JPH10133422A - Electrostatic charge image developing toner and fixing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fixed image with excellent smoothness of the surface without applying a large amt. of oil, and to provide an electrostatic charge image developing toner having both of such a high strength that is not broken by the stress of stirring in a developing device and such a high hardness that does not generate embedding of an external additive, etc. SOLUTION: This electrostatic charge image developing toner consists of at least a resin and a coloring agent, and the resin consists of a vinyl polymer. The component of the resin soluble with tetrahydrofuran(THF) shows mol.wt. peaks in the region between >=5000 and <15000mol.wt. and in the region between >=30×10<4> and <40×10<4> mol.wt. The storage elastic modulus G'160 of the toner at 160 deg.C ranges 500 to 1200dyn/cm<2> , while the loss elastic modulus G"160 at 160 deg.C ranges 1500 to 30000dyn/cm<2> .

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 an image forming method such as electrophotography, electrostatic recording, electrostatic printing, and a fixing method by heating under pressure.

[0002]

2. Description of the Related Art Conventionally, in forming a full-color image,
Color reproducibility, glossiness, and light transmittance of an image (especially in the case of an image for an HP (overhead projector)) are required.

In order to improve these characteristics, it is necessary to minimize the internal stress and crack of the toner image after fixing, which is the final image, and to smooth the image surface in order to minimize irregular reflection inside and on the image. There is.

[0004] From such a viewpoint, since heat can be easily transmitted and heat fixing can be sufficiently performed, it is a type of pressure heat fixing using a soft roller which has a good follow-up property to unevenness due to toner on the surface of an unfixed image. A heat roller fusing process is preferred. On the other hand, the color toner used for full-color copying is required to have a smooth surface easily formed by heating under pressure during fixing, that is, to have low elasticity at the heating temperature. You.

However, a color toner having low elasticity at the melting temperature tends to cause hot offset, and thus has a problem that the temperature range in which fixation is possible is narrowed.
To cope with such a problem, in the related art, it is necessary to suppress the occurrence of hot offset by applying a large amount of oil on the fixing roller at the time of fixing the toner. In addition, a color toner having low elasticity at a heating temperature has a low molecular weight of a binder resin constituting the color toner, and does not have sufficient mechanical strength as toner particles.

For example, Japanese Patent Application Laid-Open No. 2-135959 discloses a technique in which a styrene-acrylic resin having a low molecular weight and a low softening point is used as a binder resin. Such a resin is very brittle and has a low hardness. It is low. Therefore, when a color toner using such a binder resin is used, the toner particles are crushed by stirring in the developing device, and fine powder is easily generated. Further, the external additive particles are easily buried on the surface of the toner particles having low hardness.

[0007] The fine particles generated by the crushing and the toner particles in which the external additive particles are embedded have a large adhesive force to the carrier, so that the developability on the photoreceptor is reduced. Further, there is also a problem that the generated fine particles and the toner particles embedded with the external additive have a large adhesive force to the surface of the photoreceptor, thereby causing a decrease in transferability.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide:
An object is to provide a fixed image having excellent surface smoothness without applying a large amount of oil. It is another object of the present invention to provide a toner having high strength that is not crushed even by stress caused by stirring in a developing device and high hardness that does not cause burying of an external additive.

[0009]

The object of the present invention is attained by adopting one of the following constitutions.

(1) In a toner for developing an electrostatic charge image comprising at least a resin and a colorant, the resin comprises a vinyl polymer, and the molecular weight of a tetrahydrofuran (THF) -soluble component is 5,000 or more and 15,000 or more. Molecular weight range less than 1,000 and 3
A resin having a peak molecular weight in the molecular weight range of not less than 100,000 and less than 400,000, and having a storage elastic modulus G ′ ₁₆₀ at 160 ° C. of 500 to 1200 dyn / cm ² at 160 ° C.
Modulus of elasticity G ″ ₁₆₀ at 1500 to 3000 dy
n / cm ² , the toner for developing an electrostatic image.

(2) The area (SLp) of the low molecular weight component having a molecular weight of 0.150,000 or more and less than 80,000 and the molecular weight of 80,000 or more,
The ratio (SL) of the area (SHp) of the high molecular weight components of less than one million
(p / SHp) is 5 to 15 (1)
The toner for developing an electrostatic image according to the above.

(3) The toner according to (2), wherein the low molecular weight component of the polymer is an ionomer.

(4) The polymer according to (2) or (3), wherein the low molecular weight component is an ionomer and is a polymer having a structural unit obtained from a monomer represented by the general formula (a) and / or (b). An electrostatic image developing toner.

[0014]

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(In the general formula (a), R _{1 to} R ₈ represent a hydrogen atom,
A halogen atom, a substituted or unsubstituted alkyl group, cycloalkyl group, and aryl group each having 1 to 10 carbon atoms; R ₉ , R
₁₀ is a hydrogen atom, a chain or cyclic alkyl group having 1 to 6 carbon atoms. X represents a chain alkylene group having 1 to 6 carbon atoms, a polymethylene group, a chain or cyclic alkylidene group having 2 to 6 carbon atoms, or a simple bond. Y has 1 carbon atom each
A chain alkylene group, a polymethylene group, or a chain or cyclic alkylidene group having 2 to 10 carbon atoms, an aryl-substituted alkylidene group, a sulfonyl group, a sulfide group, -O-, or a mere bond. n is 1 to 5
Is the number of

In the general formula (b), R ₁₁ and R ₁₂ represent a hydrogen atom,
A chain or cyclic alkyl group having 1 to 6 carbon atoms. R ₁₃ ,
R ₁₄ represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group,
R ₁₃ and R ₁₄ may be the same or different. Further, R ₁₃ and R ₁₄ may be mutually bonded to form a ring. m is a number from 3 to 20. (5) A toner image developed and formed with the toner for developing an electrostatic image according to any one of (1) to (4) is fixed on a recording material by a pressure and heat fixing device. How to fix.

(6) In the fixing method using a pressure and heat fixing device, the toner has a storage elastic modulus G ' ₁₈₀ at 180 ° C. of 300 to 1000 dyn / cm ² and a loss elastic modulus G ″ _{180 at} 180 ° C. of 800 to 800. 2300 dyn /
cm ² , and the storage elastic modulus G ′ _{160 at} 160 ° C. is 5
00~1200dyn / cm ^2, 160 losses in ℃ modulus G _"160 is _{^{1500~3000dyn / cm 2, G '160}} >G' 180, G" fixing method according to claim _160> G "it is ₁₈₀ .

(7) The colorant is a yellow, magenta, cyan, or black colorant (1).
The toner for developing an electrostatic charge image according to any one of (1) to (4).

(8) The colorant is yellow, magenta, cyan, or black colorant (5).
Or the fixing method according to (6).

In the present invention, having a peak molecular weight is defined as gel permeation chromatography (GP).
In the chromatogram obtained by measuring the molecular weight on the horizontal axis and the number of molecules corresponding to each molecular weight component on the horizontal axis measured by C), it means that there is a molecular weight that clearly shows a peak-like maximum value.

In the measurement, a resin is dissolved in tetrahydrofuran (THF), and the soluble component is measured.

<GPC Measurement Method> The molecular weight distribution of the resin in the present invention refers to the tetrahydrofuran (TH
F) The soluble component is measured by the molecular weight distribution of a chromatogram by GPC using THF as a solvent, and is measured under the following conditions.

The measurement sample is prepared as follows.

A sample and tetrahydrofuran (THF) are mixed at a concentration of 0.5 to 5 mg / ml (for example, 5 mg / ml), left at room temperature for several hours (for example, 5 to 6 hours), and then shaken sufficiently. Mix with THF and mix until the sample no longer clumps, then at room temperature for more than 12 hours (for example,
Let stand for 24 hours). At this time, the time from the mixing of the sample and THF to the end of the standing is set to be 24 hours or more (for example, 24 to 30 hours).

Thereafter, a sample processing filter (pore size: 0.45 to 0.5 μm, for example, Mikuroridisk H-25-5 manufactured by Tosoh Corporation, Exiclodisk 25C)
R, which can be used as a GPC sample. The sample concentration is adjusted so that the toner component is 0.5 to 5 mg / ml.

In the GPC measuring apparatus, the column was stabilized in a heat chamber at 40 ° C., and THF was passed through the column at this temperature at a flow rate of 1 ml per minute as a solvent.
About 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number.

As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used.
It is appropriate to use about a few standard polystyrene samples. An RI (refractive index) detector is used as the detector. As the column, a combination of a plurality of commercially available polystyrene gel columns may be used. For example, a Showa Denko
x GPC KF-801, 802, 803, 804,
805, 806, 807, 800P, TSKgel G1000H (H _XL ), G2000
H (H _XL ), G3000H (H _XL ), G4000H (H
_{XL), G5000H (H XL)} , G6000H (H XL),
G7000H (H _XL ), TSK guardcolumn
n can be mentioned.

<Method of Measuring Viscoelasticity> The storage elastic modulus G ′ and the loss elastic modulus G ″ were measured using a rheometer “Solid meter: M
The value (dyne / cm ² ) measured by the cone plate method using “R-500 type” (manufactured by Nippon Rheology Co., Ltd.).
Shall be referred to. Here, as the measurement conditions, the cone angle was 2.0 deg, the cone diameter was 4.0 cm, and the frequency was 1.
0Hz, twist angle 0.5deg, gap length 50μ
m, the measurement start temperature was 100 ° C., and the heating rate was 3 ° C./min.

The storage elastic modulus at 160 ° C. of the toner is G ′ ₁₆₀ , and the loss elastic modulus at 160 ° C. is G ″ ₁₆₀ , 18
The storage elastic modulus at 0 ° C. is G ′ ₁₈₀ and the loss elastic modulus at 180 ° C. is G ″ ₁₈₀ .

In the present invention, the storage elastic modulus G ' _{160 at} 160 ° C. exceeds 1200 dyn / cm ^2, and the loss elastic modulus G ″ _{160 at} 160 ° C. becomes 3000.
If it exceeds dyn / cm ² , the smoothness of the image surface becomes insufficient,
A good image cannot be obtained due to insufficient glossiness of the image.

On the other hand, the storage elastic modulus G ′ ₁₆₀ of the toner at 160 ° C. is less than 500 dyn / cm ² ,
Elastic modulus G ″ ₁₆₀ at 1500 dyn / cm ²
If it is less than 1, the smoothness of the image surface is good, but the glossiness becomes strong due to excessive smoothness, making it difficult to view the image and easily causing problems such as offset. Further, the burial of the external additive is increased, and the durability is reduced.

In another embodiment of the present invention, a temperature of 180 ° C.
Storage modulus G ' ₁₆₀ of the toner at 1000 dyn
/ Cm ^2, and the loss modulus G ″ at 180 ° C.
_{If 160} exceeds 2300 dyn / cm ² , the wettability and adhesion to the transfer material will be low, and problems such as under-fixing will easily occur.

On the other hand, the storage elastic modulus G ′ ₁₈₀ of the toner at 180 ° C. is less than 300 dyn / cm ² ,
If the loss elastic modulus G ″ ₁₈₀ at is less than 800 dyn / cm ² , problems such as offset tend to occur similarly to the above.

Here, G ′ ₁₆₀ > G ′ ₁₈₀ , G ″
It is preferred that ₁₆₀ > G ″ ₁₈₀ to stabilize the gloss.

In the chromatogram of the toner resin measured by gel permeation chromatography (GPC), the area (SLp) of the low molecular weight component having a molecular weight of 0.150,000 to 80,000 and the area of the low molecular weight component having a molecular weight of 80,000 to 200,000 The ratio (SLp / SHp) of the area (SHp) of the high molecular weight component is 5 to 1
5 is desirable. In this case, SLp / SHp is 5
If it is less than the above range, it becomes difficult to obtain a glossy fixed image in the pressure and heat fixing range from the above range. Further, when SLp / SHp exceeds 15, it becomes difficult to maintain hot offset resistance better than the above range.

In the present invention, when the toner resin (binder resin) is a polymer having a low molecular weight component as an ionomer and having an ionic cross-linking structure and a covalent cross-linking structure, the toner particles have very toughness at room temperature. It will be excellent. Such toner particles are not crushed even by the stress caused by stirring in the developing device, and do not cause burying of the external additive and the like. Excellent transferability is stably exhibited over a long period of time.

Hereinafter, the present invention will be described specifically.

As described above, the binder resin constituting the toner of the present invention is preferably made of a polymer having an ionic crosslinked structure and / or a crosslinked structure.

<Monomer Component> Monomers used to obtain a polymer having such an ionic cross-linking structure and a covalent cross-linking structure include styrene monomers,
Examples thereof include (meth) acrylate monomers, half-ester compounds represented by the following formula 3, and compounds represented by the general formula (a) or (b).

[0040]

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[In the formula, R represents a hydrogen atom or a methyl group, and L represents a divalent linking group having an ester bond in the molecular chain and having 3 or more carbon atoms. As the styrene monomer, alkylstyrene such as styrene, methylstyrene and diethylstyrene, halogenated styrene such as chlorostyrene and the like can be used.

As the (meth) acrylic acid for obtaining the (meth) acrylic ester monomer, acrylic acid,
Methacrylic acid, α-ethylacrylic acid and the like can be used. As alcohols for obtaining (meth) acrylate monomers, alkyl alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol;
Alcohols having 1 to 4 carbon atoms, such as halogenated alkyl alcohols obtained by partially halogenating these alkyl alcohols, can be preferably used.

<Specific half-ester compound> The specific half-ester compound is a compound contained in the monomer component for introducing an ionic cross-linking structure into the polymer. This specific half-ester compound can be obtained by an esterification reaction of a derivative of a (meth) acrylic acid having a hydroxyl group with a dicarboxylic acid, and specifically, monomethacryloyloxyethyl succinate and monomethacryloyloxyethyl fumarate Esters and the like can be mentioned.

Although the introduction of an ionic crosslinked structure into a polymer can be carried out by a usual (meth) acrylic acid monomer, a polymer obtained by using a specific half-ester compound has a long side chain to be formed. Is preferred because the position of the carboxyl group moves away from the main chain and is less susceptible to steric hindrance in the chemical structure. Thereby, ionic crosslinking between the polymer and the polyvalent metal compound can be efficiently generated.

In order to introduce an ionic crosslinked structure, a polymer obtained from a monomer component containing a specific half-ester compound may be reacted with a polyvalent metal, and a coordination bond between a carboxyl group and a metal ion ( An ionic cross-linking structure is formed by ionic bonding. Examples of suitable polyvalent metal compounds include, for example, acetates and oxides of alkaline earth metals and zinc group metals.

The polymer into which the ionic cross-linking and covalent cross-linking structures have been introduced has reduced brittleness and exhibits toughness at room temperature. As a result, it is not crushed even by the stress caused by stirring in the developing device, and the external additive is not buried.

Next, specific examples of the compound represented by formula (a) or (b) will be given.

[0048]

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[0049]

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[0050]

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<Colorant> The colorant constituting the toner of the present invention is not particularly limited, and a commonly used dye or pigment can be used.

As the colorant for color, carbon black, magnetic substance, dye, pigment and the like can be used.

Examples of the black colorant include carbon black and magnetic substances. Examples of carbon black include channel black, furnace black, acetylene black, thermal black, lamp black and the like. As the magnetic material, ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, an alloy of a type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, or the like can be used.

Dyes that can be used as colorants for magenta include C.I. I. Solvent Red 1, 49, 52, 58, 63, 11
1, 122 and the like, and for yellow, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 10
3, 104, 112, and 162. For cyan, C.I. I. Solvent Blue 25, 36
60, 70, 93, 95 etc. can be used,
Also, a mixture of these can be used.

On the other hand, as pigments, C.I. I. Pigment Red 5, 48: 1, 53:
1, 57: 1, 122, 139, 144, 1
49, 166, 177, 178, 222, C.I.
I. Pigment Orange 31, 43 and the like. For yellow, C.I. I. Pigment Yellow 14, 1
7, 93, 94, 138 and the like. For cyan, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 60 and the like, and mixtures thereof can also be used. The number average primary particle size of these dyes and pigments varies depending on the type, but generally ranges from 10 to 10.
About 200 nm is preferable.

The amount of the coloring agent to be added is not particularly limited, as long as it is sufficient to form an image. Specifically, 1 to 1 by weight in the toner
0% is preferred.

When the color toner of the present invention is manufactured, a masterbatch in which a pigment is dispersed and contained at a high concentration in a part of the binder resin in advance by using a flushing process is prepared. Is preferably mixed with the remainder to produce a color toner.
The color toner manufactured in this manner is excellent in dispersibility of the colorant and wettability of the binder resin,
The coloring property can be improved, and the crush resistance and offset resistance of the toner can be further improved.

<Various Additives> The toner of the present invention may contain various internal additives such as a charge control agent and external additives as necessary. As the charge control agent, a conventionally known charge control agent can be used, but for the color toner particles, it is preferably colorless and white because it constitutes a part thereof. Specific examples of preferred charge control agents include zinc salts of salicylic acid derivatives.

As the external additives, generally used fine particles such as inorganic fine particles and organic fine particles, lubricants composed of fatty acids, fatty acid metal salts and the like can be used. In particular, by adding the fatty acid metal salt, the coefficient of friction between the toner particles and other substances is reduced, and as a result, the stress applied to the toner particles is reduced, so that the toner particles are crushed and the external additives are buried. This is preferable because it can be effectively prevented.

<Production Example / Particle Size Range> The method for producing the toner of the present invention is not particularly limited, and the toner can be produced by a conventionally known method. The particle size of the toner of the present invention is in the range of 1 to 30 μm, and from the viewpoint of improving the resolution and surface smoothness of the formed image, the volume average particle size is preferably in the range of 3 to 9 μm.

The toner of the present invention may be mixed with a carrier and used as a two-component developer, or may be used as a one-component developer composed of the toner alone. As such a carrier, a conventionally known carrier can be used, but by using a carrier having a low magnetization and a small specific gravity, the stress applied to the toner particles during mixing and stirring can be reduced.

Specifically, the magnetization is 15 to 40 emu /
g, a carrier having a specific gravity of ³ to 7 g / cm ³ can be preferably used. From the viewpoint of improving the durability of the carrier, a carrier in which a resin coating layer is provided on the surface of magnetic particles, or a carrier in which magnetic powder is dispersed in resin particles can be preferably used.

The toner of the present invention can be suitably used in a fixing process by pressure and heat fixing such as a heat roller. Here, the heat roller used in the fixing process has a surface layer that comes into contact with the surface of the unfixed image on the transfer material made of an elastic material, and the soft roller has a good followability to unevenness due to color toner on the surface of the unfixed image. Is preferable because the smoothness of the surface of the fixed image can be further improved.

The transfer material in the present invention can transfer an unfixed toner image formed on an electrostatic image carrier such as a photoreceptor, and can carry the transferred toner image as a final image by fixing. A thing. Most commonly, it is plain paper, but the above-mentioned transparent resin film for OHP or various papers, resin plates, etc. are of course included.

<Fixing Method> A preferable fixing method used in the present invention is, as a typical example, a heat roller fixing system, a fixedly installed heating element, and pressure contact with the heating element.
The toner image is pressed by a pressing member that rotates and presses a recording material (usually plain paper, but is not particularly limited as long as the toner image can be firmly supported by fixing) to the heating member via a film material. And a heat-fixing method for heating and fixing the toner onto a recording material.

Since the toner of the present invention is excellent in low-temperature fixing property, anti-offset property, and anti-filming property, if the toner of the present invention is used in the pressurizing and heating fixing method, the life of the heat roller fixing device or the fixing film is reduced. An image of excellent quality can be obtained over a long period without shortening.

FIG. 1 is an explanatory view showing one example of such a heat roller fixing system. In the figure, an upper roller 1 having a heat source inside a metal cylinder made of iron, aluminum, or the like having a surface coated with polytetrafluoroethylene or polytetrafluoroethylene-perfluoroalkylvinyl ether copolymer, and silicon rubber, are used. And the lower roller 2 formed. Specifically, it has a linear heater 3 as a heat source and heats the surface temperature of the upper roller 1 to about 100 to 200 ° C. In the fixing section, a pressure is applied between the upper roller 1 and the lower roller 2 to deform at least the lower roller 2 to form a so-called nip. The nip width is 1 to 10 mm, preferably 1.5 to 7 mm. Fixing linear velocity is 40-40
00 mm / sec is preferable. When the nip is narrow, heat cannot be uniformly applied to the toner, causing uneven fixing. On the other hand, if the nip width is wide, the melting of the resin is promoted, and a problem occurs in that the fixing offset becomes excessive.

FIG. 2 is an explanatory view of one example of the latter fixing method having a fixedly mounted heating element. In the figure, the low-heat-capacity line-state heating body 21 fixedly supported by the apparatus has a thickness of 0.2 to 5.0 mm, more preferably 0.5 to 3.5 mm, a width of 10 to 15 mm, and a longitudinal direction. A resistance material is applied to an alumina substrate having a length of 240 to 400 mm to a thickness of 1.0 to 2.5 mm, and electricity is supplied from both ends. The energization is performed by changing the pulse width according to the temperature and the energy release amount controlled by the temperature sensor using a pulse waveform of DC 100 V and a cycle of 25 msec. In the case of the temperature T1 detected by the temperature sensor in the low heat capacity linear heating element 21, the surface temperature T2 of the film material facing the resistance material is lower than T1. Here, T1
Is preferably 120 ° C. to 220 ° C., and the temperature of T2 is preferably 0.5 ° C. to 10 ° C. lower than the temperature of T1.
The film material surface temperature T3 at a portion where the film material is separated from the toner surface to be fixed is substantially equal to T2.

The fixing film 22 moves in the direction of the arrow in FIG. 2 in contact with the heating member whose energy and temperature have been controlled in this manner. The fixing film 22 is used as a heat-resistant film having a thickness of 10 to 35 μm, for example, polyester, polyperfluoroalkylvinyl ether, polyimide, polyetherimide and the like, and desirably a fluororesin such as polytetrafluoroethylene and a conductive material. Is an endless film coated with a release material layer having added thereto 5 to 15 μm. Generally, the total thickness is 10 to 100 μm,
The film material is transported in the direction of the arrow without wrinkles and twists by the drive and tension of the drive roller and the driven roller. The fixing linear velocity is preferably from 40 to 400 mm / sec.
The pressure roller 23 has a rubber elastic layer having a high releasability, such as silicon rubber, and presses against a heating body via a film material at a total pressure of 2 to 30 kg, and rotates under pressure.

FIG. 2 is an explanation using an endless sheet. As shown in FIG. 3, an end film 34 is wound around a sheet feed shaft 32 and a take-up shaft 33, and the film is gradually moved in the direction of an arrow every fixing. It may be moved to.
The recording material carrying the toner image is passed between the end film 34 and the pressure roller 35, and the toner image is melted and fixed to the recording material by passing through the heating element 31.

[0071]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the following, “parts” indicates “parts by weight”.

Example 1 Preparation of Polymer (Binder Resin) Toluene was placed in a separable flask equipped with a thermometer, a stirrer, a nitrogen gas inlet tube and a falling condenser, and nitrogen gas was introduced from the gas inlet tube. After that, the inside was kept under an inert atmosphere, and then heated in an oil bath to reach the reflux temperature of toluene.
Next, a solution in which styrene, methyl methacrylate and n-butyl acrylate had a molar ratio of 14: 1: 3 was reacted at a reflux temperature to obtain a high molecular weight polymer.

Next, styrene, methyl methacrylate, n-butyl acrylate, monomethacryloyloxyethyl succinate and the compound a-1 represented by the general formula (a) are placed in a flask having the high molecular weight polymer solution. , 135: 26: 19: 5: 2 (molar ratio), and the polymerization reaction was carried out while dropping. After dropping the solution, the reaction was further performed at a reflux temperature to obtain a low molecular weight polymer.

Next, zinc oxide was added to a flask having a solution comprising the high molecular weight polymer and the low molecular weight polymer, and a reaction was carried out with stirring at a reflux temperature.

After completion of the reaction, the toluene solvent was distilled off under reduced pressure to prepare a polymer resin having an ionic cross-linking structure and a covalent cross-linking structure preferably used in the present invention, in which a carboxyl group and a metal compound were reacted.

Preparation of Pigment Masterbatch A polymer resin having an ionic cross-linking structure and a covalent cross-linking structure prepared in the same manner as above and a magenta pigment “CI Pigment Red 122” in a weight ratio of 6 : 4 and a flushing treatment was performed to prepare a pigment master batch. This is referred to as “MB1”. Similarly, a pigment master batch was obtained in the same manner except that a yellow pigment “CI Pigment Yellow 17” was used. This is referred to as “MB2”. Further, a pigment master batch was obtained in the same manner except that "CI Pigment Blue 15: 3" was used as the pigment. This is "MB3"
And

Production of Toner 100 parts of the above-prepared polymer resin, 20 parts of the above-prepared pigment masterbatch, and 3 parts of zinc salt of 3,5-ditert-butylsalicylic acid were mixed with a Henschel mixer. Then, the mixture was melt-kneaded with a twin-screw extruder, cooled and solidified, and crushed, and thereafter, a volume average particle size of 8.5 μm was obtained by using a fine particle crusher of a particle collision type and an air classifier.
Colored particles were obtained. For 100 parts of the obtained colored particles, 0.5 part of hydrophobic silica "R-972" (manufactured by Nippon Aerosil Co., Ltd.) and 1.0 part of hydrophobic titania "T-805" (manufactured by Nippon Aerosil Co., Ltd.) Is added to the mixture, and the mixture is mixed using a Henschel mixer.
1 was produced.

<Examples 2 to 4> Polymers having an ionic cross-linking structure and a cross-linking structure were made to have a composition according to the formulation shown in Table 1 below. In T2 and T3, “MB2” and “MB3” were used. Carbon black was used as a coloring agent. In T2, the compound a- represented by the general formula (a)
A toner T2 of the present invention was produced in the same manner as in Example 1 except that No.2 was used. Further, in T3, a toner T3 of the present invention was produced in the same manner as in Example 1, except that the compound b-2 represented by the general formula (b) was used. Example 1 was repeated except that the compound b-7 represented by the general formula (b) was used in T4.
In the same manner as in the above, a toner T4 of the present invention was produced.

<Comparative Examples 1 to 4> The polymer and the polymerizable mixture used for preparing the pigment masterbatch had compositions according to the formulation shown in Table 1 below. Comparative toners H1 to H4 were produced in the same manner as in Example 1 except that “MB3” was used and carbon black was used as a coloring agent in H4.

[0080]

[Table 1]

St: styrene MMA: methyl methacrylate BA: butyl acrylate Ac-1: monomethacryloyloxyethyl succinate ZnO: zinc oxide

[0082]

[Table 2]

<Manufacture of Carrier> The volume average particle diameter was 45 μm.
m, on the surface of a Cu—Fe-based core particle having a specific gravity of 5.0, at a ratio of 2.0% by weight with respect to the core particle,
A resin-coated carrier composed of a styrene-methyl methacrylate resin (4/6 (molar ratio)) was formed to prepare a resin-coated carrier.

<Preparation of Developer> Each of the toners (T1 to T4 and H1 to H4) obtained in the above Examples and Comparative Examples and the above resin-coated carrier were adjusted to a toner concentration of 7%. By using a V-type mixer, developers 1 to 4 and comparative developers 1 to 4 were prepared.

<Evaluation of Developer> An image formation test and a mixing and stirring test of the developers were performed using the developers 1 to 4 and the comparative developers 1 to 4 obtained as described above, and the gloss (image quality) (Smoothness of surface), anti-offset performance, and toner particle size (crush resistance) were evaluated.

As for the glossiness and the anti-offset performance, the configuration of the fixing device was modified so that both upper and lower rollers had an LTV rubber layer.
ica-9028 "(manufactured by Konica Corporation) to form a fixed image.

The toner particle size was measured using a full-color copying machine “Konica-9028” (manufactured by Konica Corporation), which was modified so that the developing device could be driven alone. The mixture was stirred for 3 hours in an environment of a temperature of 40 ° C. and a relative humidity of 60%, and evaluated.

(Evaluation Items) Glossiness (Smoothness of Image Surface) The surface temperature of the fixing roller and the surface temperature of the pressure roller were set to 1
The temperature was set to 80 ° C., and the glossiness of the formed solid fixed image was measured according to JIS Z8741.

Anti-Offset Performance The surface temperatures of the fixing roller and the pressure roller were sequentially increased, and the temperature at which hot offset occurred was measured.

Toner Particle Size (Crush Resistance) The volume average particle size of the toner was measured before and after stirring in the developing device.

The results are shown in Table 3 below.

[0092]

[Table 3]

As understood from the results in Table 3, the toners T1 to T4 of the present invention produced according to Examples 1 to 4
Excellent in all of glossiness, anti-offset performance, and crush resistance, and a stable color-fixed image can be formed. On the other hand, the toners H1 to H
No. 4 cannot exhibit the above-mentioned performances in a well-balanced manner.

[0094]

According to the present invention, it is possible to provide a fixed image having excellent surface smoothness without applying a large amount of oil. Another advantage of the present invention is that it has a large strength that is not crushed even by the stress caused by stirring in the developing device,
An object of the present invention is to provide a toner having high hardness that does not cause burying of an external additive.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an example of a fixing method using a hot roll fixing method.

FIG. 2 is an explanatory view showing an example of a fixing method using a fixedly installed heating element (using an endless sheet).

FIG. 3 is an explanatory view showing an example of a fixing method using a fixedly installed heating element (using an edged film).

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Upper roller 2 Lower roller 3 Heater 21 Line-shaped heating body 22 Fixing film 23 Pressure roller 31 Heating body 32 Sending shaft 33 Winding shaft 34 Ended film 35 Pressure roller

Claims (8)

[Claims] 1. An electrostatic image developing toner comprising at least a resin and a colorant, wherein the resin comprises a vinyl polymer and the molecular weight of a tetrahydrofuran (THF) -soluble component is 5,000 or more and 15,000 or more. A resin having a peak molecular weight in a molecular weight range of less than 300,000 and a molecular weight range of 300,000 or more and less than 400,000, and a storage elastic modulus G ′ of the toner at 160 ° C.
₁₆₀ is 500 to 1200 dyn / cm ² , and the loss modulus G ″ at ₁₆₀ ° C. ₁₆₀ is 1500 to 3000 dyn / c
m ² , the toner for developing an electrostatic image. 2. The polymer of tetrahydrofuran (TH)
F) The ratio (SLp / S) of the area (SLp) of the low molecular weight component having a molecular weight of 0.150,000 or more and less than 80,000 and the area (SHp) of the high molecular weight component having a molecular weight of 80,000 or more and less than 1,000,000.
2. The electrostatic image developing toner according to claim 1, wherein Hp) is 5 to 15. 3. The toner according to claim 2, wherein the low molecular weight component of the polymer is an ionomer. 4. The electrostatic image according to claim 2, wherein the low molecular weight component is an ionomer and is a polymer having a structural unit obtained from a monomer represented by the general formula (a) and / or (b). Development toner. Embedded image (In the general formula (a), R _{1 to} R ₈ are a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, cycloalkyl group, or aryl group each having 1 to 10 carbon atoms. R ₉ and R ₁₀ are hydrogen atoms. A chain or cyclic alkyl group having 1 to 6 carbon atoms, X is a chain alkylene group having 1 to 6 carbon atoms, a polymethylene group,
Or a chain or cyclic alkylidene group having 2 to 6 carbon atoms, or a simple bond. Y is a chain alkylene group having 1 to 6 carbon atoms, a polymethylene group, or 2 carbon atoms;
To 10 chain or cyclic alkylidene groups, aryl-substituted alkylidene groups, sulfonyl groups, sulfide groups, -O
-Or just a bond. n is a number from 1 to 5. In the general formula (b), R ₁₁ and R ₁₂ each represent a hydrogen atom or a chain or cyclic alkyl group having 1 to 6 carbon atoms. R _13, R ₁₄ is a hydrogen atom, each substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, R _13, R
₁₄ may or may not be the same. Further, R ₁₃ and R ₁₄ may be mutually bonded to form a ring. m is a number from 3 to 20. ) 5. A toner image developed and formed with the toner for developing an electrostatic image according to claim 1, wherein the toner image is fixed on a recording material by a pressure and heat fixing device. Fixing method. 6. A fixing method using a pressure and heat fixing device, wherein a storage elastic modulus G ′ _{180 of the} toner at 180 ° C.
There 300~1000dyn / cm ^2, a loss at 180 ° C. modulus G _"180 is 800~2300dyn / cm ^2, 500~ storage modulus G _'160 at 160 ° C.
1200dyn / cm ^2, 160 losses in ℃ modulus G _"160 is 1500~3000dyn / cm ^2,
A fixing method, wherein G ′ ₁₆₀ > G ′ ₁₈₀ and G ″ ₁₆₀ > G ″ ₁₈₀ . 7. The colorant according to claim 1, wherein the colorant is a yellow, magenta, cyan, or black colorant.
The toner for developing an electrostatic charge image according to any one of claims 1 to 4. 8. The fixing method according to claim 5, wherein the colorant is a yellow, magenta, cyan, or black colorant.