both toner storage stability and hot offset resistance.

The toner particles may contain a colorant. Examples of the colorant include the following.
Examples of the black colorant include carbon black; those obtained by adjusting the color to black using a yellow colorant, a magenta colorant, and a cyan colorant.
As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.
The following are mentioned as a magenta pigment. 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. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of the cyan pigment include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.
Examples of cyan dyes include C.I. I. Solvent Blue 70 is exemplified.
Examples of the yellow pigment 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 yellow dyes include C.I. I. Solvent yellow 162 may be mentioned.
The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner particles may contain a charge control agent as necessary.
As the charge control agent, known ones can be used, but a metal compound of an aromatic carboxylic acid that is colorless, has a high charging speed of toner particles, and can stably maintain a constant charge amount is preferable.
Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Polymer compound, carboxylate or carboxylic acid ester compound in the side chain, boron compound, urea compound, silicon compound,
An example is calix arene.
Examples of positive charge control agents include quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in the side chain, guanidine compounds, and imidazole compounds.
The charge control agent may be added internally or externally to the toner particles.
The content 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.

The toner may contain inorganic fine particles as necessary.
The inorganic fine particles may be added internally to the toner particles, or may be mixed with the toner particles as an external additive.
As the external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferable.
The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
In addition, the external additive for improving fluidity is preferably inorganic fine particles having a specific surface area of 50 m ² / g or more and 400 m ² / g or less measured using the BET method. On the other hand, in order to improve durability stability, inorganic fine particles having a specific surface area measured by the BET method of 10 m ² / g or more and 50 m ² / g or less are preferable.
In order to improve fluidity and durability stability, inorganic fine particles having a specific surface area in the above range may be used in combination.
The content of these external additives is preferably 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer may be used for mixing the toner particles and the external additive.

The method for producing the toner is not particularly limited, and a known method can be used.
Hereinafter, a procedure for producing toner using the pulverization method will be described.
In the raw material mixing step, as a material constituting the toner particles, a predetermined amount of a binder resin, a fatty acid metal salt, and a release agent, a colorant, a charge control agent, and the like are weighed, blended, and mixed as necessary. To do.
Examples of the mixing apparatus 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 (manufactured by Nippon Coke Industries, Ltd.).
Next, the mixed material is melt-kneaded. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. From the advantage of continuous production, a single-screw or twin-screw extruder is the mainstream. It has become.
Specific examples of the kneading machine include a KTK type twin screw extruder (manufactured by Kobe Steel), a TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneading machine (manufactured by Ikekai Tekko), and a twin screw extruder (manufactured by Keikei). -CK Co., Ltd.), Ko Kneader (Bus Co., Ltd.), Kneedex (Nihon Coke Industries Co., Ltd.), etc. are mentioned.
The obtained melt-kneaded product is rolled with two rolls or the like and cooled with water or the like to obtain a cooled product of the resin composition.
Next, the obtained cooling product is pulverized to a desired particle size in a pulverization step.
In the pulverization step, coarse pulverization is obtained by coarse pulverization with a pulverizer such as a crusher, hammer mill, or feather mill. Further, it may be finely pulverized by a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nissin Engineering Co., Ltd.), a turbo mill (manufactured by Turbo Industry), a fine pulverizer using an air jet method, or the like.
After that, if necessary, such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification type turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles may be obtained by classification using a classifier or a sieving machine.
If necessary, an external additive may be added to the surface of the toner particles.
As a method of adding the external additive, a predetermined amount of toner particles and various known external additives are mixed, and a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechano hybrid (Nippon Coke) And a method of stirring and mixing using a mixing apparatus such as Nobilta (manufactured by Hosokawa Micron Corporation).
The toner may be used as a one-component developer, but in order to further improve dot reproducibility and to obtain a stable image over a long period of time, the toner is mixed with a two-component developer. It may be used as a system developer.

Below, it shows about the measuring method used by this invention.
<Determining resin structure>
The following method is used to determine the structure of the resin or the like.
Using ECA-400 (400 MHz) manufactured by JEOL Ltd., ¹ H-NMR and ¹³ C-NMR spectra are measured.
Measurement is performed at 25 ° C. in a deuterated solvent containing tetramethylsilane as an internal standard substance. The chemical shift value is shown as a ppm shift value (δ value) with tetramethylsilane as an internal standard substance being zero.

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

<Measuring method of number average dispersion diameter of fatty acid calcium salt>
The number average dispersion diameter of the fatty acid calcium salt in the cross section of the toner particles observed with a transmission electron microscope (TEM) is measured as follows.
By ruthenium dyeing the toner particles, the fatty acid calcium salt can be clearly identified in the cross-sectional image of the toner particles.
The reason is that the stain of the dye material into the fatty acid calcium salt is caused by a difference in density and the like, and is stronger than other organic components inside the toner particles. This is because it is dyed more strongly than organic components.
Because the amount of ruthenium atoms varies depending on the intensity of staining, the strongly stained part has many of these atoms, the electron beam does not pass through, it becomes black on the observation image, and the part that is weakly stained is The electron beam is easily transmitted and becomes white on the observation image.
The specific procedure is shown below.
The toner particles are covered with an Os film (5 nm) and a naphthalene film (20 nm) as protective films using an osmium plasma coater (filgen, OPC80T).
Then, after embedding in photocurable resin D800 (JEOL Ltd.), toner particle flakes having a film thickness of 60 nm are prepared at a cutting speed of 1 mm / s using an ultrasonic ultramicrotome (Leica, UC7).
The obtained flakes are dyed for 15 minutes in a RuO ₄ gas 500 Pa atmosphere using a vacuum electron dyeing apparatus (filgen, VSC4R1H) to prepare an observation sample.
A cross-sectional image of the toner particles is obtained by photographing the observation sample using a transmission electron microscope (JEOL, JEM2800).
The transmission electron microscope has a probe size of 1 nm and an image size of 1024 × 1024 pixels. In a cross-sectional image of 20 randomly selected toner particles, the total equivalent circle diameter of the measurable fatty acid calcium salt existing as particles is measured, and the average value is the number average dispersion diameter (nm) of the fatty acid calcium salt. ).

<Method for measuring the amount of free fatty acid contained in the fatty acid calcium salt>
The amount of free fatty acid contained in the fatty acid calcium salt is determined by using a phenolphthalein solution (1%) as an indicator, and using a mixture of a measurement sample, ethyl ether and ethyl alcohol as a 1/20 mol / L potassium hydroxide ethyl alcohol standard solution. Calculate by titrating with.

<Measurement method of fatty acid calcium salt content>
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and dissolved with a hot water bath to prepare a sucrose concentrate.
31 g of the sucrose concentrate in a tube for centrifugation, 10% by weight aqueous solution of neutral detergent for cleaning precision measuring instruments with pH 7 consisting of Contaminone N (nonionic surfactant, anionic surfactant, organic builder), 6 mL of Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion.
To this dispersion, 1.0 g of toner is added, and the mass of toner is loosened with a spatula or the like.
Next, the centrifuge tube is shaken with a shaker. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL) and separated by a centrifuge at 3500 rpm for 30 min. By this operation, the toner particles are separated from the detached external additive.
After confirming that the toner particles and the aqueous solution are sufficiently separated, the toner particles are collected, filtered with a vacuum filter, and then dried with a dryer for 1 hour or more to separate the external additives. Get.
Further, the obtained toner particles are dissolved in soluble components other than the fatty acid calcium salt with toluene or hexane, and the amount of fatty acid calcium salt remaining after filtration is measured.
Note that the fatty acid calcium salt structure of the remaining amount is determined using nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), and fluorescent X-ray measurement.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these at all. All parts and percentages in the examples are based on mass unless otherwise specified.
<Example of production of hybrid resin 1>
As shown in Table 1, bisphenol A propylene oxide 2 mol adduct (described as BPA-PO in the table), bisphenol A ethylene oxide 2 mol adduct (described as BPA-EO in the table), fumaric acid, terephthalic acid, And acrylic acid and 15 parts of tin (II) dioctanoate were placed in a four-necked flask equipped with a thermometer, a stir bar, a condenser and a nitrogen inlet tube, and polymerized at 230 ° C. for 4.5 hours under a nitrogen atmosphere. .
Thereafter, once it was cooled to 160 ° C., trimellitic acid was added.
Next, a mixture of 450 parts of styrene, 200 parts of 2-ethylhexyl acrylate, and 30 parts of dicumyl peroxide as a polymerization initiator was added dropwise at 160 ° C. over 2 hours. After completion of the dropwise addition, the temperature was further raised to 200 ° C. and the reaction was performed for 3 hours to obtain a hybrid resin 1 having a softening point of 115 ° C.

<Examples of production of hybrid resins 2-8>
The reaction was carried out in the same manner as in the production example of the hybrid resin 1 except that the raw materials and the amounts used were changed as shown in Table 1. In either case, the reaction was carried out by appropriately changing the reaction time until the softening point reached 115 ° C. to obtain hybrid resins 2 to 8.

<Production Example of Toner 1>
・ Hybrid resin 1 100 parts ・ Fischer Tropsch wax 5 parts (Maximum endothermic peak temperature is 78 ℃)
・ Copper phthalocyanine 7 parts (CI Pigment Blue 15: 3)
Calcium laurate (manufactured by Sakai Chemical Co., Ltd.) 1 part3,5-di-t-butylsalicylic acid aluminum compound 0.5 part (Bontron E88, manufactured by Orient Chemical Co., Ltd.)
The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, and then a twin-screw kneader (PCM-30) set at a temperature of 130 ° C. And kneaded at a rotation speed of 200 rpm.
The obtained kneaded product was cooled to 25 ° C. and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Furthermore, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1.
To 100 parts of toner particles 1, 1.8 parts of silica fine particles having a specific surface area measured by the BET method of 200 m ² / g and hydrophobized with silicone oil were dry-mixed with a Henschel mixer (Mitsui Mine). A toner 1 to which an external additive was added was obtained.

<Production Examples of Toners 2 to 8>
In the production example of toner 1, toners 2 to 8 were obtained in the same manner as in the production example of toner 1 except that the types and addition amounts of the hybrid resin and fatty acid metal salt were adjusted according to Table 2.

<Production Examples of Toners 9 to 17>
In the production example of toner 1, toners 9 to 17 were obtained in the same manner as in the production example of toner 1 except that the types and addition amounts of the hybrid resin and fatty acid metal salt were adjusted according to Table 2.

<Production Example of Toner 18>
In the toner 1 production example, the type and addition amount of the hybrid resin and fatty acid metal salt were adjusted according to Table 2, and the rotational speed of the biaxial kneader at the time of kneading was changed to 300 rpm. Thus, toner 18 was obtained.

<Production Example of Toner 19>
In the toner 1 production example, the types and addition amounts of the hybrid resin and fatty acid metal salt were adjusted according to Table 2, and the biaxial kneader rotation speed at the time of kneading was changed to 50 rpm. Thus, toner 19 was obtained.

<Examples 1-8 and Comparative Examples 1-11>
The following evaluation was performed using the obtained toner.

<Evaluation of low-temperature fixability>
A toner and a ferrite carrier surface-coated with a silicone resin (average particle size 42 μm) were mixed so that the toner concentration was 8% by mass to prepare a two-component developer.
The two-component developer was filled in a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.) to form an unfixed toner image (0.6 mg / cm ² ) on the image receiving paper (64 g / m ² ).
On the other hand, a fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon Inc.) was remodeled so that the fixing temperature could be adjusted, and a fixing test for unfixed images was performed using this.
Under normal temperature and humidity, the process speed was set to 246 mm / sec, and the state when the unfixed image was fixed was visually evaluated. The evaluation results are shown in Table 3.
(Evaluation criteria)
A: Fixing is possible in a temperature range of 140 ° C. or lower B: Fixing is possible in a temperature range higher than 140 ° C. and 160 ° C. or lower C: There is a fixable region only in a temperature range higher than 160 ° C.

<Evaluation of hot offset resistance>
Similar to the evaluation of low-temperature fixability, an unfixed image for evaluation was created using a full-color digital copying machine (CLC1100, manufactured by Canon Inc.).
After that, a commercially available full-color digital copier (imageRUNNER ADVANCE)
The fixing unit removed from C5051 (manufactured by Canon Inc.) was remodeled so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using this.
The reflectivity of the evaluation paper before image printing is reflected by the reflectometer ("REFLECTOMETER"
“MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), and the average value measured at five locations was DA (%).
The fixing temperature in the fixing evaluation jig is adjusted every 5 ° C. within the range of 100 to 200 ° C., the reflectance of the white background portion of the fixed image at each fixing temperature is measured with a reflectometer, and the maximum value is DB (%). It was.
The difference between DA (%) and DB (%) did not exceed 0.5%, and the highest fixing temperature was set as the upper limit fixing temperature, and hot offset resistance was evaluated according to the following criteria. The evaluation results are shown in Table 3.
(Evaluation criteria)
A: 200 ° C. or higher B: 180 ° C. or higher and lower than 200 ° C. C: 160 ° C. or higher and lower than 180 ° C. D: Less than 160 ° C.

<Evaluation of preservability>
10 g of toner was put in a 100 mL polypropylene container and left in a temperature and humidity variable temperature thermostat for 48 hours, and the temperature at which the toner aggregated after being left was evaluated.
When the powder tester PT-X manufactured by Hosokawa Micron Co., Ltd. was shaken with a mesh having a mesh size of 250 μm for 60 seconds with an amplitude of 1.0 mm, it was judged that aggregation was present when 10% by mass or more remained. The humidity in the thermostatic chamber was 10% Rh or less, and the temperature was increased from 40 ° C. in increments of 2.5 ° C. The evaluation results are shown in Table 3.
(Evaluation criteria)
A: 60 ° C. or higher B: 55 ° C. or higher and lower than 60 ° C. C: 45 ° C. or higher and lower than 55 ° C. D: Less than 45 ° C.

Claims (4)

A toner having toner particles containing a binder resin and a fatty acid metal salt,
The binder resin contains a hybrid resin having a polyester moiety and a styrene acrylic copolymer moiety,
The fatty acid metal salt is a fatty acid calcium salt;
The number of carbon atoms of the fatty acid in the fatty acid calcium salt is from 8 to 28;
The fatty acid calcium salt content is 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.
In the cross section of the toner particles observed with a transmission electron microscope,
The number average dispersion diameter of the fatty acid calcium salt is 50 nm or more and 500 nm or less,
The content of the styrene acrylic copolymer site in the binder resin is 5% by mass or more and 50% by mass or less,
A toner wherein the binder resin has an acid value of 5 mgKOH / g or more and 30 mgKOH / g or less.   The toner according to claim 1, wherein the amount of free fatty acid contained in the fatty acid calcium salt is 0.1% by mass or more and 20% by mass or less.   The toner according to claim 1, wherein the fatty acid calcium salt contains at least one fatty acid calcium salt selected from the group consisting of calcium laurate, calcium myristate, calcium palmitate, and calcium stearate. The toner according to claim 1, wherein the polyester portion contains monomer units derived from terephthalic acid, fumaric acid, and trimellitic acid.