JPH11305489A - Toner for developing electrostatic charge image and two-component developer using the toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner whose rise in electrification is quick and whose lowering of the electrification amount of developer with the lapse of time is restrained by specifying the relation of the storage elastic modulus of binder resin and charge control resin. SOLUTION: The storage elastic modulus G' of the binder resin and the charge control agent consisting of resin having an electrifiable functional group at 150 deg.C satisfies relation expressed by an expression; Log10 (G'B)-Log(G'C)>=0.5. In the expression, G'B and G'C respectively mean the storage elastic modulus of the binder resin and the charge control agent at 150 deg.C. When the loss elastic modulus G'' of the binder resin and the change control agent consisting of the resin having the electrifiable functional group at 150 deg.C satisfies relation expressed by an expression; |Log10 (G''B)-Log(G''C)|<=0.5, the toner which has sufficient electrification amount, whose electrification amount distribution is sharp and by which fogging at the time of consecutive copying is reduced is obtained. In the expression, G''B and G''C respectively mean the loss elastic modulus of the binder resin and the charge control agent at 150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image used in electrophotography, electrostatic printing, and the like, and a two-component developer for developing an electrostatic image using the toner.

[0002]

2. Description of the Related Art Conventionally, a method of developing an electrostatic image using toner as disclosed in Japanese Patent Application Laid-Open No. 61-147261 is roughly classified into a so-called two-component method in which a toner and a carrier are mixed. There are a method using a developer and a method using a one-component developer that is used alone without being mixed with a carrier.

[0003] The two-component developer charges the toner and the carrier with different polarities by stirring and friction, and the charged toner makes an electrostatic image having the opposite polarity visible by the charged toner. Depending on the type of carrier, there are a magnet brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method, and the like.

As the toner, a fine powder in which a coloring agent such as carbon black is dispersed in a binder resin made of a natural resin or a synthetic resin is used. For example, a dispersion of a colorant in a binder resin such as polystyrene
Particles pulverized to about 30 μm are used as toner. Further, those in which a magnetic material such as magnetite is further added to these components are used as a magnetic toner. The toner carries positive or negative charge depending on the polarity of the electrostatic charge image to be developed. In order to retain the electric charge in the toner, it is possible to use the frictional charging property of the resin which is a component of the toner.However, in this method, since the charging property of the toner is small, an image obtained by development is easily fogged and unclear. It will be. Therefore, in order to impart a desired triboelectric charging property to the toner, a dye, a pigment, or a charge control agent that imparts charging property is added. In the case of a one-component developer, it is necessary to quickly reach a desired charge amount by contact with a member such as a blade, and in particular, in the case of a two-component developer, the toner in the developer is consumed and newly The replenished toner needs to quickly reach a desired charge amount due to frictional charging with the carrier.

Hitherto, examples of positive charge control agents include nigrosine, fatty acid-modified nigrosine, amines, ammonium compounds, phosphonium compounds, and pyridinium compounds. Examples of negative charge control agents include Co, Ni, Cr, and Ni.
There are metal complexes such as Zn and Fe, metal salts, sulfonated copper phthalocyanine pigments, and the like, but these compounds have complicated structures, inconsistent properties, and poor stability. Furthermore, it is easily decomposed or deteriorated due to decomposition, mechanical shock, friction, changes in temperature and humidity conditions during heat kneading, and the phenomenon that charge controllability is likely to be reduced. Furthermore, there are many materials whose chargeability changes depending on the environment. In addition, the above-mentioned metal complexes and metal salts include:
Some contain harmful heavy metals, and if disposed of, there is a concern about the impact on the environment. Charge control agents that do not contain harmful heavy metals include Fe complexes of monoazo dyes,
Although there are Fe and Al complexes of salicylic acid, it is hard to say that these charge control agents have sufficient charge controllability.

When these charge control agents are used in a one-component developer, there is a problem that a charge imparting member such as a blade is contaminated with the charge control agent, so that a desired charge amount cannot be obtained. When the charge control agent is used in the toner for a two-component developer, the charge control agent is insoluble in the binder resin, so the mechanical control moves from the toner surface to the carrier surface, and the carrier in the developer is contaminated. There is a problem that the charge amount of the developer is reduced.

As charge control agents having relatively good compatibility with the binder resin and less polluting the carrier, JP-A-6-43685 and JP-A-63-18476 disclose a charge control agent.
No. 2, JP-A-63-60458, resin charge control agents in which a chargeable functional group is added to a silicone resin skeleton or a styrene / acrylic resin skeleton, so-called charge control resins. I have. One of the problems of these charge control resins is that a sufficient amount of charge cannot be obtained, or even if obtained, the charge rising characteristics are poor, or part of the charge control resin detached from the toner surface over time is contained in the developer. And the charge amount of the developer is reduced.

[0008] In a two-component dry developer, fine toner particles are held on a relatively large particle surface by an electric force generated by friction between the two particles. The attraction force in the latent image direction on the toner particles due to the electric field formed overcomes the bonding force between the toner particles and the carrier particles, and the toner particles are attracted and adhered on the electrostatic latent image to visualize the electrostatic latent image. Things. And
Since the developer is repeatedly used while replenishing the toner consumed by the development, the carrier must always triboelectrically charge the toner particles to a desired polarity and to a sufficient charge amount during a long-term use. However, in the conventional developer, a toner film is formed on the carrier surface by mechanical collision such as collision between particles, or collision of particles with a developing machine, or heat generated by these actions, so-called spent is caused, and carrier Of the developer decreases with use time, and it is necessary to replace the entire developer.

In order to prevent such spent,
Conventionally, methods for coating the carrier surface with various resins have been proposed, but no satisfactory method has yet been obtained. For example, a carrier coated with a resin such as a styrene-methacrylate copolymer or a styrene polymer has excellent charging characteristics, but has a relatively high critical surface tension of the surface, and also causes spent during repeated copying. The life as a developer was not so long.

On the other hand, a carrier coated with a silicone resin having a low surface tension has been proposed. However, since the silicone resin has low mechanical strength, for example, strong stirring such as in a high-speed copying machine, or the inside of a developing unit is not performed. If the carrier particles collide with the inner wall of the developing unit or the surface of the photoreceptor, or collide with each other due to long-term stirring in the silicone resin coating layer, the silicone resin coating layer wears and separates over time, and the triboelectric charge is applied to the toner and silicone. Since the charge between the resins changes to the charge between the toner and the carrier core particles, there has been a problem that the charge amount of the developer cannot be kept constant and the image quality deteriorates. In addition, when the carrier particles are coated with a silicone resin, the electrical resistance of the silicone resin itself is high, so that when used as a developer, there is a disadvantage that the image quality is inferior due to an edge phenomenon or a charge accumulation phenomenon.

[0011] The disadvantages of such coated carriers can be ameliorated by dispersing a conductive substance in the coating layer. That is, when a certain degree of conductivity is imparted to the carrier, the carrier acts as a developing electrode, and the developing is performed in a state where the developing electrode and the surface of the photoreceptor to be developed are in close contact with each other. Even a large area black part is faithfully reproduced as the original.

Conventionally, carbon, tin oxide and the like have been used as such a conductive material. However, when such a conductive material is dispersed in a coating layer of a carrier, the following defects occur. . Generally, the toner and the carrier are charged when they come into contact with each other. In this case, when the electric resistance of the carrier decreases, the charge generated in the toner is attenuated through the carrier, and the charge amount cannot be maintained. Also,
There has been a problem that the conductive material is separated from the coating layer due to use over time, and the charge amount is changed. In order to solve this problem, Japanese Patent Application Laid-Open No. 62-182759 discloses that carbon is improved by treating it with aminosilane, amino-modified silicone oil, or the like. It was a problem.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances of the prior art, and its object is to provide a good charge rising property, and to prevent background contamination and toner scattering even during continuous use. Another object of the present invention is to provide a two-component developer which has stable triboelectricity and can provide an image having high fidelity equivalent to the initial image even after use over time.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies, and as a result, have found that a binder resin and a charge control resin of 150 or less can be used.
It has been found that when there is a certain difference in the storage elastic modulus at ° C., a toner can be obtained in which the rise of charge is fast and the amount of charge of the developer is small with time. This is because when the compatibility between the binder resin and the charge control resin is inferior, the charge control agent disperses in a sea-island structure, whereas the storage elastic modulus of the two during melt-kneading has a certain difference. If the elasticity of the resin is high, it is considered that a strong kneading shear acts on the island structure of the charge control resin, and the charge control resin is more uniformly dispersed. More specifically, the above relationship is expressed as follows. The storage elastic modulus G ′ at 150 ° C. of the binder resin and the charge control agent composed of a resin having a chargeable functional group satisfies the following expression (1).

Log ₁₀ (G ′ _B ) −Log ₁₀ (G ′ _C ) ≧ 0.5 (1) (where, G ′ _B : storage elastic modulus of the binder resin at 150 ° C. G ′ _C : 150 ° C.) Represents the storage elastic modulus of the charge control agent at.

Next, the present inventors have conducted intensive studies and found that when the difference between the loss elastic modulus at 150 ° C. of the binder resin and the charge control resin is small, the binder resin has a sufficient charge amount,
It has been found that a toner having a sharp charge distribution and low fog during continuous copying can be obtained. This is presumably because, when there is a difference in viscosity between the binder resin and the charge control agent during melt-kneading, uniform dispersion of both is impeded.
More specifically, the above relationship is expressed as follows. The loss elastic modulus G ″ at 150 ° C. of the binder resin and the charge control agent composed of a resin having a chargeable functional group satisfies the following relational expression.

| Log ₁₀ (G ″ _B ) −Log ₁₀ (G ″ _C ) | ≦ 0.5 (2) (where, G ″ _B : loss modulus of elasticity of binder resin at 150 ° C. G ″ _C : Represents the loss modulus of the charge control agent at 150 ° C.)

Further, the present inventors have found that the storage elastic modulus G ′ and the loss elastic modulus G ″ at 150 ° C. of the binder resin and the charge control resin simultaneously satisfy the following equations (1) and (2). It has been found that a toner having a very good rise of charging and having a very small decrease in the amount of charge of the developer over time can be obtained.

## EQU1 ## Log ₁₀ (G ′ _B ) −Log ₁₀ (G ′ _C ) ≧ 0.5 (1)

| Log ₁₀ (G ″ _B ) −Log ₁₀ (G ″ _C ) | ≦ 0.5 (2) (where G ′ _B , G ′ _C , G ″ _B and G ″ _C are the same as above) This means that the charge control resin is finely dispersed and has excellent compatibility with the binder resin, so that not only a sufficient charge amount can be obtained at the initial stage, but also the detachment from the toner surface hardly occurs. It is thought to be.

Further, when the chargeable functional group of the charge control resin is a monomer unit represented by the following general formula (I):
Good positively chargeable toner can be obtained.

Embedded image

Further, when the chargeable functional group of the charge control resin is a monomer unit represented by the following formula (II), a good negative chargeable toner can be obtained.

Embedded image

Further, the toner comprises the carrier and the toner.
By using a component developer, a two-component developer for electrophotography can be obtained in which the rise of charging is extremely good and the amount of charge with time is extremely small.

Further, the toner comprises the carrier and the toner.
In the component developer, the carrier has a silicone resin coating layer, and the silicone resin coating layer of the carrier contains a conductive fine powder and a silane coupling agent, thereby providing durability, edge phenomena and the like. A two-component developer for electrophotography can be obtained which does not deteriorate image quality due to the charge accumulation phenomenon and exhibits stable triboelectric charging even when used over time. Further, the present invention maintains the advantages of the conventional silicone resin-coated carrier by coating the surface of the core particles with a silicone resin containing a conductive fine powder and a silane coupling agent, so that the carrier can be used as a carrier. By imparting conductivity, the charge accumulation phenomenon in the carrier, the peeling of the coating layer, and the desorption of the conductive fine powder are effectively suppressed.

Incidentally, the storage elastic modulus of the resin in the present invention,
The loss modulus is DYNAMIC S manufactured by Rheometrics.
Using SPECTROMETER RDS-7700,
The sample was heated at 200 ° C, the frequency was 100 rad / sec and the strain was
% For 10 minutes, then gradually lower the temperature to 8%.
The storage elastic modulus and the loss elastic modulus at 150 ° C. were obtained by measuring up to 0 ° C.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As the binder resin used in the present invention, first, a polyester resin is exemplified. As the polyester resin, all known polyesters obtained by condensation polymerization of an alcohol and a carboxylic acid can be used. For example, alcohols include polyethylene glycol, diethylene glycol, triethylene glycol,
Diols such as 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol, neopentyl glycol, 1,4-butenediol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, Etherified bisphenols such as hydrogenated bisphenol A, polyoxyethylenated bisphenol A, and polyoxypropylene bisphenol A, and dihydric alcohol monomers obtained by substituting these with a saturated or unsaturated hydrocarbon group having 3 to 22 carbon atoms Body, other dihydric alcohol monomers, sorbitol, 1,2,2
3,6-hexanetetrol, 1,4-sarbitan, pentaesritol, dipentaesritol, tripetaesritol, sucrose, 1,2,4-butanetriol,
1,2,5-pentanetriol, glycerol, 2-
Methylpropanetriol, 2-methyl-1,2,4-
Examples thereof include trihydric or higher polyhydric alcohol monomers such as butanetriol, trimethylolethane, trimetalolpropane, and 1,3,5-trihydroxymethylbenzene. Examples of the carboxylic acid used to obtain the polyester resin include, for example, monocarboxylic acids such as palmitic acid, stearic acid, and oleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, and phthalic acid. , Isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, which have 3 to 22 carbon atoms.
Divalent organic acid monomers substituted with saturated or unsaturated hydrocarbon groups, anhydrides of these acids, dimers of lower alkyl esters and linoleic acid, other divalent organic acid monomers, 1,2,4-benzenetricarboxylic acid, 1,2,5
-Benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,
2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8- Octanetetracarboxylic acid embol trimer acid, trivalent or higher polyvalent carboxylic acid monomers such as anhydrides of these acids can be cited, in particular, polyesters having excellent low-temperature fixability and hot offset resistance. As the resin, the main component is a polyester resin containing (a) a polycarboxylic acid component and (b) a polyol component as constituent units, and (b) at least a part of the polyol component is an oxyalkylene ether of a novolak-type phenol resin (b1) The polyester which is is mentioned.

The binder resins other than polyester used in the present invention include polystyrene and poly-p.
A homopolymer of styrene such as chlorostyrene and polyvinyltoluene and a substituted product thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , Styrene-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 ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile- Styrene-based copolymers such as indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyurethane Emissions, polyamide, epoxy resin,
Polyvinyl butyral, polyacrylic acid resin, rosin,
Modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, 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:
95-70), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer) Coalesce, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone resin and the like, and these can be used alone or as a mixture.

Examples of the charge control resin in the present invention include resins having a chargeable functional group such as a carboxyl group, a phenolic hydroxyl group, a naphthol hydroxyl group, a sulfonic acid group, an amino group, and a quaternary ammonium salt. When a resin containing a monomer unit represented by the general formula (I) is used in a positively chargeable toner, charge controllability is good. When a resin containing the monomer unit represented by the general formula (II) is used in a negatively chargeable toner, charge controllability is good.

The amount of the charge control resin used in the present invention is determined by the type of the binder resin, the presence or absence of additives used as required, and the toner production method including the dispersion method. Although not particularly limited, 0.1 parts by weight with respect to 100 parts by weight of the binder resin.
It is used in the range of 10 to 10 parts by weight. Preferably, 1 to 5
The range of parts by weight is good. If the amount is less than 0.1 part by weight, the charge rising property is insufficient, which is not practical. If the amount exceeds 10 parts by weight, the chargeability of the toner is too large, and the electrostatic attraction with the carrier is increased, so that the fluidity of the developer is reduced, the image density is reduced, or the toner is fixed. Inhibits properties.

The coloring agents used in the present invention include carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6
G, lake, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye, disazo dye, pigment, etc. obtain.

The toner of the present invention further contains a magnetic material and can be used as a magnetic toner. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, and aluminum, cobalt, copper, lead, magnesium, tin, and zinc of these metals. , Antimony, beryllium, bismuth, cadmium, calcium,
Examples include alloys of metals such as manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.
These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 μm, and are contained in the toner in an amount of about 20 to 200 parts by weight, particularly preferably 100 to 100 parts by weight of the resin component. It is 40 to 150 parts by weight based on parts by weight.

Further, the toner of the present invention may optionally contain additives. Examples of the additive include a lubricant such as tetrafluoroethylene resin and zinc stearate or an abrasive such as cerium oxide and silicon carbide; or a fluidity imparting agent such as colloidal silica and aluminum oxide; a caking inhibitor; or a carbonaceous agent. Examples include a conductivity-imparting agent such as black and tin oxide, and a fixing aid such as low-molecular-weight polyolefin.

In the present invention, the carrier core particles coated with the silicone resin may be those conventionally known, for example, ferromagnetic metals such as iron, cobalt and nickel;
Alloys and compounds such as magnetite, hematite, and ferrite; glass beads; The average particle diameter of these core particles is usually 10 to 1000 μm, preferably 30 to 1000 μm.
It is 500 μm. The amount of the silicone resin used is usually 1 to 10% by weight based on the carrier core particles.

The silicone resin used in the present invention may be any conventionally known silicone resin. For example, KR261, KR275, KR280, KR2 manufactured by Shin-Etsu Silicone Co., Ltd. which are commercially available.
82, KR285, KR251, KR155, KR22
0, KR201, KR204, KR206, SA-4,
ES1001, ES1001N, ES1002T, KR
3093 or SR2 manufactured by Toray Dow Corning Silicone
100, SR2101, SR2107, SR2110,
SR2108, SR2109, SR2115, SR24
00, SR2410, SR2411, SH805, SH
806A, SH804 and the like are used.

As a method for forming the silicone resin layer, the silicone resin may be applied to the surface of the carrier core particles by a spraying method, an immersion method, or the like, as in the prior art. The coating layer composition is prepared by adding a conductive fine powder and a silane coupling agent to a silicone resin solution and dispersing the mixture with an appropriate mixer. The conductive fine powder dispersed in the coating layer is 0.0%
It is preferable that the particles have a particle size of about 1 to 5.0 μm, and it is preferable to add 0.01 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the silicone resin. As the conductive fine powder, conventionally known carbon black may be used, and examples thereof include contact black, furnace black, and thermal black.

The silane coupling agent is a compound represented by the formula X-Si (OR) ₃ , where X is a functional group that reacts with organic substances, and R is a hydrolyzable group. As the carrier for a negatively chargeable toner, an aminosilane coupling agent having an amino group is particularly desirable. These silane coupling agents are used in an amount of 0.1 to 100 parts by weight of the silicone resin.
It is preferable to add 1 to 10 parts by weight, preferably 0.2 to 5 parts by weight. Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-
Aminoethyl) aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride and the like.

The storage elastic modulus and the loss elastic modulus of the binder resin and the charge control resin in the present invention are determined by the polymerization conditions of the resin,
Although it can be easily controlled by the monomer composition and the like, there is no general rule common to all resins, and it is desirable to adjust appropriately.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In addition, all the parts shown below are based on weight.

<Production of Polyester Resin> Polyester Resin A Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 700 g fumaric acid 130 g n-dodecenyl succinic anhydride 53.4 g hydroquinone 0.1 g The above was placed in a glass flask, heated to 230 ° C. in a mantle heater, and reacted while stirring in a nitrogen stream. Further, 63.5 g of trimellitic anhydride was added to about 8.
The reaction was allowed to proceed for 5 hours, and when the acid value reached 4.0, the reaction was terminated to obtain a polyester resin A having a softening point of 118 ° C.
When the storage elastic modulus G ′ and the loss elastic modulus G ″ of the resin at 150 ° C. were measured, Log ₁₀ (G ′ _B ) = 4.6.
Log ₁₀ (G ″ _B ) = 4.7.

Polyester Resin B Polyoxypropylene (2) -2,2-bis (hydroxyphenyl) propane 650 g Fumaric acid 120 g Isodocenyl succinic anhydride 53.4 g The above was reacted at 220 ° C. in the same manner as polyester A.
Further, 79.0 g of trimellitic anhydride was added and reacted at 200 ° C. to obtain a polyester resin B having a softening point of 119 ° C. When the storage elastic modulus G ′ and the loss elastic modulus G ″ of this resin at 150 ° C. were measured, Log ₁₀ (G ′ _B ) = 4.
8, Log ₁₀ (G ″ _B ) = 4.0.

Polyester resin C Polyoxypropylene (3,1) -2,2-bis (4-hydroxyphenyl) propane 940 g Polyoxyalkylene ether of novolak phenol 60 g Terephthalic acid 376 g Dibutyltin oxide 0.3 g or more is polyester A The reaction was carried out at 230 ° C. in the same manner as in the above to obtain a polyester resin C having a softening point of 115 ° C. When the storage elastic modulus G ′ and the loss elastic modulus G ″ of this resin at 150 ° C. were measured, Log ₁₀ (G ′ _B ) = 4.8, and Log ₁₀ (G ′ _B ) = 4.8.
₁₀ (G ″ _B ) = 4.2.

Polyester resin D Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 600 g Polyoxyalkylene ether of novolak phenol 400 g Isophthalic acid 392 g Dibutyltin oxide 0.3 g The reaction was carried out at 230 ° C. in the same manner as in the above to obtain a polyester resin D having a softening point of 120 ° C. When the storage elastic modulus G ′ and the loss elastic modulus G ″ of this resin at 150 ° C. were measured, Log ₁₀ (G ′ _B ) = 4.7, and Log ₁₀ (G ′ _B ) = 4.7.
₁₀ (G ″ _B ) = 3.8.

<Production of Charge Control Agent> Charge control agents A-1 to A-1
No. 3 was prepared by bonding a monomer unit having a chargeable functional group to an organopolysiloxane resin polymerized by a known method.

Charge control agent A-1 N- (2-aminoethyl) -3 obtained by allowing an organopolysiloxane resin and N- (2-aminoethyl) -3-aminopropyldimethoxysilane to react by heating under reflux.
An aminopropyl group-bonded organopolysiloxane resin.
The storage elastic modulus G ′ of this charge control resin at 150 ° C.,
When the loss modulus G ″ was measured, Log ₁₀ (G ′ _C ) =
4.0, Log ₁₀ (G ″ _C ) = 4.0.

Charge control agent A-2 8-phenyl-4, obtained in the same manner as charge control agent A-1
7-diazaoctyl group-bonded organopolysiloxane resin. Log ₁₀ (G ′ _C ) = 4.6, Log ₁₀ (G ″ _C ) = 4.
3

Charge control agent A-3 A 3-chloropropyl group-bonded organopolysiloxane resin obtained in the same manner as charge control agent A-1. Log ₁₀ (G ' _C )
= 3.7, Log ₁₀ (G ″ _C ) = 3.8

Charge control agent B-1 95 parts of styrene 5 parts of t-butyl methacrylate 5 parts of methacryloyloxyethyl (diethyl) (methyl) ammonium paratoluenesulfonate 5 parts Copolymer having a weight average molecular weight of 8,000 constituted as above Coalescing. Log ₁₀ (G ′ _C ) = 4.0, Log ₁₀ (G ″ _C ) = 4.0

Charge control agent B-2 95 parts of styrene 5 parts of methyl methacrylate 5 parts of methacryloyloxyethyl (diethyl) (methyl) ammonium paratoluenesulfonate 5 parts Copolymer having a weight average molecular weight of 8,500 constituted as described above. Log ₁₀ (G ′ _C ) = 4.3, Log ₁₀ (G ″ _C ) = 4.4

Charge Control Agent B-3 90 parts of styrene 10 parts of methacryloyloxyethyl (diethyl) (methyl) ammonium paratoluenesulfonate 10 parts of the above copolymer having a weight average molecular weight of 9,300. Log ₁₀ (G ′ _C ) = 4.6, Log ₁₀ (G ″ _C ) = 4.1

Charge control agent B-4 90 parts of styrene Methacryloyloxyethyl (diethyl) (methyl) ammonium paratoluenesulfonate 10 parts Copolymer composed of the above and having a weight average molecular weight of 7,600. Log ₁₀ (G ′ _C ) = 4.7, Log ₁₀ (G ″ _C ) = 4.4

Charge control agent B-5 95 parts of styrene 5 parts of t-BMA 5 parts of 2-acrylamido-3-methylpropanesulfonic acid A copolymer composed of the above and having a weight average molecular weight of 8,000. Log ₁₀ (G ′ _C ) = 3.6, Log ₁₀ (G ″ _C ) = 4.3

<Manufacture of Carrier> An example of manufacturing a carrier having several silicone resins in the coating layer will be described below.
These can be performed by known means.

Carrier A Composition of coating layer forming liquid Silicone resin (KR206: manufactured by Shin-Etsu Silicone Co., Ltd.) 100 parts Carbon black (# 44: manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 3.5 parts The above formulation was dispersed with a homomixer for 30 minutes. A coating layer forming liquid was prepared. The coating layer forming liquid was prepared by adding an average particle diameter of 100 μm.
A coating layer was formed on the surface of 1,000 parts of the spherical ferrite of m using a fluidized bed type coating apparatus to obtain a carrier A.

Carriers B to D Each of the following components and 100 parts of toluene were mixed and dispersed with a homomixer for 30 minutes to prepare a coating layer forming liquid.

Carrier B Silicone resin (SR2400: Toray Dow Corning Silicone Co., Ltd.) 100 parts Carbon black (Ketjen Black: Lion Akzo Co., Ltd.) 1.5 parts γ-chloropropyltrimethoxysilane (SZ6083: Toray Dow Corning Silicone Co., Ltd.) 0.3 parts

Carrier C Silicone resin (KR206: manufactured by Shin-Etsu Silicone Co., Ltd.) 100 parts Carbon black (# 44: manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 1 part γ-chloropropyltrimethoxysilane (SZ6083: manufactured by Toray Dow Corning Silicone Co., Ltd.) 3 copies

Carrier D Silicone resin (KR206: manufactured by Shin-Etsu Silicone Co., Ltd.) 100 parts Carbon black (# 44: manufactured by Mitsubishi Kasei Kogyo Co., Ltd.) 1.5 parts γ- (2-aminoethyl) aminopropylmethyl dimethoxysilane (SH6020: Toray) 0.4 parts by Dow Corning Silicone

Using the coating layer forming solution, a coating layer was formed on the surface of 1000 parts of spherical ferrite having an average particle diameter of 70 μm using a fluidized bed type coating apparatus, and carriers B, C and D were obtained.

A toner was prepared using the obtained polyester resin and charge control agent, and a two-component developer was prepared using the obtained carrier, and the following items were evaluated. Image test (fog) Developer life

<Image test> The occurrence of fog was evaluated by visual observation of the worst sample among 100 sheets during continuous copying.

<Developer Life> The image density of the copy image is, on average, 10 images before and after the image density of the original image of 1.2.
The life of the developer was defined as the time when the value was reduced to 1.0 or less.

Example 1 100 parts of a polyester resin A 10 parts of a carbon black 10 parts of a charge control resin A-1 1 part of a mixture of the above composition was sufficiently stirred and mixed in a Henschel mixer, and then roll-milled at a temperature of 130 to 140 ° C. to about 3 parts.
After heating and melting for 0 minutes and cooling to room temperature, the obtained kneaded material was pulverized and classified to obtain a black toner A having a particle size of 5 to 20 μm. Carrier A 97.5 for 2.5 parts of toner A
Parts were mixed by a ball mill to obtain a developer.

Next, the above-mentioned developer was used with Imagio FT6 manufactured by our company.
When the image was set at 500 and developed, a good image was obtained, and the image did not change even after 70,000 sheets of image were output. The life of the developer as defined above was 80,000. When the charge amount of the toner was measured by a blow-off method, the initial charge amount was −23.2 μC / g, and the charge amount of the toner after running 70,000 sheets was −21.1 μC.
C / g was little different from the initial value. Also, there was no toner filming on the photoconductor.

Examples 2 to 14 and Comparative Examples 1 and 2 The developer compositions and physical properties of Examples 2 to 14 and Comparative Examples 1 and 2 tested in the same manner as in Example 1 are shown in Table 1, and the results are shown in Table 1. 2
Put together. The amounts of the binder resin, carbon black, and charge control resin used, and the toner preparation conditions were all the same.
Styrene / acrylic resin A used in Examples 13 and 14
And B have the following configuration. Styrene / acrylic resin A Styrene: 2-ethylhexyl acrylate (80:
20) Weight average molecular weight: 9,000 Styrene / acrylic resin B Styrene: 2-ethylhexyl acrylate (90:
10) Weight average molecular weight: 6,500

[0061]

[Table 1]

[0062]

[Table 2]

[0063]

According to the first aspect of the present invention, the charge control agent is a resin having a chargeable functional group, and the binder resin and the charge control resin have a storage elastic modulus at 150 ° C. of 0.5. Based on the above differences,
The toner has a fast charging rise and has a small decrease in the charge amount of the developer over time.

In the toner for developing an electrostatic image according to the second aspect, the charge control agent is a resin having a chargeable functional group, and the difference (absolute value) in the loss elastic modulus between the binder resin and the charge control resin at 150 ° C. Is 0.5 or less, the toner has a sufficient charge amount, has a sharp charge amount distribution, and has little fog during continuous copying.

According to a third aspect of the present invention, the charge control agent is a resin having a chargeable functional group, and the binder resin and the charge control resin have a storage elastic modulus at 150 ° C. of 0.5 or more. Since there is a difference and the difference (absolute value) of the loss elastic modulus at the same temperature is 0.5 or less,
The toner has a very good rise in charge and has a very small decrease in the charge amount of the developer over time.

The toner for developing an electrostatic charge image according to claim 4, wherein the chargeable functional group of the charge control resin further has the formula (I)
Since the monomer unit shown in (1) is used, a favorable positively chargeable toner can be obtained.

The toner for developing an electrostatic charge image according to claim 5, wherein the chargeable functional group of the charge control resin further comprises the general formula (II)
As a result, a favorable negatively chargeable toner can be obtained.

The two-component developer for developing an electrostatic image according to claim 6 is composed of the toner and the carrier, so that the two-component developer has a very good rise of charge and a very small decrease in the amount of charge with time. Agent.

In the two-component developer for developing an electrostatic charge image according to claim 7, the carrier has a silicone resin coating layer, and the silicone resin coating layer of the carrier contains conductive fine powder and a silane coupling agent. Therefore, the two-component developer is durable, has no deterioration in image quality due to an edge phenomenon or a charge accumulation phenomenon, and exhibits stable triboelectric charging even when used over time.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 9/10 362

Claims (7)

[Claims] 1. A toner mainly comprising a binder resin, a colorant and a charge control agent, wherein the charge control agent is a resin having a chargeable functional group, and the storage elasticity of the binder resin and the charge control agent at 150 ° C. The toner for developing an electrostatic image, wherein the ratio G ′ has a relationship represented by the following equation (1). Log ₁₀ (G ′ _B ) −Log ₁₀ (G ′ _C ) ≧ 0.5 (1) (where, G ′ _B : storage elastic modulus of the binder resin at 150 ° C. G ′ _C : 150 ° C.) Represents the storage elastic modulus of the charge control agent at. 2. A toner mainly comprising a binder resin, a colorant and a charge control agent, wherein the charge control agent is a resin having a chargeable functional group, and the binder resin and the charge control agent have a loss elasticity at 150 ° C. The toner for developing an electrostatic image, wherein the ratio G ″ has a relationship represented by the following formula (2): | Log ₁₀ (G ″ _B ) −Log ₁₀ (G ″ _C ) | ≦ 0. 5 (2) (wherein, G ″ _B : loss elastic modulus of the binder resin at 150 ° C. G ″ _C : loss elastic modulus of the charge control agent at 150 ° C.) 3. A toner mainly comprising a binder resin, a colorant and a charge control agent, wherein the charge control agent is a resin having a chargeable functional group, and the storage elasticity of the binder resin and the charge control agent at 150 ° C. The toner for developing an electrostatic image, wherein the modulus G ′ and the loss elastic modulus G ″ simultaneously satisfy the relations of the following formulas (1) and (2): Log ₁₀ (G ′ _B ) −Log ₁₀ (G ′ _C ) ≧ 0.5 (1) | Log ₁₀ (G ″ _B ) −Log ₁₀ (G ″ _C ) | ≦ 0.5 (2) (where G ′ _B and G ′ _C , G ″ _B and G ″ _C represent the same elastic modulus as described above.) 4. An electrostatic image developing toner, wherein the resin having a chargeable functional group according to claim 1 contains a monomer unit represented by the following general formula (I). Embedded image 5. An electrostatic image developing toner, wherein the resin having a chargeable functional group according to any one of claims 1 to 3 contains a monomer unit represented by the following general formula (II). Embedded image 6. A two-component developer for developing electrostatic images, comprising a carrier and the toner according to claim 1. Description: 7. The two-component developer according to claim 6, wherein
A two-component developer for electrostatic image development, wherein the carrier has a silicone resin coating layer, and the silicone resin coating layer contains a conductive fine powder and a silane coupling agent.