JPH0844112A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To provide a toner excellent in low-temp. fixability, anti-offsetting property and image characteristics. CONSTITUTION:This toner contains at least a binding resin and wax and has at least one peak in each of a mol.wt. region (A) of <1X10<3> and the mol.wt. region (B) of 5X10<3>-1X10<5> in its mol.wt. distribution measured by the gel permeation chromatography of a THF(tetrahydrofuran)-soluble component. When the height of the max. peak in the region A and that in the region B are represented by HA and HB, respectively, the condition of 0.25<=HA/HB<1 is satisfied and a mol.wt. region of >=1X10<6> accounts for 6-30%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used for developing an electrostatic charge image in an image forming method such as an electrophotographic method or an electrostatic printing method. The present invention further provides a magnetic ink symbol identification (Magnetic).
Ink Character Recognitio
n) Toner for developing an electrostatic image suitable for printing magnetic characters used in a system.

[0002]

2. Description of the Related Art Conventionally, US Pat.
As described in Japanese Patent Publication No. 297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748, many methods are known, but generally, a photoconductive substance is used, An electric latent image is formed on the photoconductor by various means, the latent image is then developed with toner, and the toner image is transferred to a transfer material such as paper, if necessary, followed by heating, pressure or solvent. It is fixed by steam to obtain a copy.

Various methods and devices have been developed for the final step of fixing the toner image on a sheet such as paper. The most popular method at present is a pressure heating method using a heating roller.

In recent years, from the viewpoint of energy saving, a special film (for example, polyimide) fixing method has been developed and put into practical use in order to reduce power consumption in the fixing process.

On the other hand, the present situation is that various improvements have been made to toners from the above viewpoint.

[0006] For example, in Japanese Patent Laid-Open No. 5-6029, G
In the molecular weight distribution by PC, the region having a molecular weight of 5,000 or less is less than 15%, the region having a molecular weight of 5,000,000 or more is 5% or more, and the molecular weight is 5,000 to 100,0.
A toner is proposed which has a main peak in the region of 00 and has a weight average molecular weight of 5,000,000 or more. With this toner, it was possible to expand the high temperature side (high temperature offset) area in the fixing area, but it was still unsatisfactory to expand the fixing area to the low temperature side.

Further, in Japanese Patent Laid-Open No. 5-241370,
In the molecular weight distribution by GPC, the molecular weight is 2 × 10 ^3.
The region of 6 × 10 ⁴ and the molecular weight of 3 × 10 ⁵ to 2 × 10 ⁶
Has a peak in the region of and has a molecular weight of 2 × 10 ^{3 to} 6 × 10 ^4.
A resin having a shoulder in a region less than the peak of the above region has been proposed. When the resin is used as a toner, the resin may be fused by fusion of the toner to the photoreceptor in durability evaluation under high temperature and high humidity environment, or fusion of the resin in a device such as a crusher or a classifier during manufacturing. There is concern about adverse effects caused by low molecular weight components.

In order to overcome the above problems and make the toner suitable for the MICR system, the following problems must be taken into consideration.

First of all, the securities printed with MICR characters average about 10 on the MICR reader / sorter.
It is passed about once. It is rubbed against the magnetic head at high speed every time the paper is passed for magnetic reading. Therefore, in order to improve the recognition rate, it is necessary that the printing toner of MICR characters does not cause the printing to be faint (hereinafter referred to as smearing. The occurrence portion is shown in FIG. 1) due to rubbing.

The smearing is caused by the abrasion of the toner caused by the rubbing of the magnetic head and the toner on the paper, and the smearing of the toner on the magnetic head due to the softening of the surface layer of the toner due to the heat of the rubbing. In order to improve this phenomenon with toner, it is necessary to make the toner harder, improve the lubricity of the surface of the printed toner, and reduce the frictional force with the head.

Secondly, the separation of the toner from the paper due to the bending when securities are distributed between users and the separation of the toner from the paper due to the bending when passing through the leader / sorter. It is necessary to consider preventing the above from the viewpoint of ensuring reliability. To prevent this phenomenon, it is necessary to use a toner having good adhesion to paper.

Thirdly, in order to achieve a high recognition rate in printing MICR characters, it is necessary to use a toner containing a magnetic material having a remanent magnetization δr which is relatively larger than that of a generally used magnetic material. Inevitably, the residual magnetization of the toner also has to be increased, the developing ability of the toner is suppressed, and the image density tends to decrease. Therefore, it is necessary to consider measures for that.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image, which solves the above problems.

That is, the object of the present invention is to provide low-temperature fixability,
An object of the present invention is to provide a toner for developing an electrostatic image which is excellent in offset resistance and image characteristics.

A further object of the present invention is to provide a toner for developing an electrostatic charge image which does not cause toner fusion on the photosensitive drum even when it is durable in a high temperature and high humidity environment.

A further object of the present invention is to provide a toner for developing an electrostatic charge image, which has high image density and good adhesion to paper, and forms MICR characters which are difficult to separate from the paper.

A further object of the present invention is that smearing does not occur even when the paper is repeatedly passed through the MICR leader / sorter, the magnetic head of the leader / sorter is not contaminated, and the recognition rate of the leader / sorter is good. An object of the present invention is to provide a toner for developing an electrostatic charge image capable of forming MICR characters.

[0018]

The present invention achieves the above object by the following constitution. That is, the present invention provides a toner for developing an electrostatic charge image containing at least a binder resin and a wax, which includes tetrahydrofuran (TH
F) The molecular weight distribution measured by gel permeation chromatography (GPC) of the soluble component has a molecular weight of 1 × 10
There is at least one peak in the area A of less than ^{3 and} the area B of 5 × 10 ³ to 1 × 10 ⁵ , and the maximum peak height of the area A is H _A and the maximum peak height of the area B is H _B. In this case, the present invention relates to a toner for developing an electrostatic charge image, which satisfies the following condition 0.25 ≦ H _A / H _B <1, and the area of 1 × 10 ⁶ or more is 6 to 30%.

In the present invention, the molecular weight distributions of the toner composition, resin and wax described later are measured by GPC under the following conditions.

<GPC measurement conditions for toner composition and resin> Device: GPC-150C (manufactured by Waters) Column: KF801-7 (manufactured by Showdex) 7 consecutive temperatures: 40 ° C Solvent: THF (tetrahydrofuran) Flow rate: 1.0 ml / min. Sample: 0.1 m of a sample having a concentration of 0.05 to 0.6% by weight
l injection

<GPC measurement conditions for wax> Apparatus: GPC-150C (manufactured by Waters Co.) Column: GMH-HT (manufactured by Tosoh Corp.) Dual temperature: 135 ° C. Solvent: o-dichlorobenzene (addition of 0.1% ionol) ) Flow rate: 1.0 ml / min. Sample: Inject 0.4 ml of a sample with a concentration of 0.15% by weight

The molecular weight calibration curve prepared from the monodisperse polystyrene standard sample is used for the measurement of the molecular weight of the sample measured under the above conditions. Furthermore, the molecular weight of the wax is calculated by converting it with a conversion formula derived from the Mark-Houwink viscosity formula.

The molecular weight in GPC is 1.0 × 10 ^6.
The content of the above resin component can be calculated by obtaining the ratio of the integral value of the molecular weight of 1.0 × 10 ⁶ or more to the integral value of the chromatogram of the resin component.

The first feature of the present invention is that it has a clear peak below 1 × 10 ³ . The molecular constitution of less than 1 × 10 ³ is the original constitutional component of the binder resin, and a part of the binder resin component is reduced in molecular weight by breaking the molecular chain due to mechanical shearing force during melt kneading during toner production. It is considered that the component, the original component of the wax, and a part of the component of the wax are composed of a component in which the molecular chain is broken by the mechanical shearing force at the time of melt kneading at the time of toner production and the molecular weight is lowered.

An important constituent element corresponding to the peak of the present invention is an aliphatic hydrocarbon wax described later, and this wax forms the main constituent element of this peak, so that it is unique to the above-mentioned complex low molecular weight component. The heat resistance and sharp melt properties of As a result, the toner of the present invention achieves low-temperature fixing which is not found in conventional electrostatic image developing toners, and at the same time, imparts the effect of preventing toner fusion, offset and smearing to the photoconductor even in this low molecular weight region. I am letting you.

The second characteristic is that when the peak has a peak at 5 × 10 ³ to 1 × 10 ⁵ , and the height of this peak is H _B and the peak less than 1.0 × 10 ³ is H _A , it is 0. .25 ≦ H _A / H _B <1.
This is a point that satisfies 0. The molecular weight component in the range of 5 × 10 ³ to 1 × 10 ⁵ is due to the main peak of the binder resin used in the present invention, and the toner has good rigidity, which results in good charging characteristics and developability. It becomes possible to have The peak heights on both the high molecular weight side and the low molecular weight side are defined in order to basically maintain the balance between the fixing property and the developing property of the toner. This balance adjustment must take into consideration the molecular weight distribution of the binder resin used and the wax amount described above. When H _A / H _B is less than 0.25, sufficient low temperature fixing performance cannot be obtained, and when H _A / H _B is 1 or more, the developing power is lowered. Preferably 0.2
The range is 5 to 0.85, and more preferably 0.3 to
This is the case of 0.8.

The third feature is that 6 to 30% of a component of 1.0 × 10 ⁶ or more is contained. This improves offset resistance, blocking resistance, and smearing resistance, which is an MICR characteristic. The case is preferably 7 to 27%, more preferably 8 to 25%.

Further, the toner of the present invention is the THF described below.
It is preferable that the content of insoluble matter is 30 to 70% by weight. The insoluble component is a chemical bond between the component originally held by the binder resin and the carboxyl group of the binder resin during melt-kneading and the organometallic compound used as the charge control agent (crosslinking during kneading).
The component generated by is considered. In such a case, the rigidity of the toner is further increased, and the offset resistance, blocking resistance, and smearing resistance are further improved.

When cross-linking occurs during kneading, the melt viscosity can be easily lowered particularly during kneading, and the dispersibility of the resin and wax can be improved. As a result, good dispersibility can be maintained even if the wax content in the toner is increased to some extent. If the amount of insolubles is less than 30% by weight, the above-mentioned remarkable effects are not observed, and if it exceeds 70% by weight, the toner becomes too hard and the pulverizability is lowered, which is not preferable in production. More preferably, it is 35 to 65% by weight.

THF of the toner for developing an electrostatic image according to the present invention
The insoluble content refers to a weight ratio of a polymer component (substantially a crosslinked polymer) which becomes insoluble in the THF solvent in the resin composition in the toner, and indicates a degree of crosslinking of the resin composition including the crosslinking component. Can be used as a parameter.
The THF-insoluble matter is defined as a value measured as follows.

That is, about 0.5 g of toner sample (W
₁ g), is a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.)
And impregnate it in a container containing about 100 ml of THF solution in a sealed state for about 30 hours. Then, the cylindrical filter paper is taken out of the THF solution, left for about 6 hours, vacuum dried at 100 ° C. for about 90 minutes, and weighed to obtain the THF-soluble resin component amount (W ₂ g). The weight of the components other than the resin component such as the magnetic substance or pigment in the toner (W ₃ g)
And The THF insoluble content is calculated by the following formula.

THF insoluble matter (%) = ((W ₁ − (W ₃ + W
_{2)) / (W 1 -W} 3) × 100

Next, the binder resin favorably used in the present invention will be described. The binder resin used in the present invention is JI
It preferably has an acid value of 5 to 50 mmKOH / g according to SK-0070. When the acid value is less than 5 mmKOH / g, the crosslinking reaction does not proceed sufficiently during kneading, and
When the acid value is larger than mmKOH / g, the cross-linking reaction proceeds too much during kneading, which causes the same adverse effects as described above for the THF-insoluble matter. Preferably 5-40 mm KO
H / g range, more preferably 10 to 30 mmK
It is in the range of OH / g.

The JIS acid value can be determined by the following method.

2 to 10 g of sample to 200 to 300 ml
Weigh it in an Erlenmeyer flask and ethanol: benzene = 1:
About 50 ml of the mixed solvent of 2 is added to dissolve the resin. If the solubility seems to be poor, a small amount of acetone may be added. Pre-standardized N / 10 potency potassium with indicator
Titration is performed with an alcohol solution, and the acid value is calculated from the consumption amount of the caustic potash-alcohol solution by the following formula.

Acid value = KOH (ml number) × N × 56.1 / Sample weight (where N is a factor of N / 10 KOH)

Further, it is preferable that the binder resin is a mixture of two kinds of binder resins having different main effects, rather than being composed of one kind of binder resin. For example, the low-temperature fixing property and the developing property, and the adhesion properties to paper relating to MICR properties and the smearing resistance, which are generally difficult to achieve at the same time, are required to be achieved at a high level, which are the objectives of the present invention. Therefore, such a resin mixture is suitable.

The binder resin preferably used in the present invention is
A binder resin having a main peak below 1 × 10 ³ ~1.5 × 10 ⁴ in ^{GPC, 1.5 × 10 4 ~1 ×} 10 5
It is preferable to use it as a mixed resin of a binder resin having a main peak in a region below.

The former resin mainly acts effectively for low temperature fixing and adhesion to paper. Main peak is 1
If it is less than × 10 ³ , adverse effects such as offset and toner fusion to the drum are likely to occur. If it is 1.5 × 10 ⁴ or more, the effect of low temperature fixing and adhesion to paper decreases. Particularly preferably, it is obtained by a suspension polymerization method, contains 10 to 50% by weight of THF insoluble matter, and has an offset resistance effect.

The latter resin mainly acts effectively to improve the developability. If the main peak is less than 1.5 × 10 ⁴ , the effect of improving developability cannot be expected. 1.0 x 10
^When it is ⁵ or more, the toner becomes too hard and the pulverizability is lowered, which is not preferable in terms of production cost. Particularly preferably, those obtained by a solution polymerization method, containing no THF insoluble matter and having an acid value of 10 to 50 mgKOH / g, and causing crosslinking during kneading in the presence of an organometallic compound,
It can be expected to improve mutual dispersibility with other materials such as wax, and to have a high level of offset resistance and smearing resistance.

Even when used alone as described above, by using a mixed resin composed of two kinds of resins which have the basic performance as a binder resin and have different main effects, The charge image developing toner can be expected to have the effect of combining both resins.

The two types of mixing ratio of the resin, Resin 1 having a main peak in 1.0 × 10 ³ ~1.5 × 10 below ^{4] / [1.5 × 10 4} ~1.0 × 10 5 Resin 2 having a main peak at less than 1] is preferably in the range of 1/4 to 4. Resin 1 / Resin 2 is 1 /
When it is less than 4, low-temperature fixing and adhesion to paper cannot be satisfied, and when it is more than 4, developability and smearing resistance are deteriorated. The range is more preferably 3/7 to 7/3.

The THF insoluble content of the binder resin used in the present invention was measured as follows. About 0.5 g of resin composition (W
₁ ) is weighed, and a cylindrical filter paper (Toyo Roshi Kaisha No. 86R: 2
(8 × 100 mm), put on a Soxhlet extractor, and extracted with 200 ml of THF as a solvent for 6 hours. The THF extraction cycle in the Soxhlet extractor was once every about 4 minutes.

The THF-soluble component extracted with THF was evaporated and then dried under reduced pressure at a temperature of 100 ° C. to obtain TH.
The weight of the F-soluble component (W ₂ ) was weighed.

[0045]

[Equation 1]

As the binder resin of the toner according to the present invention,
Polystyrene, homopolymers of styrene such as polyvinyltoluene and its substitution products; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate acrylic acid copolymer, styrene-methacrylic acid Ethyl acid copolymer,
Styrene-butyl methacrylate copolymer, styrene-
Dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-
Isoprene copolymer, styrene-maleic acid copolymer,
Styrene-based copolymers such as styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid Resin, rosin, modified rosin, tempel resin,
Phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, paraffin wax, carnauba wax and the like can be used alone or in combination. Styrene-based copolymers and polyester resins are preferable in terms of development characteristics, fixing properties and the like.

It is particularly preferable that the binder resin used in the present invention has a carboxyl group-containing monomer or a monomer having a group derived from a carboxyl group as a constituent component.

For example, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride. Unsaturated dibasic acid anhydride such as; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester (eg, mono-n-butyl maleate), citraconic acid methyl half ester, citraconic acid ethyl half ester, Half ester of unsaturated dibasic acid such as butyl citraconic acid half ester, methyl itaconic acid half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, dimethyl fumaric acid It includes unsaturated dibasic acid diesters such as.

Further, α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride; An anhydride of β-unsaturated acid and lower fatty acid; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof and monoesters thereof can be mentioned.

Among these, maleic acid, fumaric acid,
Monoesters of α, β-unsaturated dibasic acid having a structure such as succinic acid are particularly preferably used as a monomer for obtaining the binder resin used in the present invention.

The wax used in the present invention is (i) to
The wax (v) can be used.

(I) Low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure (ii) Alkylene polymer obtained by thermal decomposition of high molecular weight alkylene polymer (iii) From coal gas A hydrocarbon wax obtained by extracting and fractionating a specific component from a material such as a synthetic hydrocarbon obtained by hydrogenating a distillation residue of the hydrocarbon obtained by the Arge method from the obtained synthesis gas consisting of carbon monoxide and hydrogen (iv ) Alcohol wax having a complete long chain saturated hydrocarbon as a main chain, which is considered to be obtained from an alkylene polymer using a Ziegler catalyst (v) Carboxyl group, ester group derived from the alcohol wax obtained by (iv), Aliphatic hydrocarbons having functional groups such as ether groups and sulfonyl groups

The wax preferably used in the present invention is
In the DSC curve measured by a differential scanning calorimeter,
A wax characterized by having at least one endothermic peak at the time of temperature rise in the range of 90 to 120 ° C. and having a maximum exothermic peak at the time of temperature fall within the peak temperature of the endothermic peak ± 9 ° C. is there.

The presence of an endothermic peak at a temperature rise within the range of 90 to 120 ° C. means that the wax is melted in this temperature range and the releasing effect is exhibited and the MICR reader / sorter is repeatedly passed. MICR characters are less likely to be faint or missing even when printed on paper, and the magnetic head of MICR reader / sorter is hard to contaminate.

When the endothermic peak temperature at the time of temperature rise exists only below 90 ° C., it is shown that the plasticizing effect by melting of the wax appears from a low temperature and the mechanical strength of the binder resin is remarkably lowered. In this case, although the release effect is exhibited when the paper is passed through the MICR reader / sorter, the MICR character may be faint when rubbing against the magnetic head of the MICR reader / sorter due to the decrease in mechanical strength of the binder resin. Are likely to occur and at the same time contaminate the magnetic head, which is not preferable.

The endothermic peak at the time of temperature increase may exist in the region exceeding 120 ° C. However, when the endothermic peak temperature exists only in the region exceeding 120 ° C., the melting temperature of the wax is It is too expensive, and MICR readers can be easily released from the paper in MICR printing.
When the paper is passed through the sorter, MICR characters are apt to be lost due to rubbing against the magnetic head, and as a result, the magnetic head is easily contaminated. Here, when the endothermic peak below 90 ° C. becomes the maximum peak, the same behavior as when there is an endothermic peak only in this region is exhibited, so an endothermic peak may exist in this region, but in that case, It must be smaller than the endothermic peak in the range of 90 to 120 ° C.

When the temperature is lowered, changes in the wax during cooling and the state at room temperature can be observed, and exothermic peaks associated with the solidification, crystallization and transition of the wax are observed. The exothermic peak at the time of cooling is the maximum exothermic peak due to the solidification and crystallization of the wax. The existence of an endothermic peak due to melting at the time of temperature rise near the exothermic peak temperature indicates that the wax is more homogeneous in terms of physical properties such as crystal structure and molecular weight distribution. Difference is preferably within 9 ° C., preferably 8
Within ℃. By reducing this difference, the wax has a sharp melting property, that is, it is hard at low temperatures, melts quickly at melting, and the melt viscosity is greatly reduced, resulting in excellent release effect. And MI
Even if you repeatedly pass through the CR leader / sorter,
MICR characters are less likely to be faint or missing, and the MICR reader / sorter magnetic head is less likely to be contaminated. The maximum exothermic peak temperature is in the range of 85 to 115 ° C, preferably 90 to 110 ° C.

In the DSC measurement of the present invention, since the heat exchange of the toner is measured and its behavior is observed, it is necessary to measure with a highly accurate internal heat type input compensation type differential scanning calorimeter from the principle of measurement. As such a measuring instrument, for example, DSC-7 manufactured by Perkin Elmer Co. can be used.

The measuring method is ASTM D3418-82.
Carry out according to. As the DSC curve used in the present invention, the DSC curve measured when the temperature is raised once and the previous history is taken, and then the temperature is lowered and the temperature is raised at a temperature rate of 10 ° C./min is used.
The definition of each temperature is defined as follows.

Endothermic peak temperature: The temperature at the peak top is defined as endothermic in the positive direction of the DSC curve.

Exothermic peak temperature: The peak top temperature is defined as the negative direction of the DSC curve.

The preferred range of the molecular weight distribution of the wax used in the present invention is that the number average molecular weight (Mn) is 550 to 1
The weight average molecular weight (Mw) is preferably 200.
Is preferably 800 to 3000, more preferably 900 to 2500, and further preferably Mw / Mn is 3 or less, more preferably 2.5 or less. By having such a molecular weight distribution, it is possible to give the toner favorable thermal characteristics. That is, when the molecular weight is smaller than the above range, the toner is likely to be excessively affected by heat and the blocking resistance and fluidity of the toner are deteriorated, and smearing is likely to occur in MICR characteristics, and at the same time, the magnetic head is easily contaminated. If the molecular weight is larger than the above range, the adhesion to paper deteriorates, and as a result, if the paper is bent when it is passed through a MICR reader / sorter, the toner may come off from the paper. Not preferable.

The content of the wax is preferably 5 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the binder resin. When the amount is less than 5 parts by weight, the above-mentioned effects are difficult to be exhibited,
If it exceeds 20 parts by weight, the fluidity of the toner is lowered and the dispersion with the binder resin is deteriorated, which is not preferable.

The wax used in the present invention has the following general formula RY [R: a hydrocarbon group having a weight average molecular weight of 3000 or less according to gel permeation chromatograph.

Y: hydrogen atom, hydroxyl group, carboxyl group,
An alkyl ether group, an ester group, and a sulfonyl group are shown. ] It is preferable that the compound containing

Specific examples of the compound include (A) CH ₃ (CH ₂ ) _n CH ₂ OH (n = about 20 to about 20).
_{0) (B) CH 3 (} CH 2) n CH 2 COOH (n = about 20 to about _{200) (C) CH 3 (} CH 2) n CH 2 OCH 2 (CH 2) m CH 3 (n = about 20 to about 200, m = 0 to about _{100) (D) CH 3 (} CH 2) n H (n = about 20 to about _{200) (E) CH 3 (} CH 2) n CH 2 COO (CH 2) m CH ₃ (n = about 20 to about 200, m = 0 to about 100) (F) CH ₃ (CH ₂ ) _n CH ₂ OSO ₃ H (n = about 20 to
About 200) and the like. These compounds are derivatives of the compound (A), and the main chain is a linear saturated hydrocarbon. Compounds other than those shown in the above examples can be used as long as they are compounds derived from the compound (A). By using the above wax, the toner of the present invention satisfies the fixability at low temperature, the adhesion to paper, the smearing resistance, and the developability, and on the other hand, the effect of preventing the toner fusion to the photosensitive drum. Have.

Among the above compounds, especially (A) formula CH
_The toner using the polymer alcohol represented by ₃ (CH ₂ ) _n CH ₂ OH (n = about 20 to about 200) exhibits the extremely excellent above-mentioned effects.

In terms of molecular weight distribution, Mn is 200 to 2
It is preferably 000, and more preferably 230 to
1800, and Mw is preferably 400 to 3000, more preferably 420 to 2500. Further, Mw / Mn is preferably 3.0 or less, more preferably 2.5 or less.

By having such a molecular weight distribution, the toner can have preferable thermal characteristics.
If it is smaller than the above-mentioned molecular weight, smearing tends to occur, and if it is larger, the fixability is deteriorated. If Mw / Mn is larger than 3.0, the effect of preventing toner fusion to the photosensitive drum and smearing is lowered. The content of these waxes relative to 100 parts by weight of the binder resin is the above-mentioned DS.
The same applies to the case of a wax having a characteristic C curve.

In the toner of the present invention, it is preferable to use an organometallic compound for charge control. Among the organometallic compounds, those containing an organic compound rich in vaporization and sublimation as a ligand or a counter ion are particularly useful. Among the organic compounds that form a ligand or counterion with a metal ion, those having the above-mentioned properties include, for example, salicylic acid, salicylamide, salicylamine, salicylaldehyde, salicylosalicylic acid, and ditert-butylsalicylic acid. , Salicylic acid and its derivatives;
Β-diketones such as acetylacetone and propionacetone; for example, low molecular weight carboxylic acid salts such as acetate and propionic acid.

As such a metal complex, there is an azo metal complex represented by the following general formula [I].

[0072]

Embedded image

In the formula, M represents a coordination center metal, and examples thereof include Cr, Co, Ni, Mn and Fe having a coordination number of 6. A
r is an aryl group, and examples thereof include a phenyl group and a naphthyl group, which may have a substituent. Examples of the substituent in this case include a nitro group, a halogen group, a carboxyl group, an anilide group, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group. X, X ', Y, Y'are -O-, -CO-,
-NH-, -NR- (R is an alkyl group having 1 to 4 carbon atoms)
Is. K ⁺ represents hydrogen, sodium, potassium, ammonium or aliphatic ammonium.

Next, specific examples of the complex will be shown.

[0075]

Embedded image

[0076]

[Chemical 3]

[0077]

[Chemical 4]

[0078]

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[0079]

[Chemical 6]

[0080]

[Chemical 7]

[0081]

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Alternatively, the basic organic acid metal complex represented by the following general formula [II] also imparts a negative charging property and can be used in the present invention.

[0083]

[Chemical 9]

[0084]

[Chemical 10]

Specific examples of the complex are shown below.

[0086]

[Chemical 11]

[0087]

[Chemical 12]

[0088]

[Chemical 13]

[0089]

Embedded image

[0090]

[Chemical 15]

[0091]

Embedded image

[0092]

[Chemical 17]

[0093]

Embedded image

[0094]

[Chemical 19]

[0095]

Embedded image

These metal complexes can be used alone or in combination of two or more.

The amount of the metal complex added to the toner particles varies depending on the type of the toner binder, whether or not the carrier is used in combination, the pigment for coloring the toner, and the reactivity of the metal complex with the binder. 0.01 to 100 parts by weight of binder, including unreacted ones
It is 20 parts by weight, preferably 0.1 to 10 parts by weight.

Further, the above metal complex is rich in decomposition and reactivity by reacting with a binder during melt-kneading,
In addition, there is an advantage that compatibility with the binder or dispersibility in the binder is excellent, and stable charging property as a toner is obtained.

In the present invention, the metal compound as the cross-linking component can have charge controllability as a toner, but if necessary, a charge control agent can be used separately from the toner, A conventionally known negative or positive charge control agent is used.

Charge control agents known in the art today include the following:

The following substances control the toner to be negatively charged.

For example, organic metal complexes and chelate compounds are effective, and as mentioned above, there are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids and aromatic dicarboxylic acid type metal complexes. Other examples are aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

The following substances control the toner to be positively charged.

For example, modified products of nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and phosphonium which is an analog thereof. Onium salts such as salts and lake pigments thereof. Triphenylmethane dyes and their lake pigments. (As a lake agent,
Metal salts of higher fatty acids, such as phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide and ferrocyanide, acetylacetone metal complexes. Diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate,
Diorgano tin borate such as dicyclohexyl tin borate and the like, and these can be used alone or in combination of two or more kinds. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

As the magnetic substance used when the electrostatic image toner of the present invention contains a magnetic substance, a metal made of a ferromagnetic element such as iron such as ferrite and magnetite, cobalt, nickel, or the like is used. It does not contain alloys or compounds containing, or elements with strong magnetic properties,
An alloy that exhibits ferromagnetism by appropriate heat treatment,
Examples thereof include manganese-copper-aluminum, manganese-copper-tin, and other types of alloys called Heusler alloys containing manganese and copper, chromium dioxide, and the like. Such magnetic fine particles can also be used as a black or brown pigment.

Particularly when the toner of the present invention is used for MICR, the coercive force Hc of such a magnetic material is preferably in the range of 130 ≦ Hc ≦ 300 in a magnetic field of 10,000 Oersted, and 140 ≦ Hc ≦. More preferably, it is in the range of 280 oersteds. Further, the residual magnetization σr is 12 ≦ in a magnetic field of 10,000 Oersted.
It is preferably in the range of σr ≦ 30 emu / g, and more preferably in the range of 14 ≦ σr ≦ 28 emu / g.

However, silicon and aluminum elements may be contained for the purpose of improving image defects (for example, low image density and fog) that occur when such a magnetic material is used.

With respect to the magnetic material, silicon element is 0.1 to 1.0% by weight in terms of SiO ₂ , and aluminum element is Al.
_It is preferable to contain 0.1 to 1.0% by weight in terms of ₂ O ₃ , more preferably 0.15 to 0.1 ₅ in terms of SiO _2.
0 in terms of 0.9% by weight of silicon element and Al ₂ O _3.
It is preferable to contain 15 to 0.9% by weight of aluminum element. The silicon element and the aluminum element are
The magnetic material according to the present invention can be added during and / or after the wet synthesis, and when heat oxidation treatment and heat reduction treatment are further performed after the wet synthesis, they can be added at that stage.

According to the magnetic toner of the present invention, the fog and blotch are not generated and the image density is improved.

Also, when used for printing MICR characters, the magnetic signal strength can be improved, and MI
It is possible to print MICR characters with a good recognition rate by a CR reader / sorter.

When the toner of the present invention is used as a two-component developer, it is used as a mixture with carrier powder. In this case, the mixing ratio of the toner and the carrier powder is 0.1 to 50% by weight as the toner concentration, preferably 0.5.
10 to 10% by weight, more preferably 3 to 5% by weight is preferable.

As the carrier that can be used in the present invention, known carriers can be used. Examples thereof include magnetic powders such as iron powders, ferrite powders, and nickel powders, and those whose surfaces are treated with a resin such as a fluorine-based resin, a vinyl-based resin, or a silicone-based resin.

In the toner of the present invention, the charging stability,
In order to improve developability, fluidity and durability, it is preferable to add an inorganic fine powder.

As the inorganic fine powder used in the present invention,
Examples thereof include fine silica powder, titanium oxide, and alumina. Among them, the specific surface area is 30 m ² / g or more (particularly 50 to 400 m ² / g) due to nitrogen adsorption measured by the BET method.
Those in the range of give good results. The inorganic fine powder is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner.

The inorganic fine powder used in the present invention is
Silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of hydrophobicizing, controlling chargeability, etc., as required. It is also preferable that the treatment is carried out with a treating agent such as the above, or in combination with various treating agents.

As other additives, lubricants such as Teflon, zinc stearate, polyvinylidene fluoride, and silicone oil particles (containing about 40% silica) are preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate are preferable, and strontium titanate is particularly preferable. Alternatively, for example, a fluidity-imparting agent such as titanium oxide or aluminum oxide, among which a hydrophobic agent is particularly preferable. A small amount of an anti-caking agent, or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, etc., or white and black fine particles of opposite polarity can be used as a developing property improver.

Further, the image forming method and apparatus of the present invention will be described with reference to FIG.

The surface of the photoconductor is negatively charged by the primary charger 302, and a digital latent image is formed by image scanning by exposure 305 by laser light.
The latent image is reversely developed with the one-component magnetic developer 310 of the developing device 309 including the developing sleeve 304 containing 11 and a magnet. Alternate bias, pulse bias and / or DC bias are applied by the bias applying means 312 between the conductive substrate of the photosensitive drum 301 and the developing sleeve 304 in the developing section. When the transfer paper P is conveyed and reaches the transfer portion, the roller transfer means 302 charges the transfer paper P from the back surface (the surface opposite to the photosensitive drum side) of the transfer paper P by the voltage application means 314, thereby developing the image on the photosensitive drum surface. The (toner image) is electrostatically transferred onto the transfer paper P.
The transfer paper P separated from the photosensitive drum 301 is subjected to a fixing process by the heating and pressure roller fixing device 307 in order to fix the toner image on the transfer paper P.

The one-component type developer remaining on the photosensitive drum after the transfer step is removed by a cleaning device 308 having a cleaning blade. The photosensitive drum 301 after cleaning is erased by the erase exposure 306, and again,
The process starting from the charging process by the primary charger 302 is repeated.

The image quality was evaluated by checking periodically during durability (about 5000 sheets). The evaluation method and its criteria are described below.

(1) Fixability test: The LJ-IV was modified so that the fixing machine temperature could be varied, and the following temperature was investigated.

Fixing start temperature: The evaluation machine is in the environment (23.5
10 degree solid black image is continuously copied in a state where the toner coat amount on the paper is adjusted from a state of being familiar with 60 ° C.) 1
The 0th sheet was used for evaluation. A drafting tape was stuck on this solid black image, and a 10-way rubbing image density reduction rate was evaluated with a jig (load of about 0.6 kg / cm ² ) as shown in FIG. The temperature at which 30% or less can be maintained was defined as the fixing start temperature.

High temperature offset generation temperature: In the fixing test, when the temperature of the fixing device is increased, an image in which the upper half of the image becomes solid black and the lower half becomes solid white is copied, and the temperature at which the solid white part is stained Was defined as the high temperature offset generation temperature.

(2) Toner fusion to the photosensitive member ... After continuous printing of 5000 sheets in a high temperature and high humidity environment (32.5 ° C., 85%), evaluation was made from a solid black image. ○: No fusion was observed at all, ○ △: 1-3 fused points in A4 solid black, △: A
4 to 9 fusion points in solid black, × ... A4 solid black 10
The fusion was made up of points or more.

(3) Image density ... Under high temperature and high humidity environment (3
20 from initial to 5000 sheets at 2.5 ° C, 85%)
A total of 26 samples per 0 sheets were measured with a Macbeth densitometer,
The average value was used as the image density.

The evaluation regarding the MICR characteristics was performed as follows.

(1) Adhesiveness ... In the above-mentioned fixing test, the data at 180 ° C. was used as the representative value of the adhesiveness. The smaller the number, the better the adhesiveness.

(2) Smearing ... JIS C 625
According to the description of 0-1980, print MICR characters 100
0 sheets are printed, and these 1000 sheets are printed on the commercial MICR.
Dma of the non-printed part (see Fig. 1) of the sample which was passed 20 times through a reader / sorter (IBM model 3890)
The x value (value obtained by subtracting the Dmax value of the non-sheet passing white background) was measured with a Macbeth reflection densitometer.

(3) Misreading rate ... JIS C 6250-1
According to the description of 980, the MICR character printing is 1,000
This is printed on 1,000 sheets, and the printed material is printed on MICR
The survey was conducted using a leader sorter (IBM model 3890). The misreading rate was calculated by the following formula.

[0130]

[Equation 2]

[0131]

EXAMPLES "Parts" means "parts by weight".

Example 1 Binder resin (A) 50 parts Binder resin (B) 50 parts Magnetic substance (Fe ₃ O ₄ ) 90 parts Monoazo dye chromium complex (complex [I] -2 in the text) 1 part Salicylic acid Chromium complex (complex [II] -9 in the text) 2 parts Wax (a) 7 parts

The binder resin (A) in the above constituent materials is obtained by dissolving a polymer obtained by solution polymerization of styrene, n-butyl acrylate and monobutyl maleate in styrene, n-butyl acrylate, monobutyl maleate monomer. , Crosslinked and suspension polymerized with divinylbenzene,
GPC has a main peak at 6450, an acid value of 17.0 mgKOH / g, and a gel content of 39%.
The Mw of the soluble component is 4.2 × 10 ⁴ .

The binder resin (B) is obtained by crosslinking solution polymerization of styrene, butyl acrylate, acrylic acid and monobutyl styrene maleate with divinylbenzene.
, Has a main peak at 35400, has no gel component, has an acid value of 18.0 mgKOH / g, and Mw of 3.3.
It is × 10 ⁵ .

The magnetic material had a residual magnetization δr of 18 emu / g and a Hc of 19 in a magnetic field of 10,000 Oersted.
A material having 0 Oersted and a magnetic permeability μ of 2.5 was used.

Regarding the wax, the main component is a straight-chain saturated hydrocarbon obtained by the Arge process, and Mn
= 820, Mw = 1260, the endothermic peak temperature in the DSC characteristics is 105 ° C., the maximum exothermic peak temperature during cooling is 104 ° C., and Mw / Mn = 1.60 (hereinafter referred to as wax a). Using.

The above constituent materials were mixed and dispersed by a Henschel mixer, and melt-kneaded by a twin-screw extruder.
The kneaded product was cooled, coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified by an air classifier to obtain a magnetic toner having a weight average particle diameter of 8 μm. Table 1 shows the GPC of the obtained toner and the constituent contents of the resin and the wax.

To 100 parts of the magnetic toner, 1.2 parts of hydrophobic silica treated with hexamethyldisilazane and then with silicone oil were added and mixed with a Henschel mixer to obtain a magnetic developer. The obtained magnetic developer was used as LJ-I.
A general image and MICR characters were printed using V, and electrophotographic characteristics and MICR characteristics were evaluated. Table 2 shows the results.

Example 2 The constituent materials other than wax were the same as in Example 1, and the mixing weight ratio was also the same as in Example 1.

With respect to the wax, about 80% is composed of the component represented by the compound (A) in the text, and the remaining about 20% is mainly composed of the component represented by the compound (D) in the text, which is average. molecular formula CH ₃ showing the Do composition (CH _{2) 48} CH
Represented by ₂ OH, Mn = 450, Mw = 880, Mw
/Mn=1.80, the endothermic peak temperature in DSC characteristics was 98 ° C., and the maximum exothermic peak was 97 ° C. when the temperature was lowered (hereinafter referred to as wax b). Hereinafter, Example 1
A magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as described above. Table 1 shows the GPC of the obtained toner and the constituent contents of the resin and the wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1.
Table 2 shows the results.

Example 3 Binder resin (A) 30 parts Binder resin (B) 70 parts Magnetic substance (Fe ₃ O ₄ ) 90 parts Monoazo dye chromium complex (complex [I] -2 in the text) 1 part Salicylic acid Chromium complex (complex [II] -9 in the text) 2 parts Wax (b) 5 parts

As described above, the binder resins A and B and the wax b
The content of was changed. Thereafter, a magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as in Example 1. Table 1 shows the GPC of the obtained toner and the constituent contents of the resin and the wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Example 4 The formulation is the same as in Example 3 except that the content of wax b is changed. Thereafter, a magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as in Example 1. G of the obtained toner
Table 1 shows the composition of PC, resin and wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Example 5 The formulation is the same as in Example 3 except that the content of wax b is 12 parts. Thereafter, a magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as in Example 1. Table 1 shows the GPC of the obtained toner and the constituent contents of the resin and the wax.
Further, as in Example 1, external addition was performed to obtain a magnetic developer,
Evaluation was carried out in the same manner as in Example 1. Table 2 shows the results.

Example 6 The formulation was the same as in Example 2 except that the content ratio of the binder resin (80 parts for A and 20 parts for B) was changed.
A magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as described above. Table 1 shows the GPC of the obtained toner and the constituent contents of the resin and the wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Example 7 The formulation is the same as in Example 6 except for the wax.

With respect to the wax, about 80% is composed of the component represented by the compound (B) in the text and the remaining about 20% is composed mainly of the component represented by the compound (A) in the text. The molecular formula showing the composition is CH ₃ (CH ₂ ) ₄₈ CH
₂ COOH, Mn = 350, Mw = 910,
Mw / Mn = 2.50, an endothermic peak temperature of 105 ° C. and a maximum exothermic peak of 98 ° C. at the time of temperature decrease in DSC characteristics (hereinafter referred to as wax c) were used.

Then, a magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as in Example 1. GP of the obtained toner
Table 1 shows the composition of C, the resin and the wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 1 Example 1 except that only 100 parts of B was used as the binder resin.
The prescription composition is the same.

Then, a magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as in Example 1. GP of the obtained toner
Table 1 shows the composition of C, the resin and the wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 2 The same as Example 1 except that the binder resin A was 100 parts and the wax a was 4 parts.

Then, a magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as in Example 1. GP of the obtained toner
Table 1 shows the composition of C, the resin and the wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

Comparative Example 3 The formulation is the same as that of Comparative Example 2 except that only wax d is changed to wax d.

The wax d is a propylene-ethylene copolymer, Mn = 3000, Mw = 15300, Mw /
A material having Mn of 5.1 and having an endothermic peak temperature of 125 ° C. and a maximum exothermic peak of 110 ° C. at the time of temperature decrease was used in DSC characteristics.

Then, a magnetic toner having a weight average particle diameter of 8 μm was obtained by the same manufacturing method as in Example 1. GP of the obtained toner
Table 1 shows the composition of C, the resin and the wax. Further, as in Example 1, external addition was performed to obtain a magnetic developer, and evaluation was performed in the same manner as in Example 1. Table 2 shows the results.

[0156]

[Table 1]

[0157]

[Table 2]

[0158]

The present invention is a toner having a very wide range of molecular weight distribution from a low molecular weight region to a high molecular weight region by containing a specific binder resin and a wax. It is effective.

(1) It is possible to provide a toner for electrostatic image development which achieves low-temperature fixing, does not cause toner fusion on the photosensitive drum, and is excellent in offset resistance.

(2) It is possible to provide an electrostatic image developing toner having a high image density even in a high temperature and high humidity environment.

(3) It is possible to provide a toner for developing an electrostatic charge image which has good adhesion to paper and can form MICR characters which are difficult to separate from paper.

(4) MICR leader ・ No smearing occurs even if paper is repeatedly passed through the sorter.
It is possible to provide an electrostatic charge image developing toner capable of forming MICR characters having a good recognition rate of a reader / sorter without contaminating the magnetic head of the sorter.

[Brief description of drawings]

[Fig.1] MIC with check etc. in leader / sorter test
It is the figure which showed typically the part in which R character is printed, and the smearing generation part.

FIG. 2 is a diagram schematically showing a jig used in an adhesion test and its state.

FIG. 3 is a diagram schematically showing a specific example of an image forming method and an image forming apparatus suitable for the present invention.

[Explanation of symbols]

 301 Photoreceptor 302 Charging Means 303 Transfer Means 304 Toner Carrier 305 Latent Image Forming Means 306 Erase Exposure 307 Heat Press Roller Fixer 308 Cleaning Means 309 Developing Means 310 Magnetic Developer 311 Magnetic Blades 312 Bias Applying Means 313 Voltage Applying Means P Transfer paper

Claims (11)

[Claims] 1. In a toner for developing an electrostatic charge image containing at least a binder resin and a wax, a tetrahydrofuran (THF) -soluble component has a molecular weight distribution measured by gel permeation chromatography (GPC) and a molecular weight of 1
The region A of less than × 10 ^{3 and} the region B of 5 × 10 ³ to 1 × 10 ⁵ each have at least one peak, the maximum peak height of the region A is H _A , and the maximum peak height of the region B is H. _{When B} is set, the following condition 0.25 ≦ H _A / H _B <1 is satisfied, and a region of 1 × 10 ⁶ or more is 6 to 30%, and an electrostatic image developing toner. 2. The toner has a THF insoluble content of 30.
The toner for developing an electrostatic charge image according to claim 1, wherein the toner is about 70% by weight. 3. The acid value of the binder resin is 10 to 50 mg KO.
The toner for developing an electrostatic charge image according to claim 1, wherein the toner is H / g. 4. The binder resin is 1 × 10 in GPC.
³ is to 1.5 × 10 resin 1 having a main peak in less than ⁴ area and 1.5 × 10 ⁴ to 1 × mixed resin of a resin 2 having a main peak in ¹⁰⁵ less than in the region, and the mixing ratio [ The (resin 1) / (resin 2)] is 1/4 to 4 and the electrostatic charge image developing toner according to claim 1. 5. The resin 1 is a resin obtained by a suspension polymerization method, contains 10 to 50% by weight of a THF insoluble matter, and the resin 2 is a resin obtained by a solution polymerization method, T
Does not contain HF insoluble matter and has an acid value of 10 to 50 mgKOH / g
5. The toner for developing an electrostatic charge image according to claim 4, wherein 6. The toner for developing an electrostatic image according to claim 1, wherein the wax is contained in an amount of 5 to 15 parts by weight based on 100 parts by weight of the binder resin. 7. The DSC curve of the wax, which is measured by a differential scanning calorimeter, has at least one endothermic peak at a temperature rise of 70 ° C. to 130 ° C., and the peak temperature of the endothermic peak ± The toner for developing an electrostatic charge image according to claim 1, which has a maximum exothermic peak when the temperature is lowered within a range of 9 ° C. 8. The wax has the following general formula RY [R: a hydrocarbon group having a weight average molecular weight of 3000 or less according to GPC. Y: represents a hydrogen atom, a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group. ] The toner for developing an electrostatic charge image according to claim 1, further comprising: 9. The wax has the following chemical formula: CH ₃ (CH ₂ ) _n CH ₂ OH (n = about 20 to about 20).
The toner for developing an electrostatic charge image according to claim 1, further comprising a compound represented by the formula (0). 10. The electrostatic image developing toner contains a magnetic material.
And has a magnetic material of 10,000 Oersted.
Remanence in the field δ r is 12 ≦ δ r ≦ 30 emu / g
And the coercive force Hc is 130 ≦ Hc ≦ 300 L
It is in the range of Steed and the magnetic permeability μ is 2.0 ≦ μ ≦
It is in the range of 4.0.
The toner for developing an electrostatic charge image according to any one of the above. 11. The electrostatic charge image developing device according to claim 10, wherein the electrostatic charge image developing device is used for printing characters used in a magnetic ink symbol identification system for reading information by magnetic characters using a magnetic reader. For toner.