JP2012088439A - Toner and developer, and image forming apparatus, image forming method and process cartridge using the developer, - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner and a developer excellent in low temperature fixability, heat-resistant storage property and capable of giving an image of high picture quality while maintaining hot offset resistance.SOLUTION: The toner for electrostatic charge image development comprises resin particles (C) produced by adsorbing fine particles (A) containing at least resin (a) or coating films obtained by dissolving or swelling the fine particles (A) to surfaces of resin particles (B) containing a resin (b). The resin (b) contains a polyhydroxy carboxylic acid skeleton. The resin (a) is a polyester resin. The fine particles (A) or coating films obtained by dissolving or swelling the fine particles (A) cover the surfaces of the resin particles (B) by at least 90% coverage. The thickness of the fine particles (A) or coating films obtained by dissolving or swelling the fine particles (A) adsorbed to the surfaces of the resin particles (B) is from 30 nm to 500 nm.

Description

  The present invention relates to a toner used for electrophotographic image formation such as a copying machine, electrostatic printing, facsimile, printer, electrostatic recording, and the like, and a developer, an image forming apparatus, an image forming method, and a process using the toner. It relates to the cartridge.

Conventionally, in an electrophotographic image forming apparatus, an electrostatic recording apparatus, or the like, an electric or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating.
In the heat-fixing image forming apparatus, a large amount of electric power is required in the process of heat-melting the toner and fixing it on a recording medium such as paper. Is one of the important characteristics.

In order to achieve low-temperature fixing of the toner, it is necessary to control the thermal characteristics of the binder resin that occupies most of the toner. In general, low-temperature fixability and heat-resistant storage stability of a toner are in a trade-off relationship, and it is a major issue in toner development to achieve both of these characteristics.
For example, in Patent Document 1, the surface of the core particle containing the first binder resin, the colorant, and the plasticizer is made of the second binder resin. A core-shell type toner coated with shell particles has been proposed. The design aims to achieve both low-temperature fixability and mechanical strength through the use of a plasticizer and the formation of a core-shell structure, but the binder resin and plasticizer are in a compatible state in the toner since the formation of the toner particles. Therefore, there has been a problem that the binder resin is plasticized and the heat resistant storage stability is deteriorated.

  In Patent Document 2, a plasticizer and a wax that are incompatible with the binder resin are contained, and these two are always incompatible, and the plasticizer is heated above the glass transition temperature of the plasticizer, or There has been proposed a toner that is prescribed to be compatible with a resin by heating at a temperature equal to or higher than the glass transition temperature of the resin. In Patent Document 2, compatibility between low-temperature fixability and heat-resistant storage stability is achieved at a certain level. However, from the viewpoint of energy saving, further improvement in low-temperature fixability is desired.

By the way, most of the binder resin occupying 70% or more of the constituent components of the toner is made from petroleum resources. This is due to the problem of exhaustion of petroleum resources, large consumption of petroleum resources, and emission of carbon dioxide into the atmosphere. There are concerns about global warming. Therefore, if a so-called plant-derived resin is used as a binder resin, which is derived from a plant that takes in carbon dioxide in the atmosphere and grows, the resulting carbon dioxide only circulates in the environment, which causes a problem of global warming. There is a possibility that the problem of depletion of petroleum resources can be solved at the same time, and various toners using such plant-derived resins as binder resins have been proposed.
Polylactic acid is a general-purpose and easy-to-obtain resin, but polylactic acid is a very hard resin, so that it is difficult to make a toner by a pulverization method, and only L-form or D-form is crystalline. Therefore, the solubility in organic solvents is extremely low, and it is difficult to make a toner by a polymerization method such as a dissolved resin suspension method. On the other hand, Patent Document 3 reports that the solubility in an organic solvent can be improved by mixing the L-form and D-form of polylactic acid to reduce crystallinity.

However, since polylactic acid has a low molecular weight of the monomer unit and a large number of polar groups per molecular weight, when a toner is produced using polylactic acid with reduced crystallinity, the humidity is higher than when the crystallinity is high. Greatly influenced by. For this reason, problems such as deterioration of toner storage stability, fluctuation of toner fluidity due to moisture absorption, and difficulty in controlling the charge amount are raised. In particular, it is difficult to maintain the charge amount at a constant level between a low temperature and low humidity condition and a high temperature and high humidity condition, and there is a problem that the image density is not stable.
As described above, the toner has a wide fixing width, is excellent in low-temperature fixability and heat-resistant storage stability, has high image density stability against changes in the usage environment such as temperature and humidity, and a toner containing polylactic acid and related matters The technology has not been obtained yet, and further improvement and development are desired.

  In the present invention, polylactic acid is used as a binder resin, and while ensuring hot offset resistance, it has excellent low-temperature fixability, excellent heat-resistant storage stability, and can provide an image with high image quality. It is an object to provide a toner and a developer.

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using the following toner, and have reached the present invention. That is, the present invention is as follows.
(1) Fine particles (A) containing at least the resin (a) or a film obtained by dissolving or swelling the fine particles (A) is adsorbed on the surface of the resin particles (B) containing the resin (b). A resin particle (C), wherein the resin (b) contains a polyhydroxycarboxylic acid skeleton, the resin (a) is a polyester resin, and the fine particles (A) or the fine particles (A) are The coating obtained by dissolution or swelling covers the surface of the resin particles (B) in a coverage of 90% or more, and the fine particles (A) or fine particles (A) adsorbed on the surface of the resin particles (B) ) Is dissolved or swollen, and the thickness of the coating film obtained is from 30 nm to 500 nm.
(2) The resin (b) contains a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and the polyhydroxycarboxylic acid skeleton composed of the optically active monomer has an optical purity X (%) = | X (L ) -X (D isomer) | [where X (L isomer) is the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) is the D isomer ratio (mol%) in terms of optically active monomer). The toner for developing electrostatic images according to (1) above, wherein the toner represents 80% or less.
(3) The electrostatic image according to (1) or (2), wherein the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by copolymerizing a hydroxycarboxylic acid having 2 to 6 carbon atoms. Development toner.
(4) A linear polyester obtained by reacting the polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton with a polyester diol (b12) other than (b11) together with an extender. The electrostatic charge image developing toner according to any one of (1) to (3) above, which contains a system resin (b1).
(5) The mass ratio of the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than (b11) is 31:69 to 90:10 (4) The toner for developing an electrostatic image according to (1).
(6) Resin (b2) obtained by reacting the precursor (b0) in the step of forming the linear polyester resin (b1) and the resin particles (C) with the resin particles (B). The toner according to (4) or (5), which is contained.
(7) The electrostatic image developing toner according to any one of (1) to (6), wherein the resin (a) is a polyester resin and contains a basic compound.
(8) A developer comprising the electrostatic image developing toner according to any one of (1) to (7).
(9) The developer as described in (8) above, further comprising a carrier.
(10) A developer storage container, wherein the developer according to (8) or (9) is stored.
(11) An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image using a developer. An image forming apparatus having at least developing means for forming a visual image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transfer image transferred to the recording medium, An image forming apparatus, wherein the agent is the developer according to (8) or (9).
(12) an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and a developing step of developing the electrostatic latent image using a developer to form a visible image; An image forming method comprising at least a transfer step of transferring the visible image to a recording medium and a fixing step of fixing the transfer image transferred to the recording medium, wherein the developer is the above (8) or ( An image forming method, which is the developer according to 9).
(13) At least an electrostatic latent image carrier and development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a visible image. A process cartridge that can be attached to and detached from a forming apparatus main body, wherein the developer is the developer according to (8) or (9).

  According to the present invention, even a toner made of a resin having polylactic acid as a structural unit is excellent in both low-temperature fixability and heat-resistant storage stability, and a toner having a narrow particle size distribution can be obtained. Can provide images.

FIG. 1 is a schematic explanatory view showing an example of a process cartridge used in the present invention. FIG. 2 is a schematic explanatory view showing an example of an image forming apparatus used in the image forming method of the present invention. FIG. 3 is a schematic explanatory view showing another example of the image forming apparatus used in the image forming method of the present invention. FIG. 4 is a schematic explanatory view showing an example of a tandem color image forming apparatus used in the image forming method of the present invention. FIG. 5 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

  The material constituting the toner of the present invention will be described. Note that it is easy for a person skilled in the art to change or modify the present invention within the scope of the claims to form other embodiments, and these changes and modifications are included in the scope of the claims, The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

(toner)
The resin particles (C) constituting the toner of the present invention have the following structure (1) or (2).
(1) Structure in which fine particles (A) containing at least resin (a) are adsorbed on the surface of resin particles (B) containing resin (b) (2) Fine particles containing at least resin (a) ( A structure in which the coating obtained by dissolving or swelling A) is adsorbed on the surface of the resin particles (B) containing the resin (b). In the toner of the present invention, the resin (a) is a polyester resin. The resin (b) contains a polyhydroxycarboxylic acid skeleton, and the coating obtained by dissolving or swelling the fine particles (A) or the fine particles (A) covers the surface of the resin particles (B) by 90% or more. The fine particles (A) coated on the surface of the resin particles (B) or the thickness of the coating obtained by dissolving or swelling the fine particles (A) is 30 nm to 500 nm. It is a feature.

  The resin (b) preferably has a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and the polyhydroxycarboxylic acid skeleton has a skeleton obtained by copolymerizing hydroxycarboxylic acid, and directly dehydrates and condenses the hydroxycarboxylic acid. It can be formed by a method or a method of ring-opening polymerization of a corresponding cyclic ester. The polymerization method is preferably ring-opening polymerization of a cyclic ester from the viewpoint of increasing the molecular weight of the polyhydroxycarboxylic acid to be polymerized. Examples of hydroxycarboxylic acids include aliphatic hydroxycarboxylic acids (such as glycolic acid, lactic acid, and hydroxybutyric acid), aromatic hydroxycarboxylic acids (such as salicylic acid, creosote acid, mandelic acid, burric acid, and syringic acid), or mixtures thereof. Corresponding cyclic esters include glycolide, lactide, γ-butyrolactone, 6-valerolactone and the like.

Among these, from the viewpoint of transparency and thermal characteristics of the resin particles (C), the monomer that forms the polyhydroxycarboxylic acid skeleton is preferably an aliphatic hydroxycarboxylic acid, more preferably a hydroxy group having 2 to 6 carbon atoms. Carboxylic acids, particularly preferred as hydroxycarboxylic acids and the corresponding cyclic esters are glycolic acid, lactic acid, glycolide, and lactide, and most preferred are glycolic acid and lactic acid.
When a cyclic ester of hydroxycarboxylic acid is used in addition to hydroxycarboxylic acid as the raw material of the polymer, the hydroxycarboxylic acid skeleton of the resin obtained by polymerization is a skeleton in which the hydroxycarboxylic acid constituting the cyclic ester is polymerized. For example, the polyhydroxycarboxylic acid skeleton of a resin obtained using lactide is a skeleton obtained by polymerizing lactic acid.

When the monomer that forms the polyhydroxycarboxylic acid skeleton is an optically active monomer such as lactic acid, the optical purity X (%) = | X (L isomer) −X (D isomer) | [where X (L Is a L-form ratio (%) in terms of optically active monomer, and X (D-form is a D-form ratio (%) in terms of optically active monomer)] is preferably 80% or less, more preferably 60% or less. Within this range, the solvent solubility and the transparency of the resin are improved, and the production method (I) described later, which is a preferred production method, can be easily applied.
Here, the method for measuring the optical purity X is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polymer or toner having a polyester skeleton is treated with pure water, 1N sodium hydroxide and isopropyl alcohol. And then hydrolyzed by heating and stirring at 70 ° C. Subsequently, the solid content in the liquid is removed by filtration and neutralized by adding sulfuric acid to obtain an aqueous solution containing L- and / or D-lactic acid decomposed from the polyester resin. The aqueous solution was measured by a high performance liquid chromatograph (HPLC) using a chiral ligand exchange type column SUMICHILAR OA-5000 (manufactured by Sumika Chemical Analysis Co., Ltd.), and a peak area S (L ) And D-lactic acid-derived peak area S (D). The optical purity X can be determined from the peak area as follows.
X (L-form)% = 100 × S (L) / (S (L) + S (D))
X (D form)% = 100 × S (D) / (S (L) + S (D))
Optical purity X% = | X (L form) -X (D form) |

When the resin (b) is used, it is easy to uniformly disperse the pigment and wax in the resin, and the transparency is high. Has a feature of improving.
In the present invention, the resin (b) is a straight chain obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton with a polyester diol (b12) other than (b11) together with an extender. It is preferable to contain a polyester resin (b1).

Linear polyester has a simple structure, and it is easy to control the molecular weight and physical properties (thermal characteristics, compatibility with other resins, etc.) generated thereby. The linear polyester resin in the present invention is composed of the units (b11) and (b12), and the physical properties of (b1) can be controlled by the polyester type, molecular weight, and structure used in the unit (b12). This is a merit and is characterized in that a physical property control means is clearly provided for a conventional composition containing lactic acid.
In order to obtain a linear polyester, each of (b11), (b12) and the extender needs to be bifunctional. If any of them is trifunctional or more, a crosslinking reaction proceeds and a linear polyester cannot be obtained.

  When the polyhydroxycarboxylic acid skeleton is formed, a polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton is obtained by adding a diol (11) described later and copolymerizing. Preferred as the diol (11) is 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) Adducts (specifically, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) (Addition mole number 2-30), and a combination thereof, more preferably 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, bisphenol A AO adduct, Particularly preferably, 1,3-propylene glycol Is Lumpur.

The polyester diol (b12) other than (b11) can be the same as the reaction product of the diol (11) and the dicarboxylic acid (13) among the polyester resins described later, and charged with the diol and the dicarboxylic acid during the polymerization. It is obtained by adjusting the ratio to make the hydroxyl group excessive. Preferred as (b12) is 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.). One or more selected from AO (EO, PO, BO, etc.) adduct (number of added moles 2 to 30) and combinations thereof, and selected from terephthalic acid, isophthalic acid, adipic acid, succinic acid, and combinations thereof It is a reaction product with one or more kinds.
The number average molecular weight (hereinafter abbreviated as Mn) of (b11) and (b12) is preferably from 500 to 30,000, more preferably from 1000 to 20,000, most preferably from 2000, from the viewpoint of adjusting the physical properties of (b1). 5000.

The extender used for the extension of (b11) and (b12) is not particularly limited as long as it has two functional groups capable of reacting with the hydroxyl groups contained in (b11) and (b12). However, among dicarboxylic acids (13) and their anhydrides, polyisocyanates (15) and polyepoxides (19) described later, bifunctional ones can be mentioned. Of these, from the viewpoint of compatibility with (b11) and (b12), preferred are diisocyanate compounds and dicarboxylic acid compounds, and more preferred are diisocyanate compounds. Specifically, succinic acid, adipic acid, maleic acid (and anhydride), fumaric acid (and anhydride), phthalic acid, isophthalic acid, terephthalic acid, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4 '-Diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), bisphenol A diglycidyl ether, etc., among which succinic acid, adipic acid, isophthalic acid, terephthalic acid, maleic acid (and anhydrous) Product), fumaric acid (and anhydride), and DI, is IPDI, most preferably maleic acid (and anhydride), fumaric acid (and anhydride), and IPDI.
The content of the extender in (b1) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, from the viewpoints of transparency and thermal characteristics.

  The content of the linear polyester resin (b1) contained in the resin (b) may be appropriately adjusted within a preferable range depending on the use. From the viewpoint of transparency and thermal characteristics of the resin particles (C), And 40 to 100% by mass, and more preferably 60 to 90% by mass with respect to the resin (b). Even when the hydroxycarboxylic acid contained in the resin (b1) is an optically active monomer such as lactic acid, the same content is preferable from the viewpoint of solvent solubility, provided that the optical purity is 80% or less in terms of monomer components. . When the optical purity in terms of monomer component exceeds 80%, from the viewpoint of solvent solubility, the content of the resin (b1) in the resin (b) is the content Y of the resin (b1) in the resin (b). It is preferable that the relationship between (%) and optical purity X (%) satisfy Y ≦ −1.5X + 220.

  The mass ratio of the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than (b11) constituting the linear polyester is preferably 31:69 to 90:10, From the viewpoint of the transparency and thermal characteristics of the resin particles (C), it is more preferably 40:60 to 80:20.

The resin contained in the resin particle (B) may be used in combination with any known resin other than the resin (b) containing the polyhydroxycarboxylic acid skeleton, and the resin used in combination depends on the use and purpose. Can be selected as appropriate. The resin used in combination may be a resin (b2) obtained by reacting the precursor (b0) in the resin particle forming step, and the precursor (b0) is used from the viewpoint of easy particle formation. Thus, a method of containing a resin to be used in combination is preferable. As the reaction method for obtaining (b2) from the precursor (b0) and (b0), those described later can be used.
In general, vinyl resins, polyester resins, polyurethane resins, epoxy resins, and combinations thereof are preferable as resins used in combination, and polyurethane resins and polyester resins are more preferable, and 1 is particularly preferable. Polyester resins and polyurethane resins containing 2-propylene glycol as structural units.
The content of the resin other than (b) containing the polyhydroxycarboxylic acid skeleton may be appropriately adjusted within a preferable range depending on the use. From the viewpoint of the transparency and thermal characteristics of the resin particles (C), (b) The content is preferably 0 to 60% by mass, and more preferably 10 to 40% by mass.

  Number average molecular weight of resin (b) (measured by gel permeation chromatography, details of measurement method will be described later. Hereinafter, abbreviated as Mn), melting point (measured by DSC), glass transition temperature (Tg), sp value ( The calculation method of the sp value may be suitably adjusted within a preferable range depending on the application, according to Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154). For example, the Mn of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of (b) is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. The Tg of (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 200 ° C. The sp value of (b) is preferably 8-16, more preferably 9-14.

Tg in the present invention is a value obtained from DSC measurement or flow tester measurement (when measurement cannot be performed by DSC).
When measuring by DSC, it measures by the method (DSC method) prescribed | regulated to ASTM D3418-82 using Seiko Denshi Kogyo Co., Ltd. DSC20 and SSC / 580.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.
(Flow tester measurement conditions)
Load: 30 kg / cm ² , heating rate: 3.0 ° C./min
Die diameter: 0.50 mm, Die length: 10.0 mm

In the polyester resin used for the resin (a), the acid value is 10 to 40 mgKOH / g, more preferably 15 to 35 mgKOH / g. When this acid value exceeds 40 mgKOH / g, the water resistance of the formed film tends to be poor. On the other hand, when the acid value is less than 10 mgKOH / g, the amount of carboxyl groups contributing to the aqueous formation is not sufficient, and there is a tendency that a good aqueous dispersion cannot be obtained.
Moreover, the weight average molecular weight measured by GPC (gel permeation chromatography, polystyrene conversion) is 9,000 or more, or 1 mass% in a mixed solvent of equivalence ratio of phenol / 1,1,2,2-tetrachloroethane. It is preferable that the relative viscosity is 1.05 or more when measured at 20 ° C. When the weight average molecular weight is less than 9,000 or the relative viscosity is less than 1.20, there is a tendency that sufficient processability is not imparted to the film formed from the aqueous dispersion of the polyester resin. Furthermore, the weight average molecular weight of the polyester resin is particularly preferably 12,000 or more, more preferably 15,000 or more. The upper limit is preferably 45,000 or less. If it exceeds 45,000, the operability during the production of the polyester resin tends to deteriorate, or the aqueous dispersion using such a polyester resin tends to be too viscous. The relative viscosity is preferably 1.22 or more, more preferably 1.24 or more. The upper limit is preferably 1.95 or less, and if this value is exceeded, the operability during the production of the polyester resin is deteriorated or the viscosity of the aqueous dispersion using such a polyester resin tends to be too high.

The polyester resin (a) is essentially water-insoluble and does not disperse or dissolve in water by itself, and is substantially synthesized from polybasic acids and polyhydric alcohols. The constituent components of these polyester resins (a) will be described below.
Examples of the aromatic dicarboxylic acid among the polybasic acids include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and the like. Sodium sulfoisophthalic acid or 5-hydroxyisophthalic acid can be used. Examples of aliphatic dicarboxylic acids include oxalic acid, (anhydrous) succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer acid, and the like, fumaric acid, (anhydrous) maleic acid, (anhydrous) ) Unsaturated dicarboxylic acids such as itaconic acid, (anhydrous) citraconic acid, dimer acid and the like. Examples of alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 2-cyclohexanedicarboxylic acid, 2,5-norbornenedicarboxylic acid (anhydride), tetrahydrophthalic acid (anhydride), and the like.

  The total content of aromatic polybasic acids in the total acid component is preferably 50 mol% or more. When this value is less than 50 mol%, the structure derived from the aliphatic polybasic acid and the alicyclic polybasic acid accounts for the majority of the resin skeleton, so the hardness, stain resistance, and water resistance of the formed film The storage stability of the aqueous dispersion may be reduced because aliphatic and / or alicyclic ester bonds have lower hydrolysis resistance than aromatic ester bonds. In order to ensure the storage stability of the aqueous dispersion, the content of the aromatic polybasic acid in the total acid component is preferably 70 mol% or more, and the processing is performed while balancing with other performances of the formed film. In order to improve the properties, water resistance, chemical resistance and weather resistance, 65 mol% or more of the total acid component constituting the polyester resin is terephthalic acid, in order to achieve the object of the present invention. Particularly preferred.

  On the other hand, about a polyhydric alcohol component, C2-C10 aliphatic glycol, C6-C12 alicyclic glycol, and ether bond containing glycol can be mentioned as glycol. Examples of the aliphatic glycol having 2 to 10 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1,5 -Pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-ethyl-2-butylpropanediol, etc. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol. Examples of the ether bond-containing glycol include diethylene glycol, triethylene glycol, dipropylene glycol, and glycols obtained by adding 1 to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, for example 2,2 -Bis (4-hydroxyethoxyphenyl) propane and the like can be mentioned. Polyethylene glycol, polypropylene glycol, and polytetramethylene glycol may be used as necessary. However, since the ether structure reduces the water resistance and weather resistance of the polyester resin coating, the amount used is preferably 10% by mass or less, more preferably 5% by mass or less of the total polyhydric alcohol component.

  In the present invention, it is preferable that 50 mol% or more, particularly 65 mol% or more of the total polyhydric alcohol component of the polyester resin is composed of ethylene glycol and / or neopentyl glycol. Since ethylene glycol and neopentyl glycol are industrially produced in large quantities, they are inexpensive and well-balanced in the performance of the coating film formed.Ethylene glycol components are particularly resistant to chemicals, and neopentyl glycol components are particularly advantageous. It has the advantage of improving weather resistance.

  The polyester resin used as the resin (a) in the present invention can copolymerize a tribasic or higher polybasic acid and / or a polyhydric alcohol as necessary. (Anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, (anhydrous) benzophenone tetracarboxylic acid, trimesic acid, ethylene glycol bis (anhydro trimellitate), glycerol tris (anhydro trimellitate), 1,2, 3,4-butanetetracarboxylic acid or the like is used. On the other hand, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like are used as the polyhydric alcohol having three or more functions. A tribasic or higher polybasic acid and / or polyhydric alcohol is copolymerized in an amount of 10 mol% or less, preferably 5 mol% or less, based on the total acid component or the total alcohol component. The high processability of the coating, which is an advantage of the polyester resin, is not expressed.

  If necessary, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and ester-forming derivatives thereof, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid , High-boiling monocarboxylic acids such as 4-hydroxyphenyl stearic acid, stearyl alcohol, high-boiling monoalcohols such as 2-phenoxyethanol, hydroxycarboxylics such as ε-caprolactone, lactic acid, β-hydroxybutyric acid, p-hydroxybenzoic acid An acid or an ester-forming derivative thereof may be used.

  Such a polyester resin is synthesized from the above monomers using a known method. For example, (a) an esterification reaction is performed by reacting all monomer components and / or a low polymer thereof in an inert atmosphere at 180 to 250 ° C. for about 2.5 to 10 hours, followed by 1 Torr in the presence of a catalyst. A method of obtaining a polyester resin by proceeding a polycondensation reaction under a reduced pressure at a temperature of 220 to 280 ° C. until a desired melt viscosity is reached, and (b) a stage before the polycondensation reaction reaches a target melt viscosity. The reaction product is mixed with a chain extender selected from polyfunctional epoxy compounds, isocyanate compounds, oxazoline compounds, etc. in the next step, and the reaction product is reacted for a short time to achieve a high molecular weight, (C) The polycondensation reaction is advanced to the target melt viscosity or higher, the monomer component is further added, and the depolymerization is performed in an inert atmosphere, normal pressure to pressurized system. The method or the like to obtain a polyester resin melt viscosity which can be exemplified.

  It is preferable from the viewpoint of the water resistance of the formed film that the carboxyl group necessary for the aqueous formation is unevenly distributed at the terminal of the resin molecular chain rather than being present in the resin skeleton. As a method for introducing a specific amount of carboxyl group into the molecular chain terminal of a high molecular weight polyester resin without causing side reaction or gelation, the polycondensation reaction in the above method (a) is used when producing a polyester resin. A method of adding a tribasic or higher polybasic acid component after the start of the step, or adding a polybasic acid anhydride immediately before the end of the polycondensation reaction, most of the molecules in the method (b) Preferred embodiments include a method of increasing the molecular weight of a low molecular weight polyester resin having a carboxyl group at the chain end using a chain extender, a method of using a polybasic acid component as a depolymerizing agent in the method (c), and the like.

  The content of the polyester resin in the polyester resin aqueous dispersion should be appropriately selected depending on the intended use, the dry film thickness, and the molding method, but is generally 0.5 to 50% by mass, particularly 1 to 40%. It is preferable to use in the range of mass%. As will be described later, the polyester resin aqueous dispersion of the present invention has an advantage of excellent storage stability even at a high solid content concentration of 20% by mass or more. However, when the content of the polyester resin exceeds 50% by mass, the viscosity of the polyester resin aqueous dispersion becomes extremely high, and it may be difficult to form the material substantially.

[Basic compounds]
The polyester resin of the resin (a) in the present invention is preferably neutralized with a basic compound when dispersed in an aqueous medium. In the present invention, neutralization reaction with the carboxyl group in the polyester resin is the starting force for aqueous formation (formation of resin fine particles), and furthermore, a very small amount of protective colloid action described later by the electric repulsion between the generated carboxy anions. By using in combination with the compound having, aggregation between the fine particles can be prevented. As the basic compound, a compound that volatilizes at the time of film formation or baking and curing by adding a curing agent is preferable, and examples thereof include ammonia and organic amine compounds having a boiling point of 250 ° C. or less. Examples of desirable organic amine compounds include triethylamine, N, N-diethylethanolamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine , Diethylamine, 3-ethoxypropylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, monoethanolamine, diethanolamine, Triethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like can be mentioned. The basic compound is preferably added in an amount that can be at least partially neutralized according to the carboxyl group contained in the polyester resin, that is, 0.2 to 1.5 times the equivalent of the carboxyl group. It is more preferable to add 4-1.3 times equivalent. When the amount is less than 0.2 times equivalent, the effect of adding a basic compound is not recognized, and when the amount exceeds 1.5 times equivalent, the polyester resin aqueous dispersion may be significantly thickened.

In the resin particles (C) in the present invention, the coating obtained by dissolving or swelling the fine particles (A) containing the resin (a) or the fine particles (A) containing the resin (a) contains the resin (b). As long as the surface of the resin particles (B) to be coated is covered, it may be obtained by any manufacturing method.
The resin particles (C) in the present invention may be resin particles produced by any method and process, but as a method for producing resin particles, the following production method (I) or (II), etc. Is mentioned.
(I): aqueous dispersion (W) of fine particles (A) containing resin (a) and [resin (b) or an organic solvent solution or dispersion thereof (hereinafter referred to as (O1)), or [ Resin (b) and precursor (b0) of resin (b2) or an organic solvent solution or dispersion thereof (hereinafter referred to as (O2)) are mixed, and (O1) or (O2) is added to (W). A method of dispersing and forming resin particles (B) containing (b) in (W).
In this case, simultaneously with the granulation of the resin particles (B), fine particles (A) or a coating adheres to the surface of (B) to form an aqueous dispersion (X) of the resin particles (C), from which the aqueous medium is removed. Built by.
(II): A method of obtaining resin particles (C) by coating resin particles (B) containing a resin (b) prepared in advance with a coating agent (W ′) containing a resin (a). In this case, the coating agent (W ′) may be liquid, solid, or any form, and after coating with the precursor (a ′) of (a), (a ′) is reacted (a ). Further, (B) to be used may be a resin particle produced by an emulsion polymerization aggregation method, a resin particle produced by a pulverization method, or any production method. . The coating method is not limited, and for example, a dispersion of resin particles (B) or (B) prepared in advance in an aqueous dispersion (W) of fine particles (A) containing resin (a) is dispersed. Examples thereof include a method and a method in which the solution (a) is applied to (B) as a coating agent. Among these, the production method (I) is preferable.

The resin particles (C) are more preferably obtained by the following production method because the resin particles have a uniform particle size.
Aqueous dispersion (W) of fine particles (A) and (O1) (resin (b) or an organic solvent solution or dispersion thereof) or (O2) (resin (b) and precursor of resin (b2) ( b0) and the organic solvent solution or dispersion thereof are mixed, and (O1) or (O2) is dispersed in (W) to form resin particles (B) containing (b). Further, by adsorbing the fine particles (A) on the surface of the resin particles (B), the resin particles (C) are prevented from being united with each other, and (C) is not easily split under high shear conditions. Thereby, the particle diameter of (C) is converged to a constant value, and the effect of improving the uniformity of the particle diameter is exhibited. Therefore, the fine particles (A) have such strength that they are not destroyed by shearing at the temperature at which they are dispersed, are not easily dissolved or swelled in water, (b), or their organic solvent solutions or dispersions As a preferable characteristic, it is difficult to dissolve in the liquid, (b) and (b0), or an organic solvent solution or dispersion thereof.

  In addition, a colorant, a release agent, and a modified layered inorganic mineral that are toner components are included in the resin particles (B). For this reason, before mixing (W) and (O) (O1 or O2), these components are dispersed in the solution of (O). The charge control agent may be included in the resin particles (B) or externally added. In the case of inclusion, it may be dispersed in the solution of (O) in the same manner as the colorant and the like, and in the case of external addition, it is externally added after the formation of the particles C.

  From the viewpoint of reducing dissolution or swelling of the fine particles (A) in water or a solvent used for dispersion, the molecular weight of the resin (a), the sp value (the calculation method of the sp value is Polymer Engineering and Science). , Feburary, 1974, VoL14, No. 2P, 147 to 154), crystallinity, molecular weight between cross-linking points, and the like are preferably adjusted as appropriate.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of a resin other than a polyurethane resin such as a polyester resin are obtained by gel permeation chromatography (GPC) for tetrahydrofuran (THF) soluble matter. And measured under the following conditions.
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
: TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (Molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

Moreover, Mn and Mw of a polyurethane resin are measured on condition of the following using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Temperature: 40 ° C
Detection device: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (Molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

  The glass transition temperature (Tg) of the resin (a) is preferably 50 ° C. to 100 ° C. from the viewpoint of the particle size uniformity of the resin particles (C), powder flowability, heat resistance during storage, and stress resistance. More preferably, it is 51 to 90 degreeC, Most preferably, it is 52 to 75 degreeC. If the Tg is lower than the temperature at which the aqueous resin dispersion is produced, the effect of preventing coalescence or preventing splitting is reduced, and the effect of improving the uniformity of particle size is reduced. The Tg of the coating obtained by dissolving or swelling the fine particles (A) and fine particles (A) containing the resin (a) is preferably 20 to 200 ° C., more preferably 30 to 100 ° C. for the same reason. Especially preferably, it is 40-85 degreeC. In addition, Tg in this invention is a value calculated | required from DSC measurement or a flow tester measurement (when it cannot measure by DSC).

When measuring by DSC, it measures by the method (DSC method) prescribed | regulated to ASTMD3418-82 using Seiko Electronics Co., Ltd. DSC20, SSC / 580.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The conditions for the flow tester measurement are as follows, and the following measurements are all performed under these conditions.
(Flow tester measurement conditions)
Load: 30 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, tie length: 10.0 mm

  The resin (a) is selected from known resins as described above. When the glass transition temperature (g) of the resin (a) is adjusted, the molecular weight of (a) and / or the simple substance constituting (a) is selected. It can be easily adjusted by changing the mass composition. As a method of adjusting the molecular weight of (a) (the higher the molecular weight, the higher the temperature), a known method may be used. For example, when polymerizing by a sequential reaction such as a polyester resin, a single amount is used. Adjustment of body charge ratio is mentioned.

  In the aqueous dispersion (W) of the fine particles (A), an organic solvent miscible with water (acetone, methyl ethyl ketone, etc.) may be contained in the organic solvent (u) described later in addition to water. In this case, the organic solvent to be contained is any type as long as it does not cause aggregation of the fine particles (A), does not dissolve the fine particles (A), and does not interfere with granulation of the resin particles (C). However, it may be any content, but it is preferably 40% by mass or less of the total amount with water and not remaining in the resin particles (C) after drying.

  The organic solvent (u) used in the present invention may be added to the aqueous dispersion as needed during the emulsification dispersion, [the oil phase (O1) containing the resin (b) or the resin (b) ) And (b0) in the oil phase (O2)]. Specific examples of the organic solvent (u) include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, and mineral spirit cyclohexane. Solvent: Halogen solvents such as methyl chloride, methyl bromide methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc .; Esters such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate or Ester ether solvents; ether solvents such as diethyl ether, tetrahydrofuran dioxane, ethyl cellosolve, ptyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl Ketone solvents such as ruketone, di-n-butylketone, cyclohexanone: alcohol solvents such as methanol, ethanol n-propanolisopropanol, n-butanol, isobutanol t-butanol, 2-ethylhexyl alcohol benzyl alcohol: dimethylformamide dimethylacetamide, etc. Amide solvents; sulfoxide solvents such as dimethyl sulfoxide; heterocyclic compound solvents such as N-methylpyrrolidone; and mixed solvents of two or more of these.

Even when the plasticizer (v) is added to an aqueous medium as necessary during emulsification and dispersion, the oil phase (O1) containing the resin (b) or the resins (b) and (b0 ) In the oil phase (O2) containing]. As a plasticizer (v), it is not limited at all, The following are illustrated.
(Vl) Phthalates [dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate diisodecyl, etc.];
(V2) Aliphatic dibasic acid ester [di-2-ethylhexyl adipate, 2-ethylhexyl sebacate, etc.];
(V3) trimellitic acid ester [tri-2-ethylhexyl trimellitic acid, trioctyl trimellitic acid, etc.];
(V4) Phosphate ester [triethyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, etc.];
(V5) fatty acid ester [butyl oleate and the like];
(V6) and a mixture of two or more of these.

  The particle size of the fine particles (A) used in the present invention is usually smaller than the particle size of the resin particles (B) to be formed. From the viewpoint of particle size uniformity, the particle size ratio [volume average particle size of the fine particles (A) The value of [diameter] / [volume average particle diameter of resin particles (B)] is preferably in the range of 0.001 to 0.3. The lower limit of the particle size ratio is more preferably 0.003, and the upper limit is more preferably 0.25. When the particle size ratio is larger than 0.3, (A) is not efficiently adsorbed on the surface of (B), so that the obtained particle size distribution of (C) tends to be wide.

The volume average particle diameter of the fine particles (A) can be appropriately adjusted within the above range of the particle diameter ratio so as to be a particle diameter suitable for obtaining the resin particles (C) having a desired particle diameter. The volume average particle size of (A) is generally preferably 10 to 500 nm. More preferably, it is 20 nm-300 nm. However, for example, when it is desired to obtain a resin particle (C) having a volume average particle size of 3 to 10 μm, it is preferably in the range of 10 nm to 200 nm, and when a resin particle (C) of 10 μm to 20 μm is obtained, Preferably it is 20 nm-400 nm. In the present invention, if improvement of cleaning properties is taken into consideration, it is preferable to use resin fine particles having a size of 100 nm or more. When the particle size of the resin fine particles becomes 100 nm or more, the factor that improves the cleaning property is not clear, but the resin fine particles tend to swell without completely dissolving, and as a result, the surface of the particles takes a mesh shape. Inferred. Taking these findings together, the resin fine particles to be used are particularly preferably 100 nm to 300 nm in view of the lower limit of fixing, heat-resistant storage stability, and cleaning properties.
In addition, the volume average particle size is determined by laser type particle size distribution measuring device LA-920 (manufactured by Horiba), Multisizer III (manufactured by Coulter), ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) using a laser Doppler method as an optical system, or the like. Can be measured. If there is a difference in the measured particle size between the measuring devices, the measured value by ELS-800 is adopted. In addition, since the said particle size ratio is easy to obtain, 0.1-15 micrometers is preferable as the volume average particle diameter of the resin particle (B) mentioned later. More preferably, it is 0.5-10 micrometers, Most preferably, it is 3-8 micrometers.

In the present invention, the thickness of the fine particles (A) adsorbed on the surface of the resin particles (B) or the film obtained by dissolving or swelling the fine particles (A) is 30 nm to 500 nm. When the thickness of the coating is less than 30 nm, the minimum fixing temperature is good, but the heat resistant storage stability is deteriorated. When the thickness exceeds 500 nm, the heat resistant storage stability is good, but the fixing minimum temperature is deteriorated.
The thickness of the film formed by dissolving or swelling the fine particles (A) to (A) adsorbed on the surface of the resin particles (C) obtained in the present invention is a cross section of a sample using a transmission electron microscope (TEM). It can be measured by observation. In the present invention, in particular, 30 resin particles (C) having a particle size in the range of 3 to 8 μm are randomly selected as samples, a cross-section by TEM is observed, and a fine particle (A ) Thru | or the thickness of the film which microparticles | fine-particles (A) melt | dissolve thru | or swell was measured as an average value of 30 samples.
The method for measuring the thickness of the coating is to take a cross-sectional photograph with a TEM, and use the average of the minimum thickness portion and the maximum thickness portion of the cross section as the thickness of the toner particle coating. This is measured for each sample toner, and the average thickness of the 30 is calculated.
In the case of fine particles (A) that are not coated, the distance from the base surface to the outermost surface of the fine particles is measured from the observation result by TEM. The method for calculating the average thickness is as described above.
For the resin particles (C) on which fine particles (A) or the fine particles (A) are dissolved or swollen and in which no coating is formed, the minimum value of the coating is 0 nm.

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). In this case, as a method of forming the resin particles (B) containing the resin (b2) obtained by reacting the precursor (b0) in the step of forming the resin particles (C), a reactive group-containing prepolymer (α ) And a curing agent (β) and optionally an organic solvent (u) are dispersed in an aqueous dispersion of the fine particles (A), and the reactive group-containing prepolymer (α) and the curing agent (β ) To form resin particles (B) containing resin (b2); reactive group-containing prepolymer (α) or an organic solvent solution or dispersion thereof in an aqueous dispersion of fine particles (A). A method of dispersing and reacting by adding a water-soluble curing agent (β) to form resin particles (B) containing the resin (b2); the reactive group-containing prepolymer (α) reacts with water. Reactive group-containing prepoly A method of forming resin particles (B) containing (b2) by dispersing (α) or an organic solvent solution or dispersion thereof in an aqueous dispersion (W) of fine particles (A) to react with water. Etc. can be illustrated.

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following [1] and [2].
[1] The reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1). The combination.
[2] A combination in which the reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group. .

  Among these, [1] is more preferable from the viewpoint of the reaction rate in water. In the combination [1], the functional group (α1) capable of reacting with the active hydrogen compound includes an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d) and And acid halide groups (α1e). Among these, (α1a), (α1b) and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable. The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]: C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; phenols [phenol, -cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] ]; Basic nitrogen-containing compounds [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine N-oxide, 2-mercaptopyridine, etc.]: and mixtures of two or more thereof . Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

  Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Among these, (αx), (αy) and (αz) are preferable, and (αx) and (αz) are particularly preferable. Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide and polytetramethylene oxide. Examples of polyester (αx) include polycondensates of diol (11) and dicarboxylic acid (13), polylactones (ring-opening polymerization products of ε-caprolactone), and the like. Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin. Examples of polyurethane (αz) include polyaddition product of diol (11) and polyisocyanate (15), polyaddition product of polyester (αx) and polyisocyanate (15), and the like.

As a method of adding a reactive group to polyester (αx), epoxy resin (αy), polyurethane (αz), etc.,
[1] A method of leaving a functional group of a constituent component at the terminal by excessively using one of two or more constituent components,
[2] A compound containing a functional group and a reactive group capable of reacting with the remaining functional group by leaving the functional group of the structural component at the terminal by excessively using one of the two or more structural components And the like.

  In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained. For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of polyol (1) to polycarboxylic acid (2) is equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. ] Is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.

  In the above method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the above method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted to cause a blocked isocyanate group-containing prepolymer. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride. The amount of the compound containing a functional group and a reactive group is, for example, when an isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 /. 1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

  The number of reactive groups contained per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. By setting it as the said range, the molecular weight of the hardened | cured material obtained by making it react with a hardening | curing agent ((beta)) becomes high. The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000. The weight average molecular weight of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 4,000 to 20,000. The viscosity of the reactive group-containing prepolymer (α) is preferably 2,000 poise or less, more preferably 1,000 poise or less at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that a sharp resin particle (C) having a particle size distribution can be obtained with a small amount of an organic solvent.

  Examples of the active hydrogen group-containing compound (βl) include polyamine (β1a), polyol (β1b), polymercaptan (β1c) and water (β1d) which may be blocked with a detachable compound. Among these, (β1a), (β1b) and (β1d) are preferable, and (β1a) and (β1d) are more preferable, and particularly preferable are blocked polyamines and (β1d). ). (Β1a) is exemplified by those similar to polyamine (16). Preferred as (β1a) are 4,4'-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine and mixtures thereof.

  Examples of the case where (β1a) is a polyamine blocked with a detachable compound include ketimine compounds obtained from the polyamines and ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And aldimine compounds, enamine compounds and oxazolidine compounds obtained from aldehyde compounds having 2 to 8 carbon atoms (formaldehyde, acetaldehyde).

  Examples of the polyol (β1b) are the same as the diol (11) and the polyol (12). Diol (11) alone or a mixture of diol (11) and a small amount of polyol (12) is preferred. Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

  If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). By using a reaction terminator in combination with (βl) at a certain ratio, it is possible to adjust (b2) to a predetermined molecular weight. As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.): monool (methanol, ethanol, isopropanol, butanol) , Phenol, etc.); monomercaptan (such as butyl mercaptan, lauryl mercaptan); monoisocyanate (such as lauryl isocyanate phenyl isocyanate): monoepoxide (such as butyl glycidyl ether).

  As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and an organic group (α2e) blocked with a compound capable of removing an amino group are preferred, and (α2b) is particularly preferred. Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

  Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polycarboxylic acid anhydride (β2d), and polyacid halide (β2e). Can be mentioned. Of these, (β2a) and (β2b) are preferable, and (β2a) is more preferable.

Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15), and preferred ones are also the same. Examples of the polyepoxide (β2b) are the same as those of the polyepoxide (19), and preferred ones are also the same.
Examples of the polycarboxylic acid (β2c) include dicarboxylic acid (β2c-1) and trivalent or higher polycarboxylic acid (β2c-2). (Β2c-1) alone and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred. Examples of the dicarboxylic acid (β2c-1) include the dicarboxylic acid (13), and examples of the trivalent or higher polycarboxylic acid (β2c-2) include those similar to the polycarboxylic acid (5). Is the same.
Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride. Examples of the polyacid halides (β2e) include the acid halides (acid chloride, acid bromide acid iodide) of the above (β2c). Furthermore, a reaction terminator (βs) can be used together with (β2) if necessary.

The ratio of the curing agent (β) is the ratio of the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) to the equivalent of the active hydrogen-containing group [β] in the curing agent (β) [α. ] / [Β] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is treated as a divalent active hydrogen compound.
Resin (b2) obtained by reacting a reactive group-containing prepolymer (α) and a precursor (b0) containing a curing agent (β) in an aqueous medium is a constituent of resin particles (B) and resin particles (C). It becomes. The weight average molecular weight of the resin (b2) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is preferably 3000 or more, more preferably 3,000 to 10,000,000, particularly preferably 5,000 to 5,000. One million.

  Further, during the reaction of the reactive group-containing prepolymer (α) and the curing agent (β) in the aqueous medium, the reactive group-containing prepolymer (α) such as the linear polyester resin (b1) and the curing agent. By including in the system a polymer that does not react with (β) [so-called dead polymer], the resin particles (B) react the reactive group-containing prepolymer (α) with the curing agent (β) in an aqueous medium. The resin (b2) obtained in this manner and a non-reacted resin such as a linear polyester resin (b1) are contained.

  The amount of the aqueous dispersion (W) used with respect to 100 parts by mass of the resin (b) is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass. If it is 50 parts by mass or more, the dispersed state of (b) is good, and if it is 2,000 parts by mass or less, it is economical.

The resin particles (C) include an aqueous dispersion (W) of the fine particles (A) containing the resin (a), the resin (b) or an organic solvent solution or dispersion (O1) thereof, or the resin (b) and Resin (b2) precursor (b0) or organic solvent solution or dispersion (O2) thereof is mixed, (O1) or (O2) is dispersed in (W), and (b0) is contained. When (b0) is reacted to form resin (b2), resin particles (C) having a structure in which resin (a) adheres to the surface of resin particles (B) containing at least resin (b) Is obtained by removing the aqueous medium from the aqueous resin dispersion (X). The state of the resin (a) adhering to the surface of the resin particles (B) may be either fine particles (A) or a coating. Whether the fine particles (A) are adsorbed on the surface of the resin particles (B) or whether the coating obtained by dissolving or swelling the fine particles (A) is adsorbed on the surfaces of the resin particles (B) Depends on the Tg of the resin (a) and the production conditions (such as the solvent removal temperature) of the resin particles (C).
The state of the fine particles (A) can be determined by surface observation with an FE-SEM. When the fine particles (A) are adsorbed on the surface of the resin (B), a network state is observed. When the fine particles (A) are completely dissolved to form a film, the network state is not observed. When the fine particles (A) are swollen to form a film, they are not completely dissolved, so that traces of fine particles remain. A tightly packed mesh state is observed.

  The shape of the resin particles (C) obtained by the production method (I) is controlled by controlling the difference in sp value between the resin (a) and the resin (b) and the molecular weight of the resin (a). The particle surface property can be controlled. When the difference in sp value is small, irregularly-shaped and smooth surface particles are easily obtained, and when the difference in sp value is large, spherical particles having a rough surface are easily obtained. Further, when the molecular weight of (a) is large, particles having a rough surface are easily obtained, and when the molecular weight is small, particles having a smooth surface are easily obtained. However, if the difference in sp value between (a) and (b) is too small or too large, granulation becomes difficult. If the molecular weight of the resin (a) is too small, granulation becomes difficult. From this, the sp value difference between (a) and (b) is preferably 0.01 to 5.0, more preferably 0.1 to 3.0, and still more preferably 0.2 to 2.0. .

  In the case of the production method (II), the shape of the resin particles (C) greatly affects the shape of the resin particles (B) prepared in advance, and the resin particles (C) have almost the same shape as the resin particles (B). become. However, when (B) is distorted, if more coating agent (W ′) is used in the production method (II), it becomes spherical.

  In the present invention, from the viewpoints of particle size uniformity, storage stability, and the like of the resin particles (C), the resin particles (C) are fine particles (A) containing 0.01 to 60% by mass of the resin (a) or It is preferable that the coating is obtained by dissolving or swelling the fine particles (A) containing the resin (a) and resin particles (B) containing 40 to 99.99% by mass of the resin (b), and more preferably. Is 0.1 to 50% by weight of (A) or coating and 50 to 99.9% by weight of (B), particularly preferably 1 to 45% by weight of (A) or coating and 55 to 99% by weight. (B). When (A) or the coating is 0.01% by mass or more, the blocking resistance is good, and when it is 60% by mass or less, the fixing characteristics, particularly the low-temperature fixing property is good.

Further, from the viewpoint of particle size uniformity, powder fluidity, storage stability, etc. of the resin particles (C), at least 80% of the surface of the resin particles (B) in the resin particles (C) is the resin (a). It is preferable that the fine particles (A) containing the resin or the fine particles (A) containing the resin (a) are covered with a film obtained by dissolving or swelling. The surface coverage of the resin particles (C) can be determined based on the following equation from image analysis of an image obtained with a scanning electron microscope (SEM).
Surface coverage (%) = [(A) or the area of the part covered with the coating / (A) or the area of the part covered with the coating + the area of the part where the resin particles (B) are exposed] × 100
The coverage of the toner particles observed on the surface by FE-SEM was observed from a region having a radius of 35% of the toner particle diameter from the center of the toner. In the SEM photograph, the outer part of the toner particles is different from the actual surface area of the toner. Therefore, in order to eliminate the error, the toner particle is observed in a range corresponding to 35% of the toner particle diameter.
The area of the covered part and the area of the exposed part divide the measurement range into a grid pattern, create 100 squares and count whether the squares are covered or not. To calculate. When the portion covered with one square overlaps even a little, it was calculated as the covered portion.

  From the viewpoint of particle size uniformity, the coefficient of variation of the volume distribution of the resin particles (C) is preferably 30% or less, and more preferably 0.1 to 15%. In addition, the value of [volume average particle diameter / number average particle diameter] of the resin particles (C) is preferably 1.0 to 1.4 in terms of particle size uniformity, and is 1.0 to 1.3. More preferably. The volume average particle size of (C) varies depending on the application, but is generally preferably 0.1 to 16 μm. The upper limit is more preferably 11 μm, particularly preferably 9 μm, and the lower limit is further preferably 0.5 μm, particularly preferably 1 μm. The volume average particle diameter and the number average particle diameter can be measured simultaneously with Multisizer III (manufactured by Coulter).

The resin particles (C) of the present invention can be obtained by changing the particle size of the fine particles (A) and the resin particles (B) and the coverage of the resin particle (B) surface by the coating containing the resin (a). Desirable irregularities can be imparted to the surface. When it is desired to improve the powder fluidity, the BET specific surface area of (C) is preferably 0.5 to 5.0 m ² / g. The BET specific surface area of the present invention is measured using a specific surface area meter such as QUANTASORB (manufactured by Yuasa Ionics) (measuring gas: He / Kr = 99.9 / 0.1 vol%, calibration gas: nitrogen). . Similarly, from the viewpoint of powder fluidity, the surface average center line roughness Ra of (C) is preferably 0.01 to 0.8 μm. Ra is a value obtained by arithmetically averaging the absolute value of the deviation between the roughness curve and its center line, and can be measured by, for example, a scanning probe microscope system (manufactured by Toyo Technica).

  The shape of the resin particles (C) is preferably spherical from the viewpoint of powder flowability, melt leveling properties and the like. In that case, the resin particles (B) are also preferably spherical. The average circularity of (C) is preferably 0.95 to 1.00. The average circularity is more preferably 0.96 to 1.0, and particularly preferably 0.97 to 1.0. The average circularity is a value obtained by optically detecting particles and dividing by the circumference of an equivalent circle having the same projected area. Specifically, it is measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 ml of water from which impure solids have been removed in advance is added, and 0.1 to 0.5 ml of a surfactant (dry well; manufactured by Fuji Photo Film Co., Ltd.) is added as a dispersant. Add about 1-9.5g. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser (Ultrasonic Cleaner Model VS-150; manufactured by Wellboclear) for about 1 to 3 minutes to obtain a dispersion concentration of 3,000 to 10,000 / μl. To measure the shape and distribution of the resin particles.

(Charge control agent: CCA)
The toner of the present invention can contain a charge control agent in the toner as needed.
For example, nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes such as C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. Basic Blue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Basic Green 4 (C.I. 42000) and the like and lake pigments of these basic dyes, C.I. I. Solvent Black 8 (C.I. 26150), quaternary ammonium salts such as benzoylmethyl hexadecyl ammonium chloride, decyl trimethyl chloride, or dialkyl tin compounds such as dibutyl or dioctyl, dialkyl tin borate compounds, guanidine derivatives, containing amino groups Polyamine resins such as vinyl polymers, condensation polymers containing amino groups, etc. Metal complex salts of monoazo dyes described, Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 59-7385, salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr , Fe, etc. Metal complex, a copper phthalocyanine pigment obtained by sulfonation, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like. Naturally, color toners other than black should avoid the use of charge control agents that impair the desired color, and white metal salts of salicylic acid derivatives are preferably used.

  The content of the charge control agent is preferably 0.01 parts by mass to 2 parts by mass and more preferably 0.02 parts by mass to 1 part by mass with respect to 100 parts by mass of the resin (b). When the content is 0.01 parts by mass or more, charge controllability is obtained, and when the content is 2 parts by mass or less, the chargeability of the toner is not excessively increased and the effect of the main charge control agent is reduced. In other words, the electrostatic attraction force with the developing roller is not increased and the fluidity of the toner and the image density are not lowered.

  The toner of the present invention preferably contains a layered inorganic mineral obtained by modifying at least part of ions between layers of the layered inorganic mineral with organic ions. The layered inorganic mineral obtained by modifying at least a part of ions between layers of the layered inorganic mineral used in the present invention with organic ions is preferably one having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

  Examples of the organic cation modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  As the organic anion modifier, branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, etc. Sulfates, sulfonates, carboxylates, or phosphates having A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least a part of the layered inorganic mineral with organic ions, the oil phase (O1), (O2) containing the toner composition has an appropriate hydrophobicity and has non-Nutnian viscosity, and the toner is deformed. I can do it. At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Further, as the layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) is, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
General formula (1)
R1 (OR2) nOSO ₃ M
[Wherein R 1 represents an alkyl group having 13 carbon atoms, and R 2 represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

(Coloring agent)
As the colorant used in the toner of the present invention, known pigments and dyes capable of obtaining toners of yellow, magenta, cyan and black colors can be used.
Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG and Tartrazine Lake. Can be mentioned.

Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.
Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC. Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides. These can use 1 type (s) or 2 or more types.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content is more than 15% by mass, poor dispersion of the pigment in the toner may occur. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. Examples of such resins include polyesters, styrene or substituted polymers thereof, styrene copolymers, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, and epoxy resins. , Epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, styrene or a substituted polymer thereof is particularly preferable.

  Examples of the polymer of styrene or a substituted product thereof include polystyrene, poly (p-chlorostyrene), and polyvinyl toluene. Examples of the styrene copolymer include styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer. Copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic copolymer Acid butyl copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene- Acrylonitrile-indene copolymer, steel Down - maleic acid copolymer, styrene - maleic acid ester copolymers and the like.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

(Release agent)
As the release agent used for the toner in the present invention, all known ones can be used, and in particular, the free fatty acid type carnauba wax, polyethylene wax, montan wax and oxidized rice wax can be used alone or in combination. . The carnauba wax is preferably a microcrystalline one, having an acid value of 5 or less and a particle size of 1 μm or less when dispersed in a toner binder. The montan wax generally refers to a montan wax refined from minerals, and like a carnauba wax, it is microcrystalline and preferably has an acid value of 5 to 14. The oxidized rice wax is obtained by air-oxidizing rice bran wax, and the acid value is preferably 10-30. The reason is that these waxes are finely dispersed in the toner binder resin of the present invention, so that it is easy to obtain a toner excellent in offset prevention, transferability and durability as described later. These waxes can be used alone or in combination of two or more.
As other mold release agents, any conventionally known mold release agents such as solid silicone wax, higher fatty acid higher alcohol, montan ester wax, polyethylene wax and polypropylene wax can be mixed and used.

  The Tg of the release agent used in the toner of the present invention is preferably 70 to 90 ° C. If it is less than 70 ° C., the heat-resistant storage stability of the toner is deteriorated, and if it exceeds 90 ° C., the releasability at a low temperature is not expressed, the cold offset resistance is deteriorated, and the paper is wound around the fixing machine. The amount of these release agents used is 1 to 20% by mass, preferably 3 to 10% by mass, based on the toner resin component. If it is less than 1% by mass, the effect of preventing offset is insufficient, and if it exceeds 20% by mass, transferability and durability are deteriorated.

(Developer)
The developer contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

(Career)
There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (weight average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

  The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.

Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in an organic solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core by a known coating method, drying, and baking. Can be formed. Examples of the application method include an immersion method, a spray method, and a brush coating method.

  There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

  The baking method is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace Etc., a method using a microwave, and the like.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.
When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. A preferable mixing ratio of the toner and the carrier is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

<Process cartridge>
The process cartridge used in the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image, and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to develop a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary. The developing means includes at least a developer container that contains the developer of the present invention, and a developer carrier that carries and conveys the developer contained in the developer container. Furthermore, a layer thickness regulating member for regulating the thickness of the toner layer to be carried may be provided.
The process cartridge can be detachably mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on an image forming apparatus used in the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further, if necessary. And other means.
In FIG. 1, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 1 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface.
The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out.
Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step. , Including recycling process, control process, etc.
The image forming apparatus used in the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. The other means, for example, a static elimination means, a cleaning means, a recycling means, a control means, etc. are provided.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.

The electrostatic latent image carrier (sometimes referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) is not particularly limited in terms of material, shape, structure, size, and the like. However, the shape is preferably a drum shape, and the material is an inorganic photosensitive material such as amorphous silicon or selenium, or an organic photosensitive material such as polysilane or phthalopolymethine. Body (OPC), and the like.
Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. Can do.
The electrostatic latent image forming means includes at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. .
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.
Further, the charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying DC and AC voltages in a superimposed manner.
Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Suitable examples include a developer that contains at least a developer and that can be applied to the electrostatic latent image in a contact or non-contact manner.
The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. Well, for example, a developer having a stirrer for charging the developer by frictional stirring and a rotatable magnet roller is preferable.

In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. .
Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force.
As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit.
The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.

The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel.
There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable.
Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.
The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.
The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.

There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

One mode of carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG.
An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.
The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt.
Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.

An intermediate transfer member cleaning blade 90 is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a visible image (toner image) to the recording medium 95 (secondary transfer) is applied. Possible transfer rollers 80 as the transfer means are arranged to face each other.
Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 in the rotation direction of the intermediate transfer member 50. The contact portion between the intermediate transfer member 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95 is disposed.

The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Yes.
The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K.
The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y.
The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M.
The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C.
Further, the developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly.
The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image.
The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image).
The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95.
As a result, a transfer image is formed on the transfer paper 95.
The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG.
The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. Except that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG.
In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG.
The tandem image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus.
The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center.
The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4.
An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15.
The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed.

An exposure device 21 is disposed in the vicinity of the tandem developing device 120.
A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed.
In the secondary transfer device 22, a secondary transfer belt 24 that is an endless belt is stretched around a pair of rollers 23, and a recording medium (transfer paper) conveyed on the secondary transfer belt 24 and an intermediate transfer member 50. Can contact each other.
A fixing device 25 is disposed in the vicinity of the secondary transfer device 22.
The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described.
That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel.
At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images.
That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed (L in FIG. 5) for each color image corresponding to each color image information. An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information.

The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer).
Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped.
Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. .

The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed.
The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper).
Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  Examples of the present invention will be described below, but the present invention is not limited to the examples. In addition, the part in an Example represents a mass part unless there is particular description.

[Production Examples 1 and 2] (Production of resin (b))
In an autoclave reaction vessel equipped with a thermometer, a stirring frame, and a nitrogen insertion tube, the raw materials shown in the polyester diol (b11) in Table 1 and 2 parts of 2-ethylhexylate were placed, and 160 ° C. for 3 hours at normal pressure. Ring-opening polymerization was performed, and the reaction was further performed at normal pressure and 130 ° C. After cooling the taken-out resin to room temperature, it was pulverized into polyester diols (b11) -1 and 2 containing a polyhydroxycarboxylic acid skeleton. Polyester diol (b12) -1 to 2 obtained by dehydrating and condensing the raw materials shown in polyester diol (b12) in Table 1 and polyester diol (b11) -1 to 2 previously obtained in methyl ethyl ketone. Dissolve, add IPDI as an extender, perform an extension reaction at 50 ° C. for 6 hours, and evaporate the solvent to obtain [Resin b-1] and [Resin b-2] of Production Examples 1 and 2. It was.
The weight average molecular weight (Mw) of [Resin b-1] was 12000, and the weight average molecular weight (Mw) of [Resin b-2] was Mw = 11000.

[Production Examples 3 and 4] (Production of resin (b))
L-lactide, D-lactide, ε-caprolactone, and tin octylate were added to the four-necked flask in the number of parts shown in Table 2, and heated and melted at 190 ° C. for 20 minutes in a nitrogen atmosphere. Thereafter, residual lactide and caprolactone were distilled off under reduced pressure to obtain [Resin b-3] and [Resin b-4].
The weight average molecular weight (Mw) of [Resin b-3] was 13000, and the weight average molecular weight (Mw) of [Resin b-4] was Mw = 10000.

[Production Example 5] Synthesis of polyester prepolymer
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 720 parts of an ethylene oxide 2-mole adduct of bisphenol A, 90 parts of a propylene oxide 2-mole adduct of bisphenol A, 290 parts of terephthalic acid, trimellitic anhydride 25 parts and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours under normal pressure, and then reacted for 7 hours under reduced pressure of 10 to 15 mmHg to synthesize an intermediate polyester resin. The obtained intermediate polyester resin has a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 10,700, a peak molecular weight of 3,400, a glass transition temperature (Tg) of 57 ° C., an acid value. Of 0.4 mgKOH / g and hydroxyl value of 49 mgKOH / g.
Next, 400 parts of intermediate polyester resin, 95 parts of isophorone diisocyanate, and 580 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 8 hours. [Polyester prepolymer] was synthesized. The obtained polyester prepolymer had a free isocyanate content of 1.42% by mass.

[Production Example 6] Synthesis of ketimine compound
In a reaction vessel equipped with a stirring bar and a thermometer, 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The obtained ketimine compound had an amine value of 423 mgKOH / g.

[Production Example 7] -Production of master batch-
1,000 parts of water, 530 parts of carbon black (Printtex 35, manufactured by Degussa) having a DBP oil absorption of 42 ml / 100 g and pH of 9.5, and 1200 parts of resin (b) were mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). And mixed). The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

[Production Example 8] (Production of resin (a))
A mixture consisting of 1,578 parts of terephthalic acid, 83 parts of isophthalic acid, 374 parts of ethylene glycol and 730 parts of neopentyl glycol was heated in an autoclave at 260 ° C. for 2.5 hours to carry out an esterification reaction. Next, 0.262 parts of germanium dioxide as a catalyst was added, the temperature of the system was raised to 280 ° C. in 30 minutes, and the pressure of the system was gradually reduced to 0.1 Torr after 1 hour. Under this condition, the polycondensation reaction is continued, and after 1.5 hours, the system is brought to atmospheric pressure with nitrogen gas. The mixture was stirred at 255 ° C. for 30 minutes and discharged into a sheet. And after fully cooling to room temperature, this was grind | pulverized with the crusher and the polyester resin of a 1-6 mm fraction was obtained as [resin a-1] using the sieve. The analysis results of [Resin a-1] are shown in Table 3.

[Production Example 9] (Production of resin (a))
Seven types of polyester resins were obtained in the same manner as [Resin a-1], and these were designated as [Resin a-2] to [Resin a-8]. Table 3 shows the analysis results of each resin.

[Production Example 10] (Production of fine particle dispersion (w))
In a 2L glass container with a jacket, 200 parts of [resin a-1], 35 parts of ethylene glycol mono-n-butyl ether, 0.5% by weight aqueous solution (hereinafter referred to as PVA) of polyvinyl alcohol (Unitika Ltd. “Unitika Poval” 050G) -1) 459 parts and N, N-dimethylethanolamine (hereinafter referred to as DMEA) corresponding to 1.2 equivalents of the total amount of carboxyl groups contained in the polyester resin were added, and this was opened in a tabletop homo When stirring at 6,000 rpm using Disper (Special Machine Industries Co., Ltd., TK Robotics), it was confirmed that no precipitation of resin particles was observed at the bottom of the container, and it was in a completely floating state. It was done. Therefore, this state was maintained, and hot water was passed through the jacket after 10 minutes for heating. When the temperature in the container reached 68 ° C., the stirring was set at 7,000 rpm, the temperature in the container was kept at 68 to 70 ° C., and the mixture was further stirred for 20 minutes to obtain a milky white uniform aqueous dispersion. Then, cold water was poured into the jacket, cooled to room temperature while stirring at 3500 rpm, and filtered using a stainless steel filter (635 mesh, plain weave). As a result, almost no resin particles remained on the filter. Table 4 shows the analysis results of the obtained filtrate (fine particle dispersion w-1).

[Production Example 11] (Production of fine particle dispersion (w))
In the same manner as in Production Example 10, fine particle dispersions were produced at the ratios shown in Table 4 to obtain (fine particle dispersion w-2) to (fine particle dispersion w-8).

[Production Example 12] (Production of fine particle dispersion (w-9))
In a reaction vessel in which a stir bar and a thermometer are set, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 20 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 6 hours. Further, 30 parts of 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours. W-9] was obtained. The volume average particle diameter of [fine particle dispersion W-9] measured by ELS-800 was 0.08 μm. A portion of [Fine Particle Dispersion W-9] was dried to isolate the resin component, and the glass transition temperature was 74 ° C. as measured by a flow tester of the resin component.

[Production Example 13] -Preparation of aqueous medium-
300 parts of ion-exchanged water, 300 parts of [fine particle dispersion w-1] and 0.2 part of sodium dodecylbenzenesulfonate were mixed and stirred to dissolve uniformly to prepare [Aqueous Medium Phase 1].
Further, [Aqueous medium phase 2] to [Aqueous medium phase 9] are similarly used except that [Fine particle dispersion w-2] to [Fine particle dispersion w-9] are used instead of [Fine particle dispersion w-1]. ] Was adjusted.

[Production Example 14] -Preparation of resin solution-
[Resin b-1] to [Resin b-4], [Polyester prepolymer], and 80 parts of ethyl acetate were added to the reaction vessel in the number of parts shown in Table 5 and stirred to prepare resin solutions 1 to 4. .

(Examples 1-10, Comparative Examples 1-8)
Preparation of toner base particles -Preparation of emulsion-
To resin solution 1, 5 parts of carnauba wax (molecular weight 1,800, acid value 2.7 mgKOH / g, penetration 1.7 mm (40 ° C.)) and master batch 5 parts were charged, and Ultraviscomil (Imex) of a bead mill. 3) under the condition that the liquid feeding speed is 1 kg / hour, the disk peripheral speed is 6 m / second, and the particle diameter is filled with 80% by volume of 0.5 mm zirconia beads. Further, 2.5 parts of a ketimine compound was added and dissolved to obtain a toner material liquid.
Next, 150 parts of [Aqueous medium phase 1] is put in a container, and 100 parts of toner material liquid is added while stirring at 12,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). The mixture was mixed for 10 minutes to obtain an emulsified slurry. Furthermore, 100 parts of the emulsified slurry was charged in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.

  Next, 100 parts of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice. After adding 20 parts of 10 mass% hydrochloric acid to the obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK type homomixer, fluorine-based quaternary ammonium salt compound, Fgent 310 (Neos) Was added with a 5% methanol solution so that the fluorine-based quaternary ammonium salt was equivalent to 0.1 part with respect to 100 parts of the solid content of the toner, stirred for 10 minutes, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake. Using a circulating dryer, the obtained filter cake was dried at 40 ° C. for 36 hours, and sieved with a mesh having an opening of 75 μm to prepare toner base particles 1.

As shown in Table 6, toner base particles 2 to 17 were prepared in the same manner as toner base particles 1 by changing the type of resin b, the amount thereof, the amount of prepolymer, and the type of fine particle dispersion. . Further, the amount of the fine particle dispersion in the toner base particles 6 is reduced, and the thickness of the coating film in which the fine particles (A) to fine particles (A) adsorbed on the surface of the resin particles (B) are dissolved or swollen is changed. Base particles 18 were produced.

-Preparation of toner-
100 parts of the obtained toner base particles 1 to 18 and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) as an external additive were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After 5 cycles of mixing at a speed of 30 m / sec for 30 seconds and resting for 1 minute, the mixture was sieved with a mesh having an opening of 35 μm to prepare toners 1 to 18.

Table 7 shows the volume average particle size (Dv) (unit: μm), number average particle size (Dn) (unit: μm), and volume average particle number / number average particle size of the obtained toner.

-Fabrication of carrier-
To 100 parts of toluene, 100 parts of silicone resin (organostraight silicone), 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added and dispersed with a homomixer for 20 minutes. A layer coating solution was prepared. Using a fluidized bed type coating apparatus, a resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having a volume average particle size of 50 μm to prepare a carrier.
-Production of developer-
Each developer of Examples 1 to 10 and Comparative Examples 1 to 8 was prepared by mixing 5 parts of each of the toners 1 to 18 and 95 parts of the carrier.

The obtained toner base particles 1 to 18 were subjected to FE-SEM surface observation. It was confirmed that a resin film was formed on the surface of each toner base particle. Moreover, the coverage was calculated | required. Next, the thickness of the coating obtained by dissolving or swelling the fine particles (A) or fine particles (A) adsorbed on the surface of the resin particles (B) was measured by SEM cross-sectional observation. The results are shown in Table 8.
Next, the fixability and heat resistant storage stability were evaluated using the obtained developers as follows. The results are shown in Table 8.
<Fixability>
As a fixing roller, an electrophotographic copying machine using a Teflon (registered trademark) roller (MF-200, manufactured by Ricoh Co., Ltd.) is used to change the temperature of the fixing belt, by changing the fixing unit. A solid image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was formed on a paper and cardboard transfer paper type 6200 (manufactured by Ricoh Co., Ltd.) and copy printing paper <135> (manufactured by NBS Ricoh Co., Ltd.). . At this time, the upper limit temperature at which hot offset does not occur on plain paper was taken as the fixing upper limit temperature. Further, the lower limit temperature at which the residual ratio of the image density after rubbing the solid image with a pad was 70% or more was defined as the minimum fixing temperature.
〔Evaluation criteria〕
AAA: Fixing lower limit of 105 ° C. or less AA: Fixing lower limit of 105 ° C. to 115 ° C.
A: Lower limit of fixing 115 ° C. to 125 ° C.
B: Lower limit of fixing 125 ° C. to 135 ° C.
C: Fixing lower limit 135 ° C. or more

<Heat resistant storage stability (Penetration)>
Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of the said penetration degree is large, and when it is less than 5 mm, possibility that a problem in use will generate | occur | produce is high.
〔Evaluation criteria〕
AAA: Needle penetration 20 mm or more AA: Needle penetration 15 mm or more but less than 20 mm A: Needle penetration 10 mm or more but less than 15 mm B: Needle penetration 5 mm or more but less than 10 mm C: Needle penetration less than 5 mm

As described above, the minimum fixing temperature is good when the thickness of the coating film in which the fine particles (A) to the fine particles (A) adsorbed on the surface of the resin particles (B) are dissolved or swollen is less than 30 nm. Is unsuitable as a toner. Further, when the thickness of the film in which the fine particles (A) to fine particles (A) adsorbed on the surface of the resin particles (B) are dissolved or swollen exceeds 500 nm, the heat resistant storage stability is good, but the minimum fixing temperature is that of the resin fine particles. Deterioration is 30 ° C. or more with respect to toner that is not attached. However, when the thickness of the coating film in which the fine particles (A) to fine particles (A) adsorbed on the surface of the resin particles (B) are dissolved or swollen is in the range of 30 nm to 500 nm, the heat resistant storage stability is good and the fixing minimum temperature is Is not significantly damaged with respect to toner to which resin fine particles are not attached. Further, in the range of 100 nm to 400 nm in the thickness of the coating film in which the fine particles (A) to fine particles (A) adsorbed on the surface of the resin particles (B) are dissolved or swollen, more preferable results are obtained in the storage stability and the lower limit of fixing. .
On the other hand, when the coverage is less than 90%, it can be seen that the storage stability is significantly lowered.

Further, the cleaning properties of the toners of Examples 1 to 10 and Comparative Examples 1 to 8 were evaluated as follows. The results are shown in Table 9 below.
<Cleanability>
Transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper using a scotch tape (manufactured by Sumitomo 3M Limited), and this is measured with a Macbeth reflection densitometer (RD514 type). The cleaning property was evaluated.
〔Evaluation criteria〕
A (particularly good): The difference from the blank is 0.005 or less.
○ (good): The difference from the blank exceeds 0.005 and is 0.01 or less.
Δ (slightly poor): The difference from the blank exceeds 0.01 and is 0.015 or less.
X (defect): The difference with a blank exceeds 0.015.

本発明において、クリーニング性の向上を考慮するならば、樹脂微粒子は１００ｎｍ以上のものを使用することが好ましい。樹脂微粒子の粒径が１００ｎｍ以上になるとクリーニング性が向上する要因は定かではないが、樹脂微粒子が完全に溶解せずに膨潤する傾向となり、結果、粒子の表面が網目状の形状をとることによるものと推察される。これらの知見を総合すると、定着下限、耐熱保存性、クリーニング性を考慮するならば、用いる樹脂微粒子としては１００ｎｍ〜３００ｎｍが特に好ましい。

In the present invention, in consideration of improvement in cleaning properties, it is preferable to use resin fine particles having a size of 100 nm or more. When the particle size of the resin fine particles becomes 100 nm or more, the factor that improves the cleaning property is not clear, but the resin fine particles tend to swell without completely dissolving, and as a result, the surface of the particles takes a mesh shape. Inferred. Taking these findings together, the resin fine particles to be used are particularly preferably 100 nm to 300 nm in view of the lower limit of fixing, heat-resistant storage stability, and cleaning properties.

  The image-forming toner of the present invention has excellent thermal characteristics (particularly low-temperature fixability) and good image quality, so that it can be used in electrophotographic systems such as copying machines, electrostatic printing, printers, facsimiles, and electrostatic recording. It can be suitably used as a toner used for image formation.

(About Figure 1)
101 Electrostatic latent image carrier 102 Charging means 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means (FIGS. 2 to 4)
10 Photoconductor (Photoconductor drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller 44Y Development roller 44M Developing roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge Tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning blade 95 Transfer paper (recording medium)
DESCRIPTION OF SYMBOLS 100 Image forming apparatus 120 Tandem type developing device 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Copier main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic Document Feeder (ADF)

JP 2007-199314 A JP 2006-330392 A JP 2008-262179 A

Claims (13)

  Resin particles in which fine particles (A) containing at least resin (a) or a film obtained by dissolving or swelling the fine particles (A) is adsorbed on the surface of resin particles (B) containing resin (b) (C), wherein the resin (b) contains a polyhydroxycarboxylic acid skeleton, the resin (a) is a polyester resin, and the fine particles (A) or the fine particles (A) are dissolved or swollen. The resulting coating covers the surface of the resin particles (B) with a coverage of 90% or more, and the fine particles (A) or fine particles (A) adsorbed on the surface of the resin particles (B) are dissolved. A toner for developing an electrostatic charge image, wherein the thickness of a film obtained by swelling is 30 nm to 500 nm.   The resin (b) contains a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and the polyhydroxycarboxylic acid skeleton composed of the optically active monomer has an optical purity X (%) = | X (L form) − X (D-form) | [where X (L-form) represents the L-form ratio (mol%) in terms of optically active monomer, and X (D-form) represents the D-form ratio (mol%) in terms of optically active monomer) The toner for developing electrostatic images according to claim 1, wherein the toner is 80% or less.   The electrostatic image developing toner according to claim 1, wherein the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by copolymerization of a hydroxycarboxylic acid having 2 to 6 carbon atoms.   The resin (b) is a linear polyester resin obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and a polyester diol (b12) other than (b11) together with an extender ( The electrostatic image developing toner according to claim 1, further comprising b1).   5. The mass ratio of the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than (b11) is 31:69 to 90:10. Toner for developing electrostatic images.   The resin particles (B) contain the linear polyester resin (b1) and the resin (b2) obtained by the reaction of the precursor (b0) in the step of forming the resin particles (C). The toner according to claim 4, wherein:   The electrostatic image developing toner according to claim 1, wherein the resin (a) is a polyester resin and contains a basic compound.   A developer comprising the electrostatic image developing toner according to claim 1.   The developer according to claim 8, further comprising a carrier.   A developer storage container in which the developer according to claim 8 or 9 is stored.   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with a developer to form a visible image An image forming apparatus having at least a developing unit to form, a transferring unit for transferring the visible image to a recording medium, and a fixing unit for fixing the transferred image transferred to the recording medium, wherein the developer is An image forming apparatus comprising the developer according to claim 8.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image using a developer to form a visible image, and the visible An image forming method comprising at least a transfer step of transferring an image to a recording medium and a fixing step of fixing the transferred image transferred to the recording medium, wherein the developer is the development according to claim 8 or 9. An image forming method characterized by being an agent.   An image forming apparatus main body having at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a visible image A process cartridge that is attachable to and detachable from the camera, wherein the developer is the developer according to claim 8 or 9.

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