JP2002278138A - Two-component developer - Google Patents

Abstract

(57) [Problem] A two-component composition that has excellent low-temperature fixability and offset resistance, has stable charging properties and electric resistance, and can form a good image without deterioration in image quality even after printing a large number of sheets. A system developer is provided. SOLUTION: The toner contains a binder resin having a glass transition temperature of at least 66 ° C. or less, and a carrier provided with a coat layer composed of a soft segment and a hard segment on the surface of a core material composed of a magnetic material. A two-component developer. The above two-component developer, wherein the toner contains two kinds of binder resins A and B and a wax, and their SP values satisfy the following relational expression. 0.8 ≦ | SP (B) −SP (wax) | <SP
(A) -SP (B)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a two-component developer used for developing an electrostatic image in electrophotography.

[0002]

2. Description of the Related Art As a fixing method in electrophotography,
Due to its good energy efficiency, the heating heat roller method is widely and generally used. However, in such a method, the offset phenomenon is likely to occur because the surface of the heating roller and the toner image in a molten state come into contact with each other under pressure. In order to prevent this, a method of adding wax to the toner to impart releasability is generally used.

In recent years, energy saving has been increasing due to environmental considerations, and low-temperature fixing type toners capable of fixing with low energy have been actively developed. Correspondingly,
Attempts have been made to use a polyester resin having good low-temperature fixability and relatively good heat preservability as a binder resin for the toner. However, the polyester resin has a disadvantage in that productivity is significantly reduced in the toner pulverization step because the resin itself has high strength. In order to improve this, Japanese Patent Application Laid-Open Nos. 8-278658 and 11-5
Japanese Patent No. 2611 and the like disclose that a hydrogenated petroleum resin as a resin component can provide a toner having excellent pulverizability while achieving both heat preservability and low-temperature fixability. However, it was insufficient in hot offset resistance.

[0004] The releasability of the toner is greatly affected by the state of dispersion of the wax in the binder resin (main resin). If the wax is compatible with the binder resin, the wax does not show the melting point of the wax and cannot exhibit releasability.
For the first time, the presence of a domain can improve the offset resistance. Therefore, in the case of a toner produced by the kneading and pulverizing method, it is more advantageous to use a wax having poor compatibility with the binder resin. The dispersion diameter of the domain is determined at the stage when the wax is melt-kneaded together with the toner composition including the binder resin, and the poorer the compatibility of the two, the worse the wax dispersibility and the larger the dispersion diameter. When the dispersion diameter of the wax is large, the proportion of the wax present near the surface of the toner particles relatively increases, and the wax easily exudes to the toner surface by heating at the time of fixing, which is effective in terms of offset resistance. At the same time, the wax part is easily exposed on the toner surface during pulverization,
There has been a problem that the wax migrates to the carrier or the photoreceptor to cause filming, or exhibits a cohesive property and deteriorates fluidity, thereby preventing a good image quality from being obtained.

In order to prevent the adverse effect of the wax exposed on the surface, a toner having a capsule type structure has been proposed. In the encapsulated toner, the wax is not exposed on the surface since the core layer made of the wax is included in the shell layer made of the binder resin. Therefore, although there are few problems such as the filming and cohesion,
Since the wax is covered with the strong shell layer, it requires energy and time for the wax to ooze from the inside of the toner at the time of fixing, and a satisfactory releasability may not be obtained.

Further, in response to the development of a low-temperature fixing type toner capable of fixing with low energy, a resin having a low glass transition temperature has been used as a binder resin of the toner. When the glass transition temperature of the binder resin is low, the toner is softened by heat generated by friction in the developing device, and toner spent on the carrier surface is likely to occur. Further, when the glass transition temperature of the binder resin is low, the viscosity becomes low in the kneading step in the production of the toner, so that there is a problem that a strong kneading force is not applied and the wax cannot be dispersed well.

As described above, in order to provide a toner that satisfies offset resistance and low-temperature fixability without causing filming or cohesion, it is essential to control the dispersion state of wax in toner particles. But not yet achieved.

In general, in an image forming method such as electrophotography and electrostatography, a toner or a toner and a carrier are stirred and mixed in order to develop an electrostatic latent image formed on a latent image carrier. The resulting developer is used. The developer is required to be a suitably charged mixture. In general, as a method for developing an electrostatic latent image, a method using a two-component developer obtained by mixing a toner and a carrier and a method using a one-component developer not containing a carrier are known. . The former developing method using a two-component developer has a disadvantage in that relatively stable and good images can be obtained, but carrier deterioration and a change in the mixture ratio of toner and carrier are apt to occur. On the other hand, the latter one-component developer does not have the disadvantage of the former, but has a disadvantage that the charging property is difficult to stabilize.

In addition, when the electrostatic latent image is repeatedly developed using a two-component developer, the toner in the developer is consumed and the toner concentration fluctuates. In addition, it is necessary to replenish the toner as needed to suppress this fluctuation. Generally, as a method of controlling the toner supply amount, a copying machine includes a transmission detection sensor, a flow detection sensor, an image density detection sensor, a bulk density detection sensor, and the like. Is the mainstream in recent years. This sensor is a system that controls a toner replenishment amount by developing a fixed image pattern on a latent image carrier and detecting an image density from reflected light.

[0010] The granular carrier used in such a two-component developing system prevents the spent toner on the carrier surface, forms a uniform surface of the carrier, prevents surface oxidation, prevents moisture sensitivity from being lowered, and extends the life of the developer. It is usually coated with a suitable resin material for the purpose of protecting the photoreceptor from scratches or abrasion by a carrier, controlling the charge polarity or adjusting the charge amount (for example, JP-A-58-108548).
Further, various additives are added to the coating layer (for example, JP-A-54-155048, JP-A-57-4704).
0267, JP-A-58-108549, JP-A-59-166968, and JP-B-1-19584.
JP, JP-B-3-628, JP-A-6-2023
No. 81, etc.), and a carrier having an additive attached to the surface of the carrier is used (for example, JP-A-5-273789).
Publication) technology is known.

However, there is still a problem in durability,
The problem is that the toner is spent on the carrier surface, the charge amount becomes unstable, and the resistance decreases due to the scraping of the coating resin.A good image can be obtained at the initial stage, but the number of copies increases. Since the image quality of the trailing copy image deteriorates, it is necessary to improve it.

[0012]

DISCLOSURE OF THE INVENTION The present invention provides both low-temperature fixability and offset resistance, and also has excellent pulverizability.
An object of the present invention is to provide a two-component developer which hardly causes toner spent on a carrier surface, has little film scraping of a carrier surface coat layer, and can form a high-quality image for a long period of time.

[0013]

In view of the above circumstances, the present inventors have conducted intensive studies and as a result, have found that a two-component developer capable of solving the above-mentioned problems can be achieved by combining a specific toner and a specific carrier. And completed the present invention.

That is, according to the present invention, at least a toner containing a binder resin having a glass transition temperature of 66 ° C. or lower and a coat layer composed of a soft segment and a hard segment are provided on the surface of a core material composed of a magnetic material. And a two-component developer containing the carrier. According to the present invention, there is provided the above two-component developer, wherein the binder resin has a glass transition temperature of 57 to 66 ° C. Further, according to the present invention, the two-component developer according to any one of the above, wherein the toner contains at least two or more kinds of binder resins, and they form a sea-island structure. Provided. According to the present invention,
The above two-component developer is provided, wherein wax is included in a resin constituting an island of the binder resin of the toner. Further, according to the invention, the toner contains two kinds of binder resins A and B and a wax, and their SP values satisfy the following relational expression. A system developer is provided. 0.8 ≦ | SP (B) −SP (wax) | <SP
(A) -SP (B) Further, according to the present invention, the toner contains two kinds of binder resins A and B and a wax, and the weight ratio of the binder resin A and the binder resin B ( A / B) is 1 to 50, and the weight ratio of the binder resin B to the wax (B / wax) is 1 to 5
0. The two-component developer according to any one of the above, which is 0. Further, according to the present invention, there is provided the two-component developer according to any one of the above, wherein the toner contains wax, and the maximum dispersion diameter of the wax is 1 μm or more. Further, according to the present invention, there is provided the two-component developer according to any of the above, wherein the toner contains a wax, and the melting point of the wax is 75 ° C. or more.

The toner constituting the two-component developer of the present invention contains at least a binder resin having a glass transition temperature of 66 ° C. or less, and preferably contains at least two or more binder resins. The glass transition temperature of at least one kind of binder resin is 66 ° C. or lower, and it is preferable that they form a sea-island structure. Further, it is preferable that wax is included in the resin constituting the islands. .

The case where two kinds of binder resins A and B are used in the toner of the developer of the present invention will be described. here,
The one with the larger SP value is the binder resin A, and the one with the smaller SP value is the binder resin B. Such a toner having a configuration in which the two types of binder resins A and B form a sea-island structure is formed when the SP value of various toner compositions satisfies the following relational expression (1). 0.8 <| SP (A) −SP (B) | (1) When the ΔSP value of the binder resin A and the binder resin B is large, the toner having the sea-island structure is formed, and the resin forming the island is In order to serve as a grinding aid, the pulverizability of the toner is improved.

Further, in the toner of the developer of the present invention,
Such a toner in the case where the two types of binder resins A and B form a sea-island structure, and furthermore, a wax is included in the resin forming the islands, the S of each component of the toner composition is used.
It is formed when the P value satisfies the following relational expression (2). 0.8 ≦ | SP (B) −SP (wax) | <SP (A) −SP (B) (2) That is, the ΔSP value of the binder resin B and the wax is 0.8 or more, more preferably 1. When the value is 0 or more and the ΔSP value of the binder resin A and the binder resin B is further larger than that, the toner having the above-mentioned sea-island structure in which wax is included in the island portion is formed.

That is, under the condition that these components of the toner composition are not compatible with each other, the wax is selectively taken into the binder resin B to form a domain. Further, the binder resin B is dispersed in the binder resin A as domains. In order to make the domain exist as a larger domain, the larger the right side of the equation (1), the better. As a result, a sea portion made of the binder resin A and an island portion made of the binder resin B containing the wax are formed, forming a sea-island structure.
Since the wax is covered with the binder resin B, it has a partial capsule structure in the toner particles, and can prevent direct exposure while existing as a large domain near the surface of the toner particles. .

At this time, the maximum dispersion diameter of the wax is 1.0.
It is desirable that it is not less than μm. Here, the dispersion diameter refers to the length of the major axis diameter of the wax. If it is less than 1.0 μm, the probability of the presence of the wax near the toner surface is reduced, and a sufficient releasing effect cannot be obtained. When the thickness is 1.0 μm or more, the probability that the wax exists near the toner surface increases, and a sufficient releasing effect can be obtained. However, when the dispersion diameter of the wax is too large, there is often a concern that the fluidity is reduced or filming is likely to occur. However, in the case of the toner of the present invention, the wax is covered with a sub-resin and the toner surface is Since these are not directly exposed to the light, these can be prevented.

Here, the weight ratio (A / B) of the binder resin A to the binder resin B is preferably 1 to 50, more preferably 2 to 50.
At 20, the binder resin A constitutes the sea portion as the main resin, and the binder resin B constitutes the island portion as the sub-resin. Similarly, the weight ratio (B / wax) between the binder resin B and the wax is preferably 1 to 50, more preferably 2 to 20.
Further, in the above-mentioned islands, the binder resin B constitutes the sea portion, and the wax constitutes the island portion as the sub-resin.

As a result of continuing studies to solve the above-mentioned problems of the prior art, the carrier constituting the two-component developer of the present invention has at least a soft segment and a core on the surface of a magnetic core material. By providing the coating layer composed of the hard segment, an abrasion-resistant coating layer having elasticity is formed, and thereby, when stirring for charging the developer by friction, the coating layer is caused by friction with toner or friction between carriers. Can absorb the contact with a strong impact on the carrier, so that it is possible to suppress the spent of the toner on the carrier and also to prevent the film from being scraped, and the effect of improving the durability becomes remarkable. Was. In the present invention, the soft segment refers to a soft phase or a soft component in the coat layer, and the hard segment is a hard phase or a molecular constrained component. The former absorbs impact, and the latter provides a reinforcing effect.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The developer of the present invention will be specifically described below. (Binder Resin) First, as a binder resin used in the toner of the present invention, polystyrene, poly p-chlorostyrene,
Homopolymers of styrene such as polyvinyltoluene and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acryl Methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer Styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl Methyl ketone copolymer, polystyrene - butadiene copolymer, styrene-isoprene copolymer, styrene - acrylonitrile - indene copolymer, styrene - maleic acid copolymer, styrene - styrene copolymer and maleic acid ester copolymer.

Further, the following resins can be mixed and used. For example, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic resin, rosin, modified rosin,
Examples include terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, and the like.

Further, as the binder resin particularly suitable for pressure fixing, the following can be mentioned, and they can be mixed and used. Polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio 5 to 30:95)
To 70), olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer) ,
Ethylene-vinyl acetate copolymer, ionomer resin),
Polyvinyl pyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin. These resins are not limited to being used alone, and may be used in combination of two or more.

The production method is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

Further, among the above resins, a polyester resin having a low-temperature fixing property is particularly preferable. The polyester resin used in the present invention is obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid. Examples of the polyhydric alcohol to be used include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, etherified bisphenols such as 1.4-bis (hydroxymethyl) cyclohexane, and bisphenol A, and other dihydric alcohols. Alcohol,
Trihydric or higher polyhydric alcohols can be mentioned. Examples of the polycarboxylic acid include divalent organic acids such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid; 1,2,4-benzenetricarboxylic acid; 2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,
Trivalent or higher polyhydric compounds such as 2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, and 1,2,7,8-octanetetracarboxylic acid And carboxylic acids.

Here, the glass transition temperature T of the main resin
g is preferably 66 ° C. or lower from the viewpoint of low-temperature fixability. On the other hand, the temperature is preferably 57 ° C. or more from the viewpoint of heat storage properties. It is more preferably at least 60 ° C. When the temperature is lower than 57 ° C., toner blocking is likely to occur during storage.

In the present invention, a resin usable as a sub-resin may be any resin as long as the solubility parameter difference (ΔSP value) with the main resin used is larger than the ΔSP value with wax and is incompatible with each other. Is 0.
Those greater than 8 are preferred. If the ΔSP value is 0.8 or less, the sub-resin and the main resin are mutually compatible, and it becomes impossible to form a partial capsule structure of wax. As the sub-resin, for example, the following can be used, but the present invention is not limited thereto. Polystyrene, chloropolystyrene, poly α-methylstyrene, styrene /
Chlorostyrene copolymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / vinyl acetate copolymer, styrene / maleic acid copolymer, styrene / acrylic acid ester copolymer Polymers (styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer, styrene / phenyl acrylate copolymer, etc.),
Styrene / methacrylic acid ester copolymer (styrene /
Methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / phenyl methacrylate copolymer), styrene / α-methyl methyl acrylate copolymer, styrene / Styrene resins such as acrylonitrile / acrylic acid ester copolymers (homopolymers or copolymers containing styrene or styrene substituents), vinyl chloride resins, styrene / vinyl acetate copolymers, rosin-modified maleic acid resins, phenolic resins , Epoxy resin, polyester resin, polyethylene resin, polypropylene resin, ionomer resin, polyurethane resin, silicone resin, ketone resin,
Petroleum resins and hydrogenated petroleum resins such as ethylene / ethyl acrylate copolymer, xylene resin and polyvinyl butyral resin. These resins are not limited to being used alone, and may be used in combination of two or more. In addition, the production method is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

The toner of the present invention preferably contains a wax or the like as a release agent. Such a release agent has a solubility parameter difference (ΔSP value) from the sub-resin used of 0.8 or more. Any known release agents such as solid silicone varnish, higher fatty acid higher alcohol, montan ester wax, and low molecular weight polypropylene wax can be used. In particular, the free fatty acid type carnauba wax, montan wax and oxidized rice wax can be used alone or in combination. The melting point of the wax used is preferably 75 ° C. or higher. If the temperature is lower than 75 ° C., sufficient offset resistance cannot be obtained. The use amount of these release agents is preferably 1 to 20 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the binder resin component of the toner.
To 10 parts by weight.

The toner of the present invention may contain a coloring agent, a charge controlling agent, a fluidity improving agent, a magnetic material, and the like, if necessary. Examples of the coloring agent include carbon black, lamp black, iron black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, and triallyl methane. Any conventionally known dyes and pigments such as dyes and pigments such as dyes can be used alone or in combination, and can be used as a black toner or a full color toner. The amount of these colorants to be used is generally 1 to 30% by weight, preferably 3 to 20% by weight, based on the toner resin component.

As the charge control agent, any conventionally known charge control agents such as a nigrosine dye, a metal complex type dye and a quaternary ammonium salt can be used alone or in combination. The amount of these charge control agents used is based on the toner resin component 1
0.1 to 10 parts by weight, preferably 1 to 100 parts by weight
-5 parts by weight.

As the fluidity improver, any conventionally known fluidity improver such as silicon oxide, titanium oxide, silicon carbide, aluminum oxide and barium titanate can be used alone or in combination. The amount of these fluidity improvers to be used is 0.1 to 5 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the toner.

Examples of the magnetic material include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, and bismuth. , Cadmium, calcium,
Alloys of metals such as manganese, selenium, titanium, tungsten, and vanadium and mixtures thereof are given.

The solubility parameter SP value (δ) in the present invention can be determined by the following method, but is not limited thereto. The SP value is defined by the following equation as a function of the cohesive energy density. δ = (ΔE / V) 1/2 (3) ΔE: intermolecular cohesive energy (heat of evaporation) V: total volume of the mixed liquid ΔE / V: cohesive energy density , The amount of heat change due to mixing ΔHm is given by the following equation. ΔHm = V (δ1−δ2) · Φ1 · Φ2 (4) δ1: SP value of solvent δ2: SP value of solute Φ1: Volume fraction of solvent Φ2: Volume fraction of solute , Δ2, the smaller the value of ΔHm and the smaller the free energy of Gibbs,
Those having a small difference in SP value are considered to have higher affinity. As a method of actually calculating the SP value, SP
By comparing the solubility of the resin with various solvents whose values are known, the SP value of the most compatible solvent is used to determine the S value of the unknown resin.
The P value was set. In addition, as a method for obtaining the SP value, when the monomer composition of the resin is known, it can be calculated using the following method of Fedor et al. SP value = (ΣΔei / ΣΔvi) 1/2 Δei: evaporation energy of an atom or an atomic group. Δvi: molar volume of an atom or atomic group. In the present invention, a value calculated mainly from the monomer composition was used.

Next, it is used for the two-component developer of the present invention.
The carrier will be described. Carry used in the present invention
A is a soft segment on the surface of a core made of magnetic material.
And a hard segment coating layer.
You. As a coating resin for forming the coating layer, a main component
Is a functional group [where Si (OR¹) Group (where R¹Is
Hydrogen atom, lower alkyl group or acyl group)
Organic compound (a) having organic compound (a)
A functional group capable of reacting with a functional group¹)
Group (R¹Have the same meanings as described above).
And / or a hydrolytic condensate thereof, represented by the following general formula
Organosilicon compound (c) and / or its hydrolytic shrinkage
Compound, Si (OR^Two)_Four  (Where R^TwoMay be the same or different, and
Or a lower alkyl group or an acyl group)
Can be exemplified. This place
(A) is a soft segment, (c) is a hard segment
(B) acts as a binder.

The organic compound (a) preferably contains an amino group in order to give the carrier a positive charge. Specific examples of the organic compound (a) having an amino group include allylamine, diallylamine, isopropylamine, diisopropylamine, iminobispropylamine, ethylamine, diethylamine, 2-ethylhexylamine,
3-ethoxypropylamine, diisobutylamine, 3
-Diethylaminopropylamine, di-2-ethylhexylamine, dibutylaminopropylamine, propylamine, dimethylaminopropylamine, methyliminobispropylamine, 3-methoxypropylamine, ethylenediamine, 1,4-diaminobutane, 1,2- Low molecular weight organic compounds having one or more amino groups such as diaminopropane, 1,3-diaminopropane, hexamethylenediamine, ethanolamine, and diethanolamine; polyethyleneimines, for example, Epomin series (Nippon Shokubai Co., Ltd. Epomin SP-006,
Epomin SP-012, Epomin SP-018, Epomin SP-103, Epomin SP-110, Epomin SP
-200, Epomin SP-300, Epomin SP-10
00, Epomin SP-1020, etc.), polyallylamines (eg, Nitto Boseki's PAA-L, PAA-H, etc.),
Homopolymers of amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, and these amino group-containing (meth) acrylates and other (meth) acrylates and (meth) acrylic Examples thereof include a copolymer with an acid, and a high molecular organic compound containing an amino group such as polyoxyethylene alkylamines.

The compound (b) binds the organic compound (a) and the organosilicon compound (c), and a functional group capable of reacting with the functional group of the organic compound (a) and Si (OR) ¹ ) A compound having a group (the meaning of R ¹ is the same as described above). Specifically, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3
4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriisopropoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysisilane, γ-glycid Epoxy group-containing compounds such as xypropylmethyldimethoxysilane and γ-glycidoxypropylmethyldiethoxysilane; or γ-isocyanopropyltrimethoxysilane, γ-isocyanopropyltriethoxysilane, γ-isocyanopropylmethyldimethoxysilane And isocyanate group-containing compounds such as γ-isocyanopropylmethyldiethoxysilane; and one or more of these can be used.

The organosilicon compound used in the present invention
As (c), if it is represented by the following general formula,
It is not limited to. Si (OR^Two)_Four  (Where R^TwoMay be the same or different, and
Represents a lower alkyl group or an acyl group). Specific examples include tetramethoxysilane, tetraethoxy
Sisilane, tetraisopropoxysilane, tetrabutoki
And silane compounds such as silane.
Alternatively, two or more kinds can be used. Among them, formed
From the point that the coated film shows good moisture resistance.
Sisilane and tetraethoxysilane are preferred.

As the coating resin used in the carrier of the present invention, although the detailed reason is not known, those having the above-mentioned constitution are preferable. The coating resin of the carrier of the present invention is completely different from a conventionally known silicone resin, and the carrier coated with the resin has very good fluidity.

In the present invention, as another method of providing a coat layer composed of a soft segment and a hard segment, for example, a method of crosslinking a thermoplastic resin such as an acrylic resin with an amino resin can be mentioned. The present inventors have been studying to solve the problems of the prior art, and as a result, at least in a carrier having a resin coat film, the resin coat film is made of a thermoplastic resin such as an acrylic resin, guanamine. By adding a charge controlling agent to a resin component crosslinked with an amino resin such as a resin, a coat film having elasticity can be obtained. As a result, during stirring for charging the developer by friction, contact with a strong impact on the coating resin due to friction with the toner or friction between the carriers can be absorbed, so that it is possible to suppress the spent of the toner on the carrier. In addition to this, film shaving can be prevented, and the improvement effect is remarkable.

As the thermoplastic resin used here, all known thermoplastic resins can be used. As an amino resin, a guanamine resin, a melamine resin, or the like can be used. Hereinafter, a case where an acrylic resin is used as the thermoplastic resin and a guanamine resin is used as the amino resin will be described. As the acrylic resin used here, any acrylic resin can be used.
It is good to use what has 20-100 degreeC, Preferably it is 25-80 degreeC. If the Tg is lower than 20 ° C., blocking occurs even at room temperature, so that the storage stability is poor, which is not preferable. On the other hand, if the Tg is higher than 100 ° C., the resin of the coat layer becomes too hard to obtain elasticity, so that impact cannot be absorbed and a sufficient improvement effect cannot be obtained.

Further, the content of the guanamine resin is 20 to 5
The elasticity of the resin of the coat layer can be adjusted by increasing or decreasing the amount within the range of 0% by weight. When the content of the guanamine resin is less than 20% by weight, a sufficient cross-linking reaction with the acrylic resin does not occur, so that the effect of improving the wear resistance cannot be obtained. On the other hand, if it exceeds 50% by weight, the crosslinking reaction with the acrylic resin proceeds too much, and the coating film resin is too hardened and elasticity cannot be obtained. I can't.

Further, by using either an aromatic sulfonic acid or a phosphoric acid as a charge controlling agent, a crosslinking reaction with a guanamine resin is brought into a preferable state, and the charge controlling effect is remarkable. Further, in addition to those mentioned here, carbon black or an acidic catalyst can be used alone or in combination as the charge control agent. As the carbon black, any of those generally used for carriers or toners can be used. As the acidic catalyst, any one having a catalytic action can be used. For example,
It has a reactive group such as a fully alkylated type, a methylol group type, an imino group type, or a methylol / imino group type, but is not limited thereto. Further, carbon black can be used for the purpose of a resistance regulator.

Further, when the content of the charge controlling agent is 10% by weight or less based on the guanamine resin, the improvement effect is remarkable. If the charge control agent exceeds 10% by weight, the reaction with the guanamine resin proceeds excessively, so that a sufficient crosslinking reaction between the guanamine resin and the acrylic resin does not occur,
The effect of improving the wear resistance cannot be sufficiently obtained.

Furthermore, the improvement effect is remarkable when the method of manufacturing the carrier uses the above conditions. Specifically, since the crosslinking reaction with the resin is promoted by including the charge control agent, it is possible to suppress the occurrence of aggregation during the production, a carrier having weak aggregation is obtained, and crushing is performed. It becomes easier and the yield is improved. However, as described above, the content of the charge control agent is preferably in the range of 10% by weight or less based on the guanamine resin. When the amount of the charge control agent exceeds 10% by weight, the reaction with the guanamine resin proceeds excessively, so that a sufficient crosslinking reaction between the guanamine resin and the acrylic resin does not occur, and the effect of improving the abrasion resistance cannot be obtained sufficiently. Problems arise.

Further, it is also possible to include particles having a primary particle diameter or a secondary particle diameter larger than the thickness of the coat layer in the coat layer. In this case, since the particles are more convex than the coating film, the agitation for frictionally charging the developer alleviates the contact with the coating resin, which has a strong impact on the coating resin due to friction with the toner or friction between the carriers. You can do it. This makes it possible to prevent the spent of the toner on the carrier, and also to prevent the coating resin, which is the place where the charge is generated, from being scraped, and the improvement effect is remarkable. When the particles are smaller than the thickness of the coating layer, the effects are significantly reduced because the particles are buried in the coating resin. If the particles are larger than 10 times the thickness of the coating layer, the contact area between the particles and the coating resin is small, so that a sufficient adhesive force cannot be obtained and the particles are easily detached. The particle content is 20 to 80% by weight, preferably 30 to 80% by weight based on the coating resin.
70% by weight. When the content is less than 20% by weight, the proportion of the particles occupied by the coating resin on the surface of the carrier particles is smaller than that of the carrier particles. Not enough. When the amount is more than 80% by weight, the proportion of the particles is too large as compared with the proportion of the coating resin on the carrier surface, so that the proportion of the coating resin, which is the place where the charge is generated, is insufficient, and the charge is insufficient. I cannot get the ability.

Further, the particles used here are alumina, titanium oxide, zinc oxide, barium titanate, iron oxide, barium sulfate, etc., but the improvement effect is remarkable, but not limited thereto. In addition, by using the surface of these particles coated with a low electric resistance material, the surface of the particles has a low electric resistance, so that excessive toner charging is suppressed, and the charged electric charges in the contact area are contactless. Easy to move to,
It contributes to the improvement of the charge exchange property and the charging speed, and even if some toner adheres to the surface of the carrier, the charge amount is not remarkably reduced, and the improvement effect is remarkable.

As the material of the core material of the carrier used in the present invention, for example, surface-oxidized or unoxidized iron, magnetic substance-dispersed resin particles, ferrite particles, magnetite particles and the like can be used. There is no particular limitation on the manufacturing method. Further, such a carrier core material may be composed of only a magnetic material, or may be composed of a combination of a magnetic material and a non-magnetic material, and may be a mixture of two or more magnetic particles. There may be.

As a method for coating the surface of the carrier core material with the coating resin, the resin is dissolved or suspended in a solvent and applied to the surface of the core material, and the resin is coated with a core material comprising magnetic particles or the like. The method of attaching to the surface is preferable, but not particularly limited. In general, the amount of the coating resin to be treated is desirably 1 to 3% by weight relative to the carrier core material in view of the film forming property and durability of the coating material. More preferably 1.5 to 2.5% by weight
Is preferred. If the content is less than 1% by weight, the surface of the carrier core material cannot be coated with the resin substantially uniformly, so that carrier adhesion or white spots due to dielectric breakdown occur in the developing region. on the other hand,
If it exceeds 3% by weight, the film formability is not improved, but rather the fluidity of the developer is reduced.

[0050]

EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples. In addition, polyester resin used for toner,
The SP value of the styrene / acrylic copolymer was changed by changing the composition of the constituent monomers. Also,
In Examples and Comparative Examples, parts are parts by weight.

Example 1 Preparation of toner  Polyester resin A-85 parts (SP value: 10.0, monomer: PO / EO adduct of bisphenol A, terephthalic acid / trimellitic acid, Tg: 64 ° C.) Styrene / acrylic copolymer B-15 parts (SP value : 9.0, monomer: styrene, methyl acrylate) 5 parts of oxidized wax (SP value: 9.1, melting point: 78 ° C) 10 parts of carbon black (# 44 manufactured by Mitsubishi Carbon Corporation) 2 parts of metal salt compound of salicylic acid Mix thoroughly with Henschel mixer
After that, at a temperature of 130 to 140 ° C., about 30
After heating and melting to room temperature, the kneaded material
Pulverized and classified by a wet mill to obtain a volume average particle size of 7.5 μm.
A toner having a particle size was obtained. Additive (R972 Nippon Aerosil)
0.5 part with respect to 100 parts of toner.
After stirring and mixing with a shell mixer, a large particle size
The particles were removed to obtain the final toner. Transmission electron microscope (T
EM), the cross section of the toner was observed.
Styrene / acrylic copolymer in the sea portion of the terresin A-
Body B- and wax islands are dispersed, the largest of the islands
The dispersion diameter was 1.1 μm. This toner is represented by a schematic diagram.
It was as shown in FIG. The polyester resin A at this time
-And the styrene / acrylic copolymer B-
1.0, styrene / acrylic copolymer B- and wax
Was 0.1.

[0052]Preparation of carrier  In a flask equipped with a stirrer, thermometer and condenser,
Ethyleneimine "Epomin SP-018" (Nippon Shokubai)
1.64 parts, γ-glycidoxypropyltrimethoxy
Charge 1.49 parts of silane and 47.05 parts of ethanol
After stirring at 50 ° C. under a nitrogen atmosphere for 24 hours,
And mixed with 1.09 parts of water and 5.53 parts of ethanol
The solution was added dropwise over 15 minutes and stirred for 1 hour. Moreover
Add the tetramethoxysilane oligomer “M Silique” to the reaction solution.
Port 51 "(manufactured by Tama Chemical) 14.30 parts and ethanol 2
Add 8.88 parts and stir at 20 ° C for 24 hours
Coating agent 1 was obtained. Core material (fired ferrite powder: F-300, manufactured by Powdertech Co., Ltd., F-300; average particle size: 50 μm) 5000 parts Coating agent 1 (non-volatile content: 17% by weight) 588 parts A rotary bottom plate disk and stirring blades were provided in a fluidized bed. Turning
Coating equipment that performs coating while forming circulating flow
Use and apply the above coating liquid on the above carrier core material
did. The obtained carrier is heated at 190 ° C. for 1 hour in an electric furnace.
During the heating, carrier particles were obtained.

[0053]Preparation of developer  A carrier is added to 5 parts of the toner, and the total amount is 100 parts.
And a two-component developer was prepared.

Example 2 Preparation of toner  Polyester resin A-85 parts (SP value: 10.0, monomer: PO / EO adduct of bisphenol A, terephthalic acid / trimellitic acid, Tg: 64 ° C.) Styrene / acrylic copolymer B-15 parts (SP value : 9.0, monomer: styrene, methyl acrylate) Paraffin wax (SP value: 8.1, melting point: 77 ° C) 5 parts Carbon black (# 44, manufactured by Mitsubishi Carbon Corporation) 10 parts Salicylic acid metal salt compound 2 parts The above composition Mix thoroughly with a Henschel mixer
After that, at a temperature of 130 to 140 ° C., about 30
After heating and melting to room temperature, the kneaded material
The particles are crushed and classified by a wet mill, and the particles having a volume average particle size of 7.5 μm are obtained.
A toner having a diameter was obtained. Additive (R972 Nippon Aerosil Co., Ltd.)
0.5 parts per 100 parts of toner
After stirring and mixing with a gel mixer, large-sized particles are passed through a mesh.
The particles were removed to obtain the final toner. Cross section of toner by TEM
As a result of the observation, the sea portion of the polyester resin A-
And styrene / acrylic copolymer B containing wax
-Islands are dispersed, and the maximum dispersion diameter of wax is
It was 1.2 μm. This toner is schematically shown in FIG.
(A) and the TEM photograph were as shown in FIG. 2 (b).
The polyester A- and styrene / acrylic
ΔSP value of polymer B- is 1.0, styrene / acrylic
The ΔSP value of copolymer B− and wax was 0.9.
Was.Preparation of developer  The same carrier as in Example 1 was used, and the above toner was used.
Except for this, a two-component developer was prepared in the same manner as in Example 1.
did.

Embodiment 3 Preparation of toner  Polyester resin A-85 parts (SP value: 10.8, monomer: PO / EO adduct of bisphenol A, fumaric acid / trimellitic acid, Tg: 62 ° C.) Styrene / acrylic copolymer B-15 parts (SP value : 9.0, monomer: styrene, methyl acrylate) Paraffin wax (SP value: 8.1, melting point: 77 ° C) 5 parts Carbon black (Mitsubishi Carbon Co. # 44) 10 parts Salicylic acid metal salt compound 2 parts SP value Using polyester resin A-
Except for the above, a toner was obtained in the same manner as in Example 2. By TEM
When the cross section of the toner was observed, the polyester resin A-
Styrene / acrylic with wax in the sea area
The islands of the copolymer B- are dispersed, and
The diameter of the dispersion was 1.8 μm. Schematic diagram of this toner
It was as shown in FIG. Poly at this time
Ester resin A- and styrene / acrylic copolymer B-
Is 1.8, styrene / acrylic copolymer B
The ΔSP value of − and the wax was 0.9.Preparation of developer  The same carrier as in Example 1 was used, and the above toner was used.
Except for this, a two-component developer was prepared in the same manner as in Example 1.
Made.

Embodiment 4 Preparation of toner  Polyester resin A-85 parts (SP value: 11.0, monomer: PO / EO adduct of bisphenol A, fumaric acid / trimellitic acid, Tg: 56 ° C.) Styrene / acrylic copolymer B-15 parts (SP value : 9.0, monomer: styrene, methyl acrylate) Paraffin wax (SP value: 8.1, melting point: 77 ° C) 5 parts Carbon black (# 44, manufactured by Mitsubishi Carbon Corporation) 10 parts Salicylic acid metal salt compound 2 parts The same but different Tg polyester resin A-
A toner was obtained in the same manner as in Example 3 except that the toner was used.
When the cross section of the toner was observed by TEM,
A polystyrene containing wax in the sea area of the terresin A-
And the islands of the acrylic / acrylic copolymer B- are dispersed,
The largest wax dispersion diameter was 2.0 μm. This
FIG. 2 (a) shows a schematic diagram of the toner. This
Polyester resin A- and styrene / acrylic
The ΔSP value of the copolymer B- was 2.0, and styrene / acrylic
The ΔSP value of copolymer B- and wax was 0.9.
Was.Preparation of developer  The same carrier as in Example 1 was used, and the above toner was used.
Except for this, a two-component developer was prepared in the same manner as in Example 1.
did.

Comparative Example 1 Preparation of toner  Polyester resin A-85 parts (SP value: 10.0, monomer: PO / EO adduct of bisphenol A, terephthalic acid / trimellitic acid, Tg: 64 ° C.) Styrene / acrylic copolymer B-15 parts (SP value : 9.3, monomer: styrene, acrylonitrile) Paraffin wax (SP value: 8.1, melting point: 77 ° C) 5 parts Carbon black (# 44, manufactured by Mitsubishi Carbon Corporation) 10 parts Salicylic acid metal salt compound 2 parts SP value Use different styrene / acrylic copolymer B-
A toner was obtained in the same manner as in Example 2 except for the fact that the toner was not used. T
When the cross section of the toner was observed by EM, the polyester
Resin A- and styrene / acrylic copolymer B-
Melts together to form the sea part, and the island of wax alone is dispersed
The largest wax dispersion diameter was 1.4 μm.
Was. This toner is schematically shown in FIG.
The photograph was as shown in FIG. Pollier at this time
Stell resin A- and styrene / acrylic copolymer B-
Is 0.7, styrene / acrylic copolymer B-
And the ΔSP value of the wax was 1.2.Preparation of developer  The same carrier as in Example 1 was used, and the above toner was used.
Except for this, a two-component developer was prepared in the same manner as in Example 1.
did.

Comparative Example 2 Preparation of toner  Polyester resin A-85 parts (SP value: 10.0, monomer: PO / EO adduct of bisphenol A, terephthalic acid / trimellitic acid, Tg: 64 ° C.) Styrene / acrylic copolymer B-15 parts (SP value : 9.3, monomer: styrene, acrylonitrile) Carnauba wax (SP value: 8.6, melting point: 83 ° C) 5 parts Carbon black (# 44, manufactured by Mitsubishi Carbon Corporation) 10 parts Salicylic acid metal salt compound 2 parts Different SP values Comparative Example 1 except that wax was used
Similarly, a toner was obtained. Observation of toner cross section by TEM
Was performed, polyester resin A-, styrene /
Acrylic copolymer B and wax are all compatible
A single phase is formed and the wax domains are not
Was not. This toner is schematically shown in FIG.
(A) and the TEM photograph were as shown in FIG. This
Polyester resin A- and styrene / acrylic
The ΔSP value of the copolymer B- was 0.7, and styrene / acrylic
The ΔSP value of the copolymer B- and the wax was 0.7.
Was.Preparation of developer  The same carrier as in Example 1 was used, and the above toner was used.
Except for this, a two-component developer was prepared in the same manner as in Example 1.
did.

Comparative Example 3 Preparation of toner  Polyester resin A-40 parts (SP value: 10.0, monomer: PO / EO adduct of bisphenol A, terephthalic acid / trimellitic acid, Tg: 64 ° C.) Styrene / acrylic copolymer B-60 parts (SP value : 9.0, monomer: styrene, methyl acrylate) Paraffin wax (SP value: 8.1, melting point: 77 ° C) 5 parts Carbon black (# 44, manufactured by Mitsubishi Carbon Corporation) 10 parts Salicylic acid metal salt compound 2 parts Polyester resin A -40 parts, styrene / acrylic
Example 2 except for containing 60 parts of copolymer B-
Similarly, a toner was obtained. Observation of toner cross section by TEM
Was performed, the main resin and sub resin were reversed,
In the sea area of styrene / acrylic copolymer B-,
The islands of the stell resin A- and the islands of wax are dispersed respectively.
Had been The largest wax dispersion diameter is 1.0 μm.
Was. This toner is schematically shown in FIG.
Was. At this time, the polyester resin A-
The ΔSP value of the cryl copolymer B- was 1.0, and styrene /
The ΔSP value of the acrylic copolymer B− and the wax was 0.9.
Met.Preparation of developer  The same carrier as in Example 1 was used, and the above toner was used.
Except for this, a two-component developer was prepared in the same manner as in Example 1.
Made.

Comparative Example 4Preparation of carrier  In the preparation of the carrier of Example 1, the coating agent 15
Instead of 88 parts, use silicone resin SR2411 (Toray
・ Dow Corning Co.) Use 500 parts of toluene solution
Carrier particles were obtained in the same manner as in Example 1 except that the procedure was repeated.Preparation of developer  The same toner as in Comparative Example 1 was used, and the above carrier was used.
Except for this, a two-component developer was prepared in the same manner as in Example 1.
did.

Table 1 shows the physical properties of the constituent components of the toners of the above Examples and Comparative Examples. The performance of the toner and the developer of Examples and Comparative Examples was evaluated by the following methods, and the results are shown in Table 2. Evaluation method: (Observation of wax dispersion state)
m, stained with ruthenium tetroxide, and then transmitted through a transmission electron microscope (TEM) at a magnification of 10,000.
Observation was performed at a magnification and photographed. By evaluating the image of the photograph, the dispersion state of the wax was observed, and the dispersion diameter and the like were measured.

(Evaluation of Fixing Property) Using a remodeling machine of Ricoh Co., Ltd. MF-4550 using a Teflon (registered trademark) roller as a fixing roller, Ricoh type 6200 paper was set in this, and a copying test was performed. Was done. The hot offset occurrence temperature was determined as follows by changing the fixing temperature. (Good) ：: 200 ° C. or more, ：: Less than 200 ° C. to 190
° C, □: less than 190 ° C-180 ° C, Δ: less than 180 ° C-
170 ° C, X: less than 170 ° C (bad)

(Evaluation of Filming) Filming generated on the photoreceptor was visually evaluated on the photoreceptor and evaluated according to the following three grades according to the situation. (Good) ○: not observed, Δ: slightly observed,
X: Observed (evil)

(Evaluation of heat resistance storage stability)
After placing in a 0 ml glass bottle and tapping the glass bottle about 50 times to solidify the sample, it is left in a high-temperature bath at 50 ° C. for 24 hours, and then the penetration is determined using a penetration tester as follows. Was. (Good) ◎: Penetration, ○: ~ 25mm, □ Less than 25mm ~ 2
0 mm, Δ: less than 20 mm to 15 mm, ×: less than 15 mm (poor)

(Pulverizability) The toner crushed to an average particle diameter of 1 mm or less is determined by a processing amount per unit time when pulverized under constant conditions by an IDS type pulverizer manufactured by Nippon Pneumatic Co., Ltd. Was evaluated. (Good) ○: 3 kg or more, Δ: less than 3 kg to 2 kg, ×:
Less than 2kg (bad)

(Toner Spent and Film Shaving) The prepared carrier and developer were transferred to a copying machine MF- manufactured by Ricoh Co., Ltd.
Set to 4550 remodeling machine, and 10
A running evaluation of 0000 sheets was performed. Then, the charge reduction amount and the resistance reduction amount of the carrier after the running were determined. The amount of decrease in the amount of charge referred to here means a sample obtained by mixing the toner at 5% by weight with respect to the initial carrier at 95% by weight and triboelectrically charging the sample by a general blow-off method [TB-200 manufactured by Toshiba Chemical Corporation: From the charge amount (Q1) measured in step [1], the charge amount (Q2) measured by the same method as described above for the carrier obtained by removing the toner in the developer after running by the blow-off device. Refers to the amount, and the target value is 7.0 (μc / g) or less. Also,
Since the cause of the decrease in the charge amount is toner spent on the carrier surface, the decrease in the charge amount can be suppressed by reducing the toner spent. The amount of decrease in resistance is a value obtained by charging an initial carrier between electrodes having a resistance measurement parallel electrode and a gap of 2 mm, applying DC 200 V, and measuring the resistance value after 30 seconds with a high resist meter into a volume resistivity ( R1) is a value obtained by subtracting a value (R2) measured by the same method as that of the carrier obtained by removing the toner in the developer after running by the blow-off device from the R1). 2.0 [Log (Ω · cm)] or less. Further, since the cause of the decrease in resistance is abrasion of the coating resin film of the carrier, the amount of decrease in resistance can be suppressed by reducing the abrasion of the film.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

EFFECT OF THE INVENTION The two-component developer of the present invention achieves both excellent low-temperature fixability and offset resistance and does not generate toner spent on the carrier surface. Since the film is not scraped, a stable electric resistance can be obtained. Therefore, the deterioration of the image quality of the image after printing a large number of sheets is greatly improved, and a good image can be obtained for a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of a toner according to a first embodiment.

FIG. 2A is a schematic sectional view of a toner according to a second embodiment.
(B) is a diagram in which a TEM photograph of a cross section of the toner of Example 2 is printed and output.

FIG. 3A is a schematic diagram of a toner of Comparative Example 1. FIG. 3B is a diagram in which a TEM photograph of a cross section of the toner of Comparative Example 1 is printed and output.

FIG. 4A is a cross-sectional view of a toner of Comparative Example 2. FIG. 4B is a diagram in which a TEM photograph of a cross section of the toner of Comparative Example 2 is printed and output.

FIG. 5 is a schematic cross-sectional view of a toner of Comparative Example 3.

Claims (8)

[Claims] 1. A toner containing a binder resin having a glass transition temperature of at least 66 ° C. or less, and a carrier having a core material made of a magnetic material and a coating layer made of a soft segment and a hard segment provided on a surface of the core material. A two-component developer, characterized in that: 2. The glass transition temperature of the binder resin is 57 to
The two-component developer according to claim 1, which is at 66 ° C. 3. The two-component developer according to claim 1, wherein the toner contains at least two kinds of binder resins, and they form a sea-island structure. 4. The two-component developer according to claim 3, wherein wax is included in a resin constituting an island of the binder resin of the toner. 5. The method according to claim 1, wherein the toner comprises two types of binder resins A and B.
The two-component developer according to any one of claims 1 to 4, wherein the two-component developer contains a wax and a wax, and their SP values satisfy the following relational expression. 0.8 ≦ | SP (B) −SP (wax) | <SP
(A) -SP (B) 6. The toner according to claim 1, wherein the toner comprises two types of binder resins A and B.
And the weight ratio (A / B) of the binder resin A and the binder resin B is 1 to 50, and the weight ratio (B / wax) of the binder resin B and the wax is The two-component developer according to any one of claims 1 to 5, wherein the number is 1 to 50. 7. The two-component developer according to claim 1, wherein the toner contains a wax, and the maximum dispersion diameter of the wax is 1 μm or more. 8. The two-component developer according to claim 1, wherein the toner contains a wax, and the melting point of the wax is 75 ° C. or higher.