JPH05297630A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To realize an electrostatic charge image developing toner having excellent low-temp. fixing property, offset resistance for a wide temp. range, and durability so that the toner can be enough used even in a high-temp. atmosphere in a small-size machine. CONSTITUTION:The toner contains a binder resin and a releasing agent. The binder resin consists of two kinds of resins. One is styrene-acryl copolymers having low viscosity and the other is styrene-acryl copolymers having high viscosity, and the mixing ratio is 50:50 to 90:10. The toner contains a THFinsoluble component by <10wt.% of the binder resin. The GPC (gel permeation chromatgraphy) of the THF-soluble component of the toner shows >=10 weight average mol.wt./number average mol.wt. (Mw/Mn), one mol.wt. peak MA between 5000-30000 mol.wt., one mol.wt peak MB between 200000-1000000, and the mol.wt. minimum Md between 30000-200000 mol.wt. with a relation of MB/MA=10 to 100. In the mol.wt. distribution curve, SA:SB:Sd=1:(0.2 to 0.8):(0.3 to 0.9).

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 electrostatic images in electrophotography, electrostatic recording, electrostatic printing and the like.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, US Pat. No. 2,297,691 and JP-B-42-23910 are known.
Many methods are known as described in JP-B No. 43-24748 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used and an electric latent image is formed on a photoreceptor by various means. And then developing the latent image with toner,
After transferring the toner image to a transfer material such as paper, if necessary,
The toner is fixed by heat, pressure, heat and pressure, or solvent vapor to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such a copying apparatus has begun to be used not only as a general-purpose copier for copying original documents but also as a printer as an output of a computer or a personal copy for individuals. ..

Therefore, smaller size, lighter weight, higher speed and higher reliability have been rigorously pursued, and machines have come to be composed of simpler elements in various respects. As a result, the performance required for the toner has become higher, and if the performance improvement of the toner cannot be achieved, a better machine cannot be established.

In order to satisfy the above requirements, it is impossible to meet unless the toner fixing property and offset resistance are further improved. This is difficult to achieve without improving the performance of the toner binder.

As a technique for fixing the toner binder and improving the offset property, for example, JP-A-56-1614 is known.
No. 4, in the molecular weight distribution by GPC, the molecular weight is 1
A toner containing a binder resin component having at least one maximum value in each region of 000 to 80,000 and a molecular weight of 100,000 to 2,000,000 has been proposed.

In JP-A-63-223662, THF-insoluble matter is contained in an amount of 10 to 60% by weight based on the binder resin, and the THF-soluble matter has a weight average molecular weight / number average molecular weight ( Mw / Mn) ≧
5, having a peak in the molecular weight range of 2,000 to 10,000, having a peak or shoulder in the molecular weight range of 15,000 to 100,000, and having a molecular weight of 10,000 or less in the binder resin.
A toner containing 50% by weight has been proposed. In this case, the pulverizability, the fixability, the filming and fusion on the photoconductor, the image property, and the offset resistance (particularly high temperature offset) are excellent, but further improvement in the offset resistance and the fixability of the toner is demanded. .. In addition, miniaturization of the machine requires that each element be accommodated in a narrow space, which reduces the space where air flows well, and the heat source of the fixing device and exposure system is very close to the toner hopper, etc. Easy to be exposed to the atmosphere. Therefore, it cannot be put to practical use unless it is a toner having more excellent blocking resistance.

For example, various performances required of a toner, such as fixing property and blocking resistance, are almost in conflict with each other, and it is more and more desired and desired to satisfy both of them in high performance. I still don't have enough.

[0009]

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, an object of the present invention is to provide a toner for developing an electrostatic charge image, which is fixed at a low temperature and has excellent offset resistance in a wide temperature range from a low temperature to a high temperature.

Another object of the present invention is to provide a toner for developing an electrostatic image which is excellent in blocking resistance and can withstand use even in a high temperature atmosphere in a small machine.

Another object of the present invention is to provide a toner for developing an electrostatic charge image which does not cause fusing, filming and the like on a photoreceptor even after long-term use.

[0012]

According to the present invention, in a toner for developing an electrostatic image containing at least a binder resin and a releasing agent, the THF insoluble content of the toner is less than 10% by weight based on the binder resin. , Toner THF
Weight average molecular weight / number average molecular weight (Mw / in GPC (gel permeation chromatography) of the soluble component
Mn) ≧ 10, one molecular weight peak value MA between the molecular weights of 50,000 and 30,000, one molecular weight peak value MB between the molecular weights of 200,000 and 1,000,000, and between the molecular weights of 30,000 and 200,000. Each has a minimum molecular weight Md, and MB / MA = 10
100, the area of the molecular weight distribution curve from molecular weight 400 to Md is SA, the area of the molecular weight distribution curve from molecular weight Md to 5 million is SB, the straight line connecting the apex of the molecular weight peak MA and the apex of the molecular weight peak MB and the molecular weight distribution When the area surrounded by the curve is Sd, SA: SB: Sd =
The toner for developing an electrostatic charge image is 1: 0.2 to 0.8: 0.3 to 0.9.

In the toner, the number average molecular weight is 3,000 or less, the weight average molecular weight is 12,500 or less, and Mw /
The toner for developing an electrostatic charge image contains 0.1 to 20 parts by weight of a release agent having Mn ≦ 4.0 and a melting point of 60 ° C. to 150 ° C. based on the binder resin.

Further, in the above toner, the low-viscosity resin is obtained by the solution polymerization method and the high-viscosity resin is obtained by the suspension polymerization method, and the both are mixed in a solvent in which both are soluble. An image developing toner.

The THF insoluble content of the toner is less than 10% by weight, preferably 5% by weight, based on the binder resin.
It is below. If the THF insoluble content is 10% by weight or more, the offset resistance is improved but the fixability tends to be deteriorated, and it is difficult to satisfy both of them to a high degree. Further, the THF-soluble content of the toner is Mw / Mn ≧ 10 as measured by GPC molecular weight, and the molecular weight is 0.5.
One molecular weight peak value MA, molecular weight 20 between 10,000 and 30,000
It has one molecular weight peak value MB between 10,000 and 1,000,000, and a minimum molecular weight Md between molecular weight 30,000 and 200,000,
MB / MA = 10-100, and as shown in FIG.
The area of the molecular weight distribution curve from molecular weight 400 to Md is S
A, where the area of the molecular weight distribution curve from the molecular weight Md to 5,000,000 is SB, and the area surrounded by the straight line connecting the apex of the molecular weight peak value MA and the apex of the molecular weight peak value MB and the molecular weight distribution curve is Sd, SA: SB: Sd = 1: 0.2-
The case of 0.8: 0.3 to 0.9 is preferable.

If any of the above conditions is not satisfied, the object of the present invention cannot be achieved.

It is a case where Mw / Mn ≧ 10, preferably 12 or more, and more preferably 15 to 30. If Mw / Mn is less than 10, the fixability tends to be improved, but the offset resistance becomes poor, and fog, scattering, and density decrease occur due to toner deterioration.

Molecular weight of 50,000 to 30,000 and molecular weight of 200,000 to
One molecular weight peak value per 1 million (MA and M
B) and has a minimum value Md between the molecular weights of 30,000 and 200,000.
And preferably MB / MA = 10-100,
More preferably, the molecular weight is from 10,000 to 20,000 and from 400,000.
Each having one molecular weight peak value between 800,000, and
It has a minimum value of 100,000 to 250,000 and MB / MA = 15 to 7
This is the case of 0.

When these conditions are not satisfied, for example, when the molecular weight peak value MA is less than 50,000, blocking resistance becomes poor and filming or fusion bonding to the photoreceptor occurs, and MA is 3 or less. If it exceeds 10,000, the fixability may be poor.

Further, when the molecular weight peak value MB is less than 200,000, the offset resistance becomes poor, and a fusion product is generated in the apparatus in the crushing process, and when it exceeds 1,000,000, the fixability becomes poor. In addition, the crushability is poor and the productivity is poor.

Ratio of peak values of molecular weight MB / MA = 10
It is 100, preferably 15-70.

If MB / MA is less than 10 or more than 100, it becomes difficult to achieve both high fixability and high offset resistance.

Area ratio SA: SB: Sd of molecular weight distribution curve
= 1: 0.2-0.8: 0.3-0.9, preferably SA: SB: Sd = 1: 0.3-0.6: 0.3-
It is 0.8. If SB is less than 0.3, the offset resistance tends to be poor, and if it exceeds 0.8, the fixability tends to be poor and the pulverizability tends to be poor. If Sd is less than 0.3, the fixability and / or offset resistance tends to be poor, and if it exceeds 0.9, the offset resistance tends to be poor.

The release agent preferably used in the toner of the present invention is Mn ≦ 3000, Mw ≦ 1.255, Mw /
Mn ≦ 4.0, melting point 60 to 150 ° C., and 0.1 to 20 wt% based on the binder resin.

More preferably, Mn ≦ 2500 and Mw ≦
7,000, Mw / Mn ≦ 3.0, melting point 60 to 120 ° C.
And the release agent is 1 to 1 based on the binder resin.
This is the case of containing 0 part by weight.

When the release agent used in the toner of the present invention does not satisfy this condition, for example, when the melting point exceeds 150 ° C., the fixability is adversely affected, and when it is less than 60 ° C., the offset resistance and the toner blocking property are deteriorated. Adversely affect.

Further, when the content of the releasing agent exceeds 20 parts by weight, the blocking property and fixing property when the toner is left at a high temperature are adversely affected, and when the content is less than 0.1 parts by weight, the toner offset occurs. The preventive effect may be insufficient.

When the melt viscosity of the toner of the present invention is measured by a flow tester, the softening temperature Ts is 60 to 85 ° C., the outflow starting point Tfb is 95 to 120 ° C., and the 1/2 method temperature T1 / 2 is 125.
It is preferably in the range of ˜160 ° C. More preferably Ts
Is 65 to 80 ° C., Tfb is 100 to 115 ° C., and T 1/2 is 130 to 150 ° C.

The THF-insoluble matter in the present invention means the weight ratio of the polymer component (substantially crosslinked polymer) which becomes insoluble in the THF solvent in the toner. The THF-insoluble matter is defined as a value measured as follows.

That is, toner sample 0.5 to 1.0
g is weighed (W ₁ g), and a cylindrical filter paper (for example, Toyo filter paper N
o. 86R), put it in a Soxhlet extractor, and extract for 6 hours using 100 to 200 ml of THF as a solvent, evaporate the soluble component extracted by the solvent, and then vacuum dry at 100 ° C. for several hours to obtain a THF soluble resin component. Weigh the amount (W ₂ g). When the THF insoluble content of the toner is measured, it is determined from the following formula, where the weight of the component other than the resin component such as the pigment is (W ₃ g).

[0031]

[Equation 1] In the present invention, the peak or / and shoulder molecular weight of a chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF as a solvent was flowed through the column at this temperature at a flow rate of 1 ml / min to adjust the sample concentration to 0.05 to 0.6% by weight. The measurement is performed by injecting 50 to 200 μl of the THF sample solution of the resin. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared using several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Press
ure Chemical Co. Manufactured or manufactured by Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 10 ² , 2.1 × 10 ³ , 4 ×
10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 ×
10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10
^It is suitable to use 6,4.48 × 10 ⁶ standard polystyrene samples and at least about 10 points.
An RI (refractive index) detector is used as the detector.

As a column, 10 ³ to 2 × 10
^In order to accurately measure the molecular weight region of ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. In the present invention, the measurement is performed under the following conditions. GPC measurement conditions Device LC-GPC 150C (manufactured by Waters) Column KF801, 802, 803, 804
805, 806, 807 (manufactured by Shodex Co., Ltd.) with 7 columns at a temperature of 40 ° C. solv. THF (tetrahydrofuran) On the other hand, SA, SB, and Sd of the molecular weight distribution curve of the toner of the present invention were calculated by cutting out the chromatogram by GPC, calculating the weight ratio, subtracting the weight% of THF insoluble matter, and calculating the area ratio.

In the present invention, the release agent has a molecular weight distribution of G
It is measured by the PC under the following conditions. (GPC measurement conditions) Device GPC-150C (Waters Co.) Column Shodex KF-80M (Showa Denko KK) Temperature 135 ° C. Solvent o-dichlorobenzene (0.1% ionol added) Flow rate 1.0 ml / min Sample 0 0.4% injection of 0.15% sample is measured under the above conditions, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Furthermore, it is calculated by polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

In the present invention, the melting point of the release agent is DSC-
7 (manufactured by Perkin Elmer) using a differential scanning calorimeter at a temperature rising rate of 10 ° C./min and ASTM (D341).
The measurement was performed according to the temperature setting pattern of 8-82), and the temperature was set as the peak top position of the maximum melting temperature.

The measurement of the melting behavior of the binder resin is shown in FIG.
Elevated flow tester shown in (Shimadzu flow tester CF
(T-500 type), a sample 3 having a weight of 1.0 g, which was first molded using a pressure molding machine, was loaded with a load of 10 kgf by a plunger 1 at a temperature rising rate of 5.0 ° C./min and a diameter of 1 m.
It was made to push out from the nozzle 4 of m and 1 mm in length, and the plunger descent amount of the flow tester was measured by this.

At this time, when the height of the S-shaped curve in the plunger drop-temperature curve of the flow tester (refer to the flow tester outflow curve in FIG. 2) is h, the temperature at h / 2 is 1/2 point. , Ts is the softening point, and the temperature Tfb at the sample outflow starting point is the outflow starting temperature.

The method for measuring the glass transition point (Tg) in the present invention is DSC-7 (Perkin Elmer (Perki).
n Elmer) temperature rising rate of 10 ° C / min
In accordance with ASTM (D3418-82).

From the DSC curve at the time of the second temperature rise, Tg has the midpoint between the base line (1) before the endothermic peak and the base line (2) after the endothermic peak and the intersection of the rising curves as shown in FIG. It was Tg.

The resin composition in the toner of the present invention is preferably one obtained by polymerizing one or more kinds of monomers selected from styrenes, acrylic acids, methacrylic acids and their derivatives, from the viewpoint of developing characteristics and charging characteristics. Examples of monomers that can be used include styrene as styrene,
Examples include α-methylstyrene, vinyltoluene and chlorostyrene. Acrylic acid, methacrylic acid and their derivatives include acrylic acid, methyl acrylate,
Ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, n-tetradecyl acrylate, n-hexadecyl acrylate, lauryl acrylate, cyclohexyl acrylate, diethylaminoethyl acrylate, dimethyl acrylate Acrylic acid esters such as aminoethyl can be mentioned, as well as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate. , Decyl methacrylate, dodecyl methacrylate,
Lauryl methacrylate, cyclohexyl methacrylate,
Phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate,
Examples thereof include methacrylic acid esters such as stearyl methacrylate. In addition to the above-mentioned monomers, a small amount of other monomers such as acrylonitrile, 2-vinylpyridine, 4-vinylpyridine, etc. within a range that can achieve the object of the present invention.
Vinylcarbazole, vinyl methyl ether, butadiene, isoprene, maleic anhydride, maleic acid, maleic acid monoesters, maleic acid diesters, vinyl acetate and the like may be used.

The above-mentioned monomers can be polymerized in the presence of an initiator and in the presence or absence of a crosslinking agent. As the initiator, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxy) (Oxycarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5-dimethyl-2,
5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, Di-t-butyldiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butyl Peroxydimethyl glutarate, di-t-butyl peroxyhexahydroterephthalate, di-t-butyl peroxyazelate, 2,5-dimethyl-2,5-di (t-butyl peroxy) hexane, diethylene glycol-bis (T-butylperoxycarbonate), di-t-butylperoxytrimethyl adipate, tris (t-butylperoxy) tri Jin, vinyltris (t-butylperoxy) silane, cumene perpivalate, dicumyl peroxide, azobisisobutyronitrile, dimethyl azoisobutyrate, and the like, may be used they are used singly or in combination.

As the cross-linking agent used in the toner of the present invention, bifunctional cross-linking agents such as divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane,
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate , Triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), And those obtained by replacing the above acrylates with methacrylates.

As a polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxy, poly Ethoxyphenyl) propane, diallyl phthalate, triallyl cyanurate,
Examples include triallyl assocyanurate, triallyl isocyanurate, triallyl trimellitate, and diaryl chlorendate.

These cross-linking agents are preferably not contained at all in order to make the THF insoluble content of the toner less than 10% by weight.
The content is less than 0.5% by weight, preferably 0.5% by weight or less, more preferably 0.2% by weight or less.

The toner used in the present invention has a number average molecular weight Mn of 3.0 × 10 ³ or less and a weight average molecular weight Mw.
Is 1.25 × 10 ⁴ or less, Mw / Mn 4.0 or less, and a melting point mp in the range of 60 to 150 ° C., at least one release agent is added in an amount of 0.1 to 20 parts by weight with respect to the toner. Used.

The release agent preferably used in the toner of the present invention is, for example, paraffin wax, low molecular weight polyethylene wax, low molecular weight propylene wax, and polyolefin graft-modified with unsaturated fatty acid, styrene derivative or unsaturated fatty acid ester. Wax etc. are mentioned. Among them, the graft-modified polyolefin wax is particularly preferable from the viewpoints of a developer, a long life of a machine such as a copying machine using the developer, and free service maintenance.

The unsaturated fatty acid or unsaturated fatty acid ester used for synthesizing the graft-modified polyolefin includes methacrylic acid and methyl methacrylate, ethyl methacrylate, propyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, dodecyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate,
Diethylaminoethyl methacrylate, methacrylic acid-
2-Hydroxyethyl, 2,2,2-trifluoroethyl methacrylate, methacrylates such as glycidyl methacrylate, acrylic acid and methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, lauryl Acrylate, stearyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, 2-chloroethyl acrylate, 2-hydroxyethyl acrylate,
Acrylates such as cyclohexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dibutylaminoethyl acrylate, 2ethoxy acrylate, 1,4-butanediol diacrylate, maleic acid, fumaric acid, itaconic acid, citraconic acid, and monoethyl acrylate. Rate, diethyl malate, monopropyl maleate, dipropyl maleate, monobutyl maleate, dibutyl maleate, di-2 ethylhexyl malate, monoethyl fumarate, diethyl fumarate, dibutyl fumarate, di-2 ethylhexyl fumarate Unsaturated dibasic acid esters such as rate, monoethyl itaconate, diethyl itaconate, monoethyl citracone, diethyl citracone, etc. can be mentioned. One of these Rui can be used in combination of two or more thereof.

As the aromatic vinyl monomer, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, 2,4 dimethylstyrene, p-ethylstyrene, pn-butylstyrene, Examples thereof include p-tert-butylstyrene, pn-dodecylstyrene, p-phenylstyrene, and p-chlorostyrene, and one or more of these can be used at the same time.

As a method for graft modification, a conventionally known method can be used. For example, by reacting the above-mentioned polyolefin with an aromatic vinyl monomer and an unsaturated fatty acid or an unsaturated fatty acid ester in a solution or in a solvent under heating in the atmosphere or under pressure in the presence or absence of a radical initiator in the presence or absence of a radical initiator. Thus, a graft-modified polyolefin is obtained. The grafting with the aromatic vinyl monomer and the unsaturated fatty acid or unsaturated fatty acid ester may be carried out simultaneously or both individually.

The initiator used in the grafting reaction is
For example, benzoyl peroxide, dichlorobenzoyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl perphenyl acetate, cumin perpivalate, azobis-isobutyronitrile, dimethylazoisobutyrate,
Dicumyl peroxide and the like can be mentioned.

The toner used in the present invention comprises the above-mentioned constituent materials and has a number average molecular weight Mn of 3.0 × 10 ³ or less,
Weight average molecular weight Mw is 1.25 × 10 ⁴ or less, Mw / M
n4.0 or less, melting point mp. In addition to the mold releasing agent having a temperature range of 60 to 150 ° C., one or more mold releasing agents similar to the above constituent materials having a melting point of 140 ° C. or more may be mixed and used.

As the charge control agent used in the toner of the present invention, conventionally known positive or negative charge control agents are used. Charge control agents known in the art today include:

(1) The following substances control the toner to be positively charged.

Nigrosine, an azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), and a basic dye (for example, CI Basic Yellow 2).
(C.I. 41000), C.I. I. Basic Yel
low 3, C.I. I. Basic Red 1 (C.
I. 45160), C.I. I. Basic Red 9
(C.I. 42500), C.I. I. Basic Vio
let 1 (C.I. 42535), C.I. I. Basi
c Violet 3 (C.I. 42555), C.I.
I. Basic Violet 10 (C.I. 45
170), C.I. I. Basic Violet 14
(C.I. 42510), C.I. I. BasicBlue
1 (C.I. 42025), C.I. I. Basic B
lue 3 (C.I. 51005), C.I. I. Basi
c Blue 5 (C.I. 42140), C.I. I. B
asic Blue 7 (C.I. 42595), C.I.
I. Basic Blue 9 (C.I. 5201
5), C.I. I. Basic Blue 24 (C.I. 5
2030), C.I. I. Basic Blue 25
(C.I. 52025), C.I. I. Basic Blu
e 26 (C.I. 44025), C.I. I. Basic
Green 1 (C.I. 42040), C.I. I. B
lake pigments of these basic dyes such as asic Green 4 (C.I. 42000) (as lakers, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricia Compound, ferrocyanide, etc.),
C. I. Sovent Black 3 (C.I. 26
150), Hansa Yellow G (C.I. 11680),
C. I. Mordant Black 11, C.I.
I. Pigment Black 1 and the like.

Alternatively, for example, benzolmethyl-hexadecylammonium chloride, decyl-trimethylammonium chloride or dialkyltin compounds such as dibutyl and dioctyl, metal salts of higher fatty acids, inorganic fine powders of glass, mica and zinc oxide, EDTA and acetylacetone. Polyamine resins such as metal complexes, vinyl monomers containing amino groups, and condensation polymers containing amino groups.

Furthermore,

[0057]

[Chemical 1] Among quaternary ammonium salts represented by (R _{1 to} R ₄ are alkyl groups, aryl groups or their derivatives), those having a cation component having a molecular weight ratio of 55% or more, for example,

[0058]

[Chemical 2] Etc. are used.

Particularly, nigrosine, quaternary ammonium salt and the like are preferable from the viewpoints of charging property and dispersibility.

(2) The following substances control the toner to be negatively charged. Japanese Patent Publication No. 41-20153, 4
2-27596, 44-6397, 45-26
Examples thereof include metal complex salts of monoazo dyes described in No. 478 and the like.

Nitrohumic acid and salts thereof described in JP-A-50-133338 or C.I. I. 1464
5, etc., Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 5
No. 8-41508, Japanese Patent Publication No. 58-7384, Japanese Patent Publication No. 5
9-7384 and the like, salicylic acid, naphthoic acid, and dicarboxylic acid Zn, Al, Co, Cr, F
Metal complexes such as e, sulfonated copper phthalocyanine pigments, nitrile groups, halogen-introduced styrene oligomers and chlorinated paraffins. Particularly, from the viewpoint of dispersibility, metal complex salts of monoazo dyes, metal complexes of salicylic acid, alkylsalicylic acid, naphthoic acid, and dicarboxylic acid are preferable.

With the toner of the present invention, good results can be obtained even when additives are mixed if necessary. As the additive, for example, a lubricant such as Teflon, zinc stearate, or polyvinylidene fluoride, preferably polyvinylidene fluoride is preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferable. Alternatively, for example, fluidity-imparting agents such as colloidal silica, aluminum oxide and titanium oxide, and among them, hydrophobic colloidal silica is particularly preferable. There are anti-caking agents, conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide, tin oxide, etc., fixing aids such as low molecular weight polyethylene, low molecular weight polypropylene, various waxes, etc. or anti-offset agents.
Also, a small amount of reverse polarity white fine particles and black fine particles can be used as a developing property improver.

When the toner of the present invention is used as a magnetic toner, magnetite, γ-iron oxide,
Iron oxides such as ferrites, iron-rich ferrites; metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin,
Examples include alloys with metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, vanadium tungsten, and mixtures thereof. These ferromagnetic materials have an average particle size of 0.1.
To 0.2 μm, preferably 0.1 to 0.5 μm
Something is used. The amount of the magnetic material contained in the toner is 2 with respect to 100 parts by weight of the resin component.
It is used in the range of 0 to 200 parts by weight, preferably 40 to 120 parts by weight.

Any appropriate pigment or dye is used as the colorant used in the toner of the present invention.

Toner colorants are well known, and examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, red iron oxide, phthalocyanine blue, and indanthrene blue.

These are used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and the amount added is 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the resin. ..

Further, a dye is further used for the same purpose.
For example, there are azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, and the like.
The added amount is 1 to 20 parts by weight, preferably 0.3 to 3 parts by weight.

To prepare the toner according to the present invention, the resin composition according to the present invention, the charge control agent, the pigment or dye as a colorant, the additives, etc. are sufficiently mixed by a ball mill or other mixing machine and then heated. , A kneader, an extruder or the like is used to melt-knead the resin or the like to make them compatible with each other, and then the pigment or dye is dispersed or melted, cooled and solidified, and then ground and classified to have an average particle diameter of 3 to 20 μm.
Can be obtained.

[0069]

EXAMPLES Hereinafter, synthesis examples of low-viscosity polymers or high-viscosity polymers, production examples of binder resins, and examples relating to the toner of the present invention will be shown. In addition, "part" means "part by weight".

(Synthesis Example 1) 300 parts of xylene was placed in a reactor and heated to the reflux temperature. To this, a mixture of 90 parts of styrene monomer, 10 parts of butyl acrylate and 4.0 parts of benzoyl peroxide was added dropwise over 3 hours. Further, solution polymerization was completed under reflux of xylene, and xylene was removed. The obtained styrene-butyl acrylate copolymer had a weight average molecular weight (Mw) of 165,000 and a molecular weight peak value (MA) of 15,000. This is designated as a low-viscosity polymer A-1 of the binder resin for the toner of the present invention.

(Synthesis Examples 2 to 5) Solution polymerization was carried out in the same manner as in Synthesis Example 1 using the monomer composition, the polymerization initiator and the solvent shown in Table 1, and the binder resin according to the present invention had a low viscosity weight. Combined A-2 to A-5 were obtained.

(Synthesis Example 6) Polyvinyl alcohol 0.2
200 parts of degassed water in which 1 part was dissolved was placed in a reactor, and 75 parts of a styrene monomer, 25 parts of a butyl acrylate monomer and 1 part of t-butyl peroxide were added to obtain a suspension dispersion liquid.

The suspension dispersion was heated under a nitrogen atmosphere and kept at 78 ° C. for 24 hours to complete the polymerization reaction. After cooling to room temperature, the polymer was filtered off, washed thoroughly with water, and then dehydrated and dried.

The obtained styrene-butyl acrylate copolymer had Mw = 863,000 and a molecular weight peak value (MB).
= 78,000.

This is designated as the high viscosity polymer B-1 of the binder resin according to the present invention.

(Synthesis Examples 7 to 10) Suspension polymerization was carried out in the same manner as in Synthesis Example 6 using the monomer composition and the polymerization initiator shown in Table 2 to give a high viscosity polymer B of the binder resin according to the present invention. -2
~ B-5 were obtained.

COMPARATIVE SYNTHESIS EXAMPLE 1 Comparison was carried out in the same manner as in Synthesis Example 1 except that 86 parts of styrene, 14 parts of butyl acrylate and 8 parts of azoisobutyronitrile were used, toluene was used as the solvent, and the reaction temperature was 110 ° C. Polymer-1 was obtained.

The Mw of this resin was 62,000 and the peak molecular weight (MA) was 56,000.

Next, production examples of the binder resin for the toner of the present invention will be described.

(Production Example 1) 80 parts of low viscosity polymer A-1 and 20 parts of polymer high viscosity B-1 are added to 200 parts of xylene with stirring. Then heat to about 60 ° C,
The low viscosity polymer A-1 and the high viscosity polymer B-1 are completely dissolved.

After stirring for about 2 hours, xylene was removed to obtain a binder resin 1.

(Production Examples 2 to 8 and Comparative Resin Production Examples 1 to 1)
3) Binder resins 2 to 8 and comparative binder resins 1 to 3 relating to the toner of the present invention were obtained in the same manner as in Production Example 1 except that the polymers shown in Table 3 were used.

Example 1 Binder resin 1 100 parts Aniline black 5 parts Quaternary ammonium salt 1 part Low molecular weight polypropylene 3 parts After premixing the above materials in a Henschel mixer, 130 parts
The mixture was melt-kneaded by a twin-screw kneading extruder heated to 0 ° C., then cooled, pulverized by an air stream type pulverizer, and classified by an air classifier to obtain a black fine powder having a weight average particle diameter of 11.5 μm. 2.0 parts of amino-modified silicon oil-treated silica was externally added to 100 parts of the black fine powder to obtain a toner.

The THF insoluble content of this toner is 2.2% by weight.
And Mw / Mn = 2 according to GPC of the THF soluble component.
5.0, molecular weight peak MA = 13,000, molecular weight peak value MB = 653,000, molecular weight distribution curve SA: SB: Sd =
It was 1: 0.25: 0.65.

Also, Mn = 5 of the release agent used in this example.
50, Mw = 1410, Mw / Mn = 2.58,
The melting point was 102 ° C.

This toner is used as a copying machine F manufactured by Canon Inc.
A C-2 developing device shown in FIG. 5 was used, and a fixing device was modified so that the temperature was variable, and a copy test was conducted to examine the minimum fixing temperature, hot offset generation temperature, image quality and the like.

(1) Minimum Fixing Temperature Evaluation Method P. S49mm, Nip distance 2.5mm, Nip pressure 0.2
Under the condition of a fixing device of 6 kg / cm, the unfixed image is passed through the fixed image by changing the fixing temperature in steps of 5 ° C.
Rubbing 10 times with 0 g rubbing tester

[0088]

[Equation 2] The temperature below 10% is the minimum fixing temperature.

(2) Hot Offset Occurrence Temperature Evaluation Method Under the same fixing device conditions as in (1), an image portion is offset to a half white portion of an image obtained from an original chart of a half character image and half solid white in an A4 image. The temperature of the fixing device at the time when it is visually confirmed that the offset occurs is the offset generation temperature.

The minimum fixing temperature of this developer was 150 ° C., and the hot offset generation temperature was 230 ° C., which was good. In addition, no fusing or fogging was observed on the developer carrier or the photoconductor even after the image formation durability of 3000 sheets under the normal fixing device setting (the same temperature as (1) and temperature of 200 ° C.). No image deterioration such as deterioration was observed.

Example 2 Binder resin 2 100 parts Magnetic material 80 parts Nigrosine dye 2 parts Graft modified wax 4 parts Black fine powder 100 using the above materials in the same manner as in Example 1.
To 1.5 parts of hydrophobically treated silica was externally added to obtain a toner.

The THF insoluble content of this toner is 3.0% by weight.
And Mw / Mn = 28.
6, molecular weight peak MA = 10,000, molecular weight peak MB =
58.0 million, area ratio of molecular weight distribution curve SA: SB: Sd
= 1: 0.43: 0.75. The graft-modified wax used in this example is a polyethylene wax graft-modified with styrene and dibutyl fumarate and has a Mn content.
= 900, Mw = 1700, Mw / Mn = 1.90, and the melting point was 100 ° C.

This developer is used as a copying machine N manufactured by Canon Inc.
When the image was evaluated on P1215, no fusion or the like was observed on the developer carrier or the photoconductor even after 1000 sheets were printed and durability, and no image deterioration such as fog or reduction in image density was observed.

With respect to the fixing property and the offset property, an unfixed image was obtained without passing through the fixing device, and the unfixed image was passed through the fixing device of the FC-2 modified machine used in Example 1 and evaluated in the same manner as in Example 1. .. The minimum fixing temperature was 140 ° C and the hot offset generation temperature was 220 ° C, which were good.

Examples 3 to 5 Toners were obtained in the same manner as in Example 1 except that the binder resin and the releasing agent shown in Tables 4 and 5 were used. The evaluation results are shown in Table 6.

[0096]

[Table 1]

[0097]

[Table 2]

[0098]

[Table 3]

[0099]

[Table 4]

[0100]

[Table 5]

[0101]

[Table 6]

[0102]

As described above, according to the toner of the present invention,
It enables low temperature fixing and has a wide non-offset area. On the other hand, even when used for a long period of time, a good image can be stably provided without causing a decrease in density, fog or the like.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an elevated flow tester.

FIG. 2 is a diagram showing a plunger drop amount-temperature curve.

FIG. 3 is a diagram showing a DSC curve for obtaining Tg.

FIG. 4 is an explanatory diagram of a molecular weight distribution curve by GPC.

FIG. 5 is a schematic view of a developing device.

(72) Inventor Masashi Jimbo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Tsutomu Onuma 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (3)

[Claims] 1. A toner for developing an electrostatic image comprising at least a binder resin and a release agent, wherein the binder resin comprises two kinds of a styrene-acrylic copolymer low viscosity resin and a high viscosity resin. Mixing ratio is 50:50
˜90: 10, the THF insoluble content of the toner is less than 10% by weight based on the binder resin, and the THF soluble content of the toner in GPC (gel permeation chromatography) weight average molecular weight / number average molecular weight (Mw). / M
n) ≧ 10, one molecular weight peak value MA in the molecular weight range of 5,000 to 30,000, one molecular weight peak value MB in the molecular weight range of 200,000 to 1,000,000, and a minimum molecular weight value in the molecular weight range of 30,000 to 200,000. Each has Md, MB / MA = 10-1
00, the area of the molecular weight distribution curve from molecular weight 400 to Md is SA, the area of the molecular weight distribution curve from molecular weight Md to 5,000,000 is SB, and a straight line connecting the apex of the molecular weight peak value MA and the apex of the molecular weight peak value MB. When the area surrounded by the molecular weight distribution curve is Sd, SA: SB: Sd =
1. 0.2 to 0.8: 0.3 to 0.9 2. A low-viscosity resin is obtained by a solution polymerization method and a high-viscosity resin is obtained by a suspension polymerization method, and both are mixed in a solvent in which both are soluble, and Mn ≦ 3000, Mw ≦ 1.
The toner according to claim 1, wherein 0.1 to 20 parts by weight of a release agent having a Mw / Mn ≦ 4 and a melting point of 60 to 150 ° C. is used on the basis of the binder resin. 3. A flow tester having a softening temperature Ts of 60 to 85 ° C. and an outflow starting temperature Tfb of 95 to 120 ° C.
The toner according to claim 1 or 2, which has a 1/2 method temperature T1 / 2 of 125 to 160 ° C and a Tg of 50 ° C or higher.