JP2000172010A - Binder resin for toner and manufacture of same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the binder resin for the toner small in odor and superior in chargeability stability and the method for manufacturing it. SOLUTION: The toner binder resin is made of a styrene-acrylic copolymer or its mixture and the total volatile component is <=1500 ppm of the binder resin. After the copolymerization of this copolymer has been performed, the copolymer is heat treated to a temperature of >=110 deg.C under pressure to eliminate the volatile component out of the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a binder resin for toner used for developing an electrostatic image or a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like, and a method for producing the same. More specifically, the present invention relates to a toner binder resin having a low odor and excellent charge stability, and a method for producing the same.

[0002]

2. Description of the Related Art In a typical image forming process by an electrophotographic method or an electrostatic printing method, a photoconductive insulating layer is uniformly charged, the insulating layer is exposed, and then a charge on an exposed portion is obtained. To form an electric latent image by dissipating the toner, and a developing step of visualizing the latent image by adhering a finely charged toner to the latent image, and transferring the obtained visible image to a transfer material such as transfer paper. It comprises a transfer step of transferring and a fixing step of permanently fixing by heating or pressing.

Various performances are required for the toner and the binder resin for the toner used in the electrophotographic method or the electrostatic printing method in each of the above steps. For example, in the development process, the toner and the binder resin for the toner maintain a charge amount suitable for a copying machine without being affected by the surrounding environment such as temperature and humidity in order to attach the toner to the electric latent image. I have to do it. Also,
In the fixing step by the heat roller fixing method, the non-offset property that does not adhere to the heat roller and the fixability to paper must be good. Further, it is required to have a blocking resistance so that the toner does not block during storage in a copying machine.

In a copying machine, a printer, a facsimile, and the like used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, usually, a toner is heated using a heating roller heated to a temperature of about 100 to 230 ° C. Is fixed on paper.
In such a fixing process, fixing is often performed on a large number of sheets of paper or the like continuously, and a very small amount of toner that does not affect non-offset properties is accumulated on the heating roller. Then, the temperature of the heating roller increases due to continuous rotation and continuous supply of paper and the like, and the toner accumulated on the heating roller is heated, thereby evaporating residual monomers and residual solvent remaining in the toner. And produces odor. recent years,
Applications of electrophotography and the like have been advanced, and copiers, printers, facsimile machines, and the like have become popular and have been used in closed offices and homes. For this reason,
Low odor during image formation and image fixation is required.
Even during the production of a toner in which a binder resin and other additives are kneaded by a kneader or a ruder, there is a strong demand for low odor.

[0005]

Conventionally, a styrene-acrylic copolymer has been frequently used as a binder resin for a toner, and such a problem of odor is caused by the residual monomer and the residual monomer contained in the binder resin for a toner. Due to the solvent, reduction of the residual monomer and the residual solvent of the binder resin is attempted.

The reduction of the residual monomer and the residual solvent of the binder resin is described, for example, in Japanese Patent Application Laid-Open No. 1-70765.
As described in Japanese Patent Application Laid-Open Publication No. H10-260, a method of heating at a temperature equal to or higher than the glass transition temperature of a resin obtained after polymerization, and distilling off a predetermined amount of water to reduce residual monomers to reduce odor and the like. Proposed. Also, JP-A-7-10
JP-A-4514 and JP-A-8-41123 also propose a method for reducing odor by reducing volatile components such as residual monomers and residual solvents. Further, Japanese Unexamined Patent Publication No.
As described in Japanese Patent No. 101745 and Japanese Patent Application Laid-Open No. 3-101746, a method has been proposed in which benzaldehyde contained in a binder resin for toner is reduced to reduce odor.

However, in the method described in Japanese Patent Application Laid-Open No. 1-70765, volatile components having a boiling point of less than 150 ° C. can be efficiently reduced, but it is difficult to remove volatile components having a high boiling point, and sufficient odor reduction is achieved. Could not be planned. Further, in the method of distilling a predetermined amount of water, the stability of the treatment may be extremely deteriorated, and about 5% by weight of resin particles having a particle size exceeding 1000 μm may be contained. Therefore, there is also a problem that the chargeability of the toner is reduced. Japanese Unexamined Patent Publication No. Hei.
No. 65, JP-A-7-104514 and JP-A-8-41123 only reduce the amount of monomers and solvents remaining in the resin after the polymerization, and consider other volatile components that cause odor. No particular consideration was given, and sufficient low odor could not be achieved. Furthermore, in the methods described in JP-A-3-101745 and JP-A-3-101746, benzaldehyde can be reduced, but other volatile components cannot be sufficiently removed, and sufficient odor reduction cannot be achieved. I couldn't do it. SUMMARY OF THE INVENTION An object of the present invention is to provide a toner binder resin having a low odor and having excellent charge stability as toner.

[0008]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies on a binder resin for toner. As a result, the problem of odor was found to be caused by the residual monomer, residual solvent and benzaldehyde contained in the binder resin. It is possible to obtain a toner having a low odor by reducing other volatile components as well as a binder resin for toner having excellent charge stability as toner. And arrived at the present invention. That is, the binder resin for a toner of the present invention comprises a styrene-acrylic copolymer or a mixture thereof, and is characterized in that the total content of volatile components is 1500 ppm or less. Further, in the method for producing a binder resin for a toner according to the present invention, after performing polymerization of a styrene-acrylic copolymer, a heat treatment is performed under pressure at a temperature of 110 ° C. or more to collect volatile components outside the reaction system. And remove it.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The binder resin for a toner according to the present invention is characterized in that the total content of volatile components is 1500 ppm or less. This is because the total content of volatile components contained in the binder resin for toner is 1500 p.
If it exceeds pm, it is possible to reduce odor at the time of forming an image or fixing an image when kneading the resin with various additives in toner production, or when using the toner in a copier, a printer, a facsimile, or the like. For this reason, the content is preferably in the range of 1000 ppm or less, and more preferably in the range of 800 ppm or less.

[0010] Among the volatile components contained in the binder resin for toner, the volatile component having a benzene ring is the main cause of the odor, and the content of the volatile component having a benzene ring among the volatile components is 1400 ppm. The content is preferably set to the following, from the viewpoint of low odor, more preferably in the range of 1000 ppm or less, and more preferably in the range of 800 ppm or less. Further, among the volatile components having a benzene ring, the volatile components having a boiling point of less than 200 ° C. particularly cause odor, and in the present invention, the content of the volatile component having a benzene ring having a boiling point of less than 200 ° C. Is preferably not more than 500 ppm, more preferably not more than 450 ppm, and still more preferably not more than 400 ppm. In the present invention, the volatile component having a benzene ring having a boiling point of less than 200 ° C. includes t-butoxybenzene. Furthermore, the boiling point that causes the most odor is 150.
The content of volatile components having a benzene ring of less than 30 ° C is 30
0 ppm or less, preferably 250 ppm or less, more preferably 200 ppm or less.
The content is particularly preferably in the range of 100 ppm or less.

In the present invention, the volatile component having a benzene ring of less than 150 ° C. includes, for example, benzene, toluene, ethylbenzene, p-xylene, m-xylene,
o-xylene, styrene and the like. Further, as the volatile component having a benzene ring having a boiling point of 150 ° C. or more and less than 200 ° C., for example, cumene, n-propylbenzene,
Examples include allylbenzene, diethylbenzene, α-methylstyrene, benzaldehyde, styrene oxide, methyl benzoate, phenol and the like. Examples of the volatile component having a benzene ring having a boiling point of 200 ° C. or higher include acetophenone, naphthalene, α-methylbenzyl alcohol, dibenzyl, benzoic acid, phenyl benzoate, biphenyl and the like. Further, as volatile components having no benzene ring, acetone, t-butanol, butyl acetate, butyl propionate, n-butanol, acetic acid 2-
Examples include ethylhexyl, 2-hexylhexanol, other (meth) acrylic monomers and their decomposed products, and decomposed products of a polymerization initiator.

The binder resin for a toner of the present invention comprises a styrene-acrylic copolymer comprising a styrene monomer and another copolymerizable vinyl monomer. In the present invention, the styrene monomer used for the polymerization of the high molecular weight polymer component and the low molecular weight polymer component includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α- Methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn
-Hexylstyrene, pn-octylstyrene, p-
n-nonylstyrene, pn-decylstyrene, pn
-Dodecylstyrene, p-phenylstyrene, 3,4-
Examples thereof include dicyclosylstyrene, and among them, styrene is preferable. These styrene monomers can be used alone or in combination of two or more.

[0013] Other copolymerizable vinyl monomers include ethyl acrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate. , Ethyl methacrylate, methyl methacrylate,
Unsaturated monocarboxylic acid esters such as n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, dimethyl maleate, diethyl maleate,
And unsaturated dicarboxylic acid diesters such as butyl maleate, dimethyl fumarate, diethyl fumarate and dibutyl fumarate. In addition, acrylic acid, methacrylic acid, unsaturated monocarboxylic acids such as cinnamic acid, maleic acid,
Fumaric acid, unsaturated dicarboxylic acids such as itaconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monoethyl fumarate,
A carboxylic acid-containing vinyl monomer such as an unsaturated monocarboxylic acid monoester such as monobutyl fumarate can be used in combination.

Further, in the binder resin for a toner of the present invention, in order to form a tetrahydrofuran-insoluble component, a crosslinkable monomer may be provided with a crosslinked structure,
Although a method such as metal cross-linking may be mentioned, it is preferable to introduce a cross-linked structure into the high molecular weight polymer component using a cross-linkable monomer. This is because when a crosslinked structure is introduced into the low molecular weight polymer component, the introduced crosslinked structure becomes brittle, and the non-offset property as a toner tends to decrease.

Examples of the crosslinking monomer used to form the tetrahydrofuran-insoluble component include divinylbenzene, ethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, tri Chi trimethylolethane tri (meth)
Acrylates and trimethylolpropane tri (meth) acrylate are exemplified.

The copolymerization ratio of these monomers is not particularly limited, but is preferably selected so that the glass transition temperature of the obtained binder resin for toner is in the range of 40 ° C. or higher. This is because if the glass transition temperature of the binder resin for a toner is less than 40 ° C., the blocking occurrence temperature of the toner is lowered, and the storage stability may be extremely lowered. Further, if the glass transition temperature of the binder resin for toner exceeds 80 ° C., the softening temperature tends to increase, and the fixability of the toner tends to decrease.
The temperature is in the range of 5 to 80 ° C, more preferably 50 to 65 ° C.
It is in the range of ° C.

The binder resin for a toner according to the present invention may have at least one peak in a molecular weight region of 4,000 to 50,000 in a chromatogram measured by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) -soluble component. It is preferable in terms of toner fixability, offset resistance and charging characteristics, and is more preferably a region having a molecular weight of 5,000 to 45,000,
More preferably, it is a region having a molecular weight of 6,000 to 40,000.

Further, from the viewpoint of the anti-offset property of the toner, a THF-insoluble component is contained in the range of 5 to 55% by weight, or the molecular weight in GPC is 80,000 to 500,000.
It is preferred that the high molecular weight polymer component having at least one peak be contained in the range of 10 to 60% by weight. This is because the content of the THF-insoluble component is 5% by weight.
If the amount is less than 50%, the melt viscosity of the toner tends to be low and sufficient offset resistance tends not to be imparted. On the other hand, if the amount exceeds 55% by weight, the melt viscosity of the toner increases and the fixability decreases. This is because the strength of the toner tends to increase and the pulverizability tends to decrease. On the other hand, if the content of the high molecular weight polymer component is less than 10% by weight, sufficient offset resistance tends not to be imparted even if the molecular weight is increased.
If the amount is more than 10% by weight, the fixability of the toner tends to decrease.

Further, the binder resin for a toner of the present invention has a weight average molecular weight in the range of 50,000 to 30,000,
The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 3 to 40, and the Z average molecular weight (M
z) and the number-average molecular weight (Mn) ratio (Mz / Mn) is 1
It is preferably in the range of 0 to 300, more preferably in the range of 70,000 to 200,000, Mw / Mn.
Is in the range of 5 to 30, and Mz / Mn is in the range of 15 to 250.

The binder resin for a toner of the present invention is prepared by subjecting a mixture of the above polymerizable monomers to a suspension polymerization method, a solution polymerization method,
It can be produced by a known polymerization method such as an emulsion polymerization method and a bulk polymerization method. Among them, those polymerized by the suspension polymerization method, without the problem of odor due to the residual solvent,
There are few ultra-low molecular weight components having a molecular weight of less than 3,000 which cause toner preservation, filming on a photoreceptor drum, and adhesion to a fixing roll, easy control of heat generation, use of a small amount of dispersant, and moisture resistance. This is preferable in that the properties are not impaired. In particular, from the viewpoint of reducing residual monomers, it is preferable to carry out suspension polymerization using two or more polymerization initiators having different half-life temperatures in combination. Furthermore, if a polymerization initiator remains in the obtained resin, the polymerization initiator may decompose during kneading or storage during toner production and generate volatile components. And 110 ° C. or higher, preferably 120 ° C. or higher, and more preferably 125 ° C. or higher, after being subjected to a heat treatment under high-temperature pressurization, gradually release the pressurized state while remaining a polymerization initiator and the like together with the remaining monomers and solvents. It is preferable to remove volatile components such as decomposition products by distilling them out of the reaction system. In order to pressurize the reaction system, pressure may be applied from the outside to the reaction system, or the reaction system may be closed using a reaction vessel such as an autoclave and heated to a desired temperature. Pressurized state. Further, the heat treatment under high temperature under pressure is not limited to performing a separate heat treatment step, and may be replaced with, for example, a step of raising the temperature to a desired temperature while keeping the reaction system closed.

The polymerization initiator used in the suspension polymerization is not particularly limited, and usually used radically polymerizable peroxides and azo compounds can be used. -Butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide Oxide, benzoyl peroxide, m-toluoyl peroxide, t-butyl peroxyacetate, t-
Butyl peroxyisobutyrate, t-butyl peroxypiparate, t-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy 3, 5,5-trimethylhexanoate, t-butyl paoxy acrylate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, azobisisobutylnitrile, 2,2-azobis-
(2,4-dimethylvaleronitrile), 2,2-bis (4,4-di-t-butylperoxycyclohexyl)
Propane, cyclohexanone peroxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, p-methane hydroperoxide, 2-
(Carbamoylazo) isobutyronitrile, 2,2-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile and the like. These polymerization initiators can be used alone or in combination of two or more.
It is preferably used in the range of 0.1 to 10 parts by weight, more preferably in the range of 0.5 to 10 parts by weight with respect to 00 parts by weight.

The suspension polymerization is preferably carried out with respect to the monomer.
10 to 10 times, more preferably about 2 to 4 times with water, adding a dispersant, a polymerization initiator, a dispersing aid or a chain transfer agent if necessary, and raising the temperature to a predetermined polymerization temperature, This is performed by continuing to heat until a predetermined polymerization rate is reached.

Examples of the dispersant used in the suspension polymerization include polyvinyl alcohol, an alkali metal salt of a homopolymer or copolymer of (meth) acrylic acid, carboxytyl cellulose, gelatin, starch, barium sulfate, calcium sulfate, and the like. Examples thereof include calcium carbonate, magnesium carbonate, and calcium phosphate. Among them, polyvinyl alcohol is preferable, and particularly preferable is partially saponified polyvinyl alcohol in which an acetic acid group and a hydroxyl group are present in a block manner. These dispersants are used in an amount of 0.0
It is preferable to use it in the range of 1 to 5 parts by weight. If the amount of the dispersant is less than 0.01 part by weight, the stability of suspension polymerization is reduced, and the polymer tends to be solidified by aggregation of the produced particles, and conversely, the amount exceeds 5 parts by weight. This is because the toner tends to have a lower environmental dependency, particularly the moisture resistance, and the content is more preferably in the range of 0.05 to 2 parts by weight. If necessary, a dispersing aid such as sodium chloride, potassium chloride, sodium sulfate and potassium sulfate can be used together with these dispersants. further,
In order to adjust the molecular weight, a chain transfer agent such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, 2-ethylhexyl thioglycolate, α-methylstyrene dimer may be used, if necessary. .

The styrene-acrylic copolymer thus obtained has an average particle diameter of 100 to 400 μm, and preferably has a particle diameter of 1000 μm or more and 5% by weight or less, more preferably. Average particle size is 1
It is in the range of 10 to 300 μm and the particle size is 1000 μm
Are in the range of 2% by weight or less. This is because if the average particle diameter is less than 100 μm, the fluidity during pre-mixing and kneading during the production of the toner is reduced, which tends to cause clogging in the feeder portion, and the scattering of fine particles. This tends to cause deterioration of the working environment. Conversely, if the average particle size exceeds 400 μm, the miscibility with additives such as pigments and charge control agents during pre-mixing during toner production tends to be impaired, and the image density of the toner tends to decrease. . Further, when the particle diameter is 1000
This is because, when the particle size of μm or more exceeds 5% by weight, the miscibility during pre-mixing during the production of toner tends to be extremely reduced.

In the present invention, the binder resin as described above can be used as a binder resin for various toners such as a two-component toner, a one-component toner, a magnetic toner and a non-magnetic toner. The toner is preferably contained in the toner in the range of 88 to 97% by weight, and more preferably in the range of 90 to 95% by weight. This is because when the content of the binder resin is less than 88% by weight, the non-offset property of the toner tends to decrease, and when it exceeds 97% by weight, the charging stability of the toner tends to deteriorate. is there.

The binder resin of the present invention can be used together with additives such as a coloring agent, a pigment, a charge control agent, an offset preventing agent, and magnetic powder, for example, by using a kneader such as a twin screw extruder or a mixer. 15-30 ° C below softening temperature
After kneading at a high temperature, fine pulverization and classification are performed to form a toner. The obtained toner particles have an average particle size of 5 to 20.
It is about μm, preferably about 8 to 15 μm, and it is preferable that the amount of fine particles having a particle size of 5 μm or less is less than 3% by weight. Colorants, pigments, charge control agents, anti-offset agents, magnetic powders used may be those that are commonly used, for example, carbon black, nigrosine dye, lamp black,
Colorants or pigments such as Sudan Black SM, Navel Yellow, Mineral First Yellow, Lithol Red, Permanent Orange 4R, etc., nigrosine, alkyl group-containing azine dyes, basic dyes, monoazo dyes or metal complexes thereof, salicylic acid or metal complexes thereof,
Charge control agents such as alkylsalicylic acid or its metal complex, naphthoic acid or its metal complex, polyethylene,
Examples include offset inhibitors such as polypropylene and ethylene-polypropylene copolymer, and magnetic powders such as ferrite and magnetite.

[0027]

The present invention will be specifically described below with reference to examples. Determination of volatile components other than benzene : 0.2 g of 3-methoxy-3-methylbutanol was added to 1 g of resin with acetone.
After adding 1 ml of the internal standard solution diluted to 0 ml, 15 ml of acetone was added, and the mixture was allowed to stand for 39 hours. Then 1
After shaking for 30 minutes and performing ultrasonic extraction for 30 minutes, shake for 6 hours and allow to stand for 68 hours, and use a supernatant as a measurement sample for gas chromatography (GC-14B manufactured by Shimadzu Corporation).
It measured using. The injection volume was 0.5 μl and SUPEL
SPWAX-10 (30m × 0.53mm ×
1.0 μm) and SUPELCO SPB-5 (30 m
× 0.53 mm × 1.5 μm) was used as a column and divided in parallel. The detector was a FID (hydrogen flame ion detector), and He was used as a carrier gas at a pressure of 0.3 kg / cm ² . The inlet temperature is 150 ° C and the detector temperature is 220 ° C.
After holding at 0 ° C for 3 minutes, 6 ° C from 40 ° C to 200 ° C
/ Min, and kept at 200 ° C. for 5 minutes.

Determination of benzene : 0.2 g of 3-methoxy-3-methylbutanol was diluted with 100 g of methyl isobutyl ketone (MIBK) in 1 g of resin and then 2 ml.
Was diluted to 100 ml with MIBK and added to 10 ml.
ml was added. Next, 5 ml of MIBK was added, shaken for 2 hours, and allowed to stand for 65 hours. Thereafter, ultrasonic extraction was performed for 30 minutes, shaken for 7 hours and allowed to stand for 41 hours, and the supernatant was used as a measurement sample using a gas chromatograph (model GC-14B manufactured by Shimadzu Corporation) in the same manner as described above. It was measured.

Measurement of THF-insoluble component : Celite 545
Glass filter (1G) filled with (Katayama Chemical Co., Ltd.)
-3 or 2G-3) was weighed (W1). Next, 50 ml of THF was added to about 0.5 g of the resin (W2) in the glass filter, and the THF solution heated at 60 ° C. for 3 hours was subjected to suction filtration. The THF-insoluble component remaining on the glass filter was completely washed away with acetone, and the glass filter filled with celite was washed at 80 ° C. for 3 hours.
Vacuum dried for more than an hour. Thereafter, the weight (W3) of the glass filter filled with the dried celite was weighed and calculated by the following equation.

THF insoluble component (% by weight) = ｛(W3-
W1) / W2｝ × 100 Molecular weight by gel permeation chromatography
Distribution : A resin solution of 0.04% by weight using THF as a solvent is coated with a PTFE membrane (Mythodisc H-25 manufactured by Tosoh Corporation).
5), and filtered through three columns (TSKgel manufactured by Tosoh Corporation).
/ GMH _XL column) and gel permeation chromatography (HCL-8020 manufactured by Tosoh Corporation)
Measured at a temperature of 38 ° C. by F2000 / F700 /
F288 / F128 / F80 / F40 / F20 / F2 /
It was determined in terms of polystyrene by a calibration curve using A1000 (polystyrene manufactured by Tosoh Corporation) and a styrene monomer. The measurement temperature was 38 ° C., and the detector was RI.

Glass transition temperature : After the sample was heated to 100 ° C. and melt quenched, the DSC method (heating rate 10
° C / min).

Softening temperature : Flow tester having a nozzle of 1 mmφ × 10 mm (CFT-50 manufactured by Shimadzu Corporation)
0), the load was 30 Kgf, and the temperature was raised at a rate of 3 ° C./min.

Fixing temperature range : An unfixed image obtained by a copying machine (GP-1570 manufactured by Panasonic Corporation) is fixed at a fixing speed of 150 mm using a fixing tester with a variable roller temperature.
Per second, the fixed toner image is rubbed nine times with a sand eraser (JIS 512), and the image density before and after that is measured with a Macbeth densitometer. (Fixing lower limit temperature) and the minimum temperature at which toner transfers to the roller (fixing upper limit temperature).

Image fog: The white portion of the image obtained at the time of evaluation of the fixing temperature region was visually evaluated according to the following criteria. ：: No problem. Δ: Somewhat problematic but practical. ×: Not reaching a practical level.

Resin odor : 10 g of resin was placed in a 200 cc closed glass container and heated at 180 ° C. for 1 hour.
The odor of the resin under heating was evaluated according to the following criteria. ：: Almost no odor is felt. Δ: Slight odor is felt. X: Odor is felt.

Toner odor : After a copier (GP-1570 manufactured by Panasonic Corporation) was installed in the center of a room of about 32 m ² and solid printing was performed on 10 sheets, a sensory test was conducted by 10 persons randomly selected. went. The sensory test was as follows: 0 if no odor was felt at all, 1 point if there was a slight odor but not unpleasant, and 2 points if it was odorous and unpleasant. The evaluation was performed based on the following criteria. ：: 0 to 5 points Δ: 5 to 10 points X: 11 to 20 points Particle diameter of resin : average particle diameter is 1000 μm,
710 μm, 500 μm, 355 μm, 250 μm, 1
50 μm and 75 μm sieves were attached in this order, and 500 g of the sample was sieved using a vibrator to show a value of the cumulative particle size distribution of 50% by weight. The amount of the particles having a particle diameter of 1000 μm or more was determined by measuring the mass of the particles remaining on the sieve having an opening of 1000 μm and dividing the g number by 500.

Example 1 A 4 liter autoclave was charged with 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). The mixed solution was charged. Then, 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.31 part of divinylbenzene
In a monomer mixture consisting of 5 parts by weight, 3 parts by weight of benzoyl peroxide as a polymerization initiator was dissolved and charged into an autoclave while stirring. Next, the reaction system was closed, the temperature was raised to 85 ° C., and suspension polymerization was performed for 4 hours. Then, heat treatment was performed while raising the temperature to 130 ° C. over 30 minutes, and the pressurized state of the reaction system was gradually reduced. While open, volatile components were distilled out of the system via a condenser for 10 minutes. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, THF-insoluble component amount, THF-soluble component molecular weight distribution peak, weight average molecular weight (Mw), weight average molecular weight (M) of the obtained styrene-acrylic copolymer
w) and the number average molecular weight (Mn) (Mw / Mn), the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) (Mz /
Table 1 shows the measurement results of Mn) and the particle diameter, and the evaluation results of the odor.
It was shown to. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Example 2 Into a 4 liter autoclave, 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were added. The mixed solution was charged. Then, 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.31 part of divinylbenzene
In a monomer mixture consisting of 5 parts by weight, 3 parts by weight of benzoyl peroxide as a polymerization initiator was dissolved and charged into an autoclave while stirring. Next, the reaction system was closed, the temperature was raised to 85 ° C., and suspension polymerization was performed for 4 hours. Then, heat treatment was performed while raising the temperature to 130 ° C. over 30 minutes, and the pressurized state of the reaction system was gradually reduced. The volatile components were distilled out of the system via the condenser for 30 minutes while being opened. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, THF-insoluble component amount, THF-soluble component molecular weight distribution peak, weight average molecular weight (Mw), weight average molecular weight (M) of the obtained styrene-acrylic copolymer
w) and the number average molecular weight (Mn) (Mw / Mn), the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) (Mz /
Table 1 shows the measurement results of Mn) and the particle diameter, and the evaluation results of the odor.
It was shown to. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Example 3 A 4 liter autoclave was charged with 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). The mixed solution was charged. Then, 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.31 part of divinylbenzene
In a monomer mixture consisting of 5 parts by weight, 3 parts by weight of benzoyl peroxide as a polymerization initiator was dissolved and charged into an autoclave while stirring. Next, the reaction system was closed, the temperature was raised to 85 ° C., and suspension polymerization was performed for 4 hours. Then, heat treatment was performed while raising the temperature to 130 ° C. over 30 minutes, and the pressurized state of the reaction system was gradually reduced. The volatile components were distilled out of the system through the condenser for 60 minutes while being opened. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, THF-insoluble component amount, THF-soluble component molecular weight distribution peak, weight average molecular weight (Mw), weight average molecular weight (M) of the obtained styrene-acrylic copolymer
w) and the number average molecular weight (Mn) (Mw / Mn), the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) (Mz /
Table 1 shows the measurement results of Mn) and the particle diameter, and the evaluation results of the odor.
It was shown to. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 140 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Example 4 A 4 liter autoclave was charged with 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.). The mixed solution was charged. Then, a monomer mixture consisting of 75 parts by weight of styrene, 25 parts by weight of n-butyl acrylate and 0.3 parts by weight of divinylbenzene was added to 3.5 parts by weight of benzoyl peroxide and 0 parts of t-butyl peroxybenzoate as a polymerization initiator. 0.5 part by weight was dissolved and charged into the autoclave while stirring. Next, the reaction system was closed, the temperature was raised to 85 ° C., and suspension polymerization was performed for 2 hours.
The heat treatment was performed while the temperature was raised to 130 ° C. over 30 minutes, and the volatile components were distilled out of the system via a condenser for 90 minutes while gradually releasing the pressurized state of the reaction system. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, THF-insoluble component amount, THF-soluble component molecular weight distribution peak, weight average molecular weight (Mw), weight average molecular weight (M) of the obtained styrene-acrylic copolymer
w) and the number average molecular weight (Mn) (Mw / Mn), the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) (Mz /
Table 1 shows the measurement results of Mn) and the particle diameter, and the evaluation results of the odor.
It was shown to. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.) and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 140 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Example 5 Into a 4 liter autoclave, 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were added. The mixed solution was charged. Then, 32.5 parts by weight of styrene,
To a monomer mixture consisting of 7.5 parts by weight of n-butyl acrylate and 0.02 parts by weight of divinylbenzene, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane was used as a polymerization initiator. 0.024 parts by weight of (Perkadox 12 manufactured by Kayaku Akzo) was dissolved and charged into an autoclave with stirring. Then, the temperature of the reaction system was increased to 130 ° C. in a closed state, and suspension polymerization of the high molecular weight polymer component was performed for 2 hours. Further, 56 parts by weight of styrene in the suspension of the high molecular weight polymer component cooled to 40 ° C.
A mixture of 4 parts by weight of n-butyl acrylate, 6 parts by weight of benzoyl peroxide and 1 part by weight of t-butyl peroxybenzoate was added, and the reaction system was kept closed. Suspension polymerization of the polymer component was performed. Then, while gradually releasing the pressurized state of the reaction system, the volatile components were distilled out of the system via the condenser for 60 minutes. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, amount of THF insoluble component, molecular weight distribution peak of THF soluble component, weight average molecular weight (Mw), weight average molecular weight (Mw) and number average molecular weight of the obtained styrene-acrylic copolymer (Mn) ratio (Mw /
Mn), Z-average molecular weight (Mz) and number-average molecular weight (Mn)
Table 1 shows the measurement results of the ratio (Mz / Mn) and the particle size, and the evaluation results of the odor. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.) and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Example 6 In a 4 liter autoclave, 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were added. The mixed solution was charged. Next, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane (a chemical agent) was added to a monomer mixture consisting of 24 parts by weight of styrene and 6 parts by weight of n-butyl acrylate as a polymerization initiator. Parkox 12 manufactured by Akzo Co., Ltd. 12) 0.018 part by weight was dissolved and charged into an autoclave with stirring. Next, the reaction system was closed, and the temperature was raised to 130 ° C., and suspension polymerization of the high molecular weight polymer component was performed for 2 hours. Further, styrene 65 was added to the suspension of the high molecular weight polymer component cooled to 40 ° C.
Parts by weight, a mixed solution of 5 parts by weight of n-butyl acrylate, 6 parts by weight of benzoyl peroxide and 1 part by weight of t-butyl peroxybenzoate were added, and the reaction system was sealed.
The temperature was raised to 30 ° C., and suspension polymerization of the low molecular weight polymer component was performed for 2 hours. Then, while gradually releasing the pressurized state of the reaction system, the volatile components were distilled out of the system via a condenser.
Performed for 0 minutes. Then, cool down to room temperature, wash thoroughly,
After dehydration and drying, a styrene-acrylic copolymer was obtained. Glass transition temperature, softening temperature, amount of THF insoluble component, molecular weight distribution peak of THF soluble component, weight average molecular weight (Mw), weight average molecular weight (Mw) and number average molecular weight of the obtained styrene-acrylic copolymer (Mn) ratio (M
w / Mn), Z-average molecular weight (Mz) and number-average molecular weight (M
Table 1 shows the measurement results of the ratio (Mz / Mn) and the particle size of n) and the evaluation results of the odor. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Comparative Example 1 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were placed in a 4 liter autoclave. The mixed solution was charged. Then, 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.31 part of divinylbenzene
In a monomer mixture consisting of 5 parts by weight, 3 parts by weight of benzoyl peroxide as a polymerization initiator was dissolved and charged into an autoclave while stirring. Next, the reaction system was closed, the temperature was raised to 85 ° C., and suspension polymerization was performed for 4 hours, then cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. I got Glass transition temperature, softening temperature, THF-insoluble component amount, THF-soluble component molecular weight distribution peak, weight average molecular weight (Mw), weight average molecular weight (M) of the obtained styrene-acrylic copolymer
w) and the number average molecular weight (Mn) (Mw / Mn), the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) (Mz /
Table 1 shows the measurement results of Mn) and the particle diameter, and the evaluation results of the odor.
It was shown to. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.) and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Comparative Example 2 In a 4 liter autoclave, 200 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were added. The mixed solution was charged. Then, 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.31 part of divinylbenzene
In a monomer mixture consisting of 5 parts by weight, 3 parts by weight of benzoyl peroxide as a polymerization initiator was dissolved and charged into an autoclave while stirring. Next, the reaction system was sealed, and the temperature was raised to 85 ° C. to perform suspension polymerization for 4 hours. Then, the temperature was raised to 130 ° C. and maintained for 120 minutes. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, THF-insoluble component amount, THF-soluble component molecular weight distribution peak, weight average molecular weight (Mw), weight average molecular weight (M) of the obtained styrene-acrylic copolymer
w) and the number average molecular weight (Mn) (Mw / Mn), the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) (Mz /
Table 1 shows the measurement results of Mn) and the particle diameter, and the evaluation results of the odor.
It was shown to. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Comparative Example 3 300 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were placed in a 4-liter glass flask. Was added. Then, 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.3 part of divinylbenzene
In a monomer mixture consisting of 15 parts by weight, 3 parts by weight of benzoyl peroxide as a polymerization initiator were dissolved and charged into a glass flask with stirring. After raising the temperature to 85 ° C. to perform suspension polymerization for 4 hours, the temperature was raised to 103 ° C. and 120% by weight of water was distilled out of the system via a condenser for 120 minutes through the condenser. did. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, THF of the obtained styrene-acrylic copolymer
Insoluble component amount, molecular weight distribution peak of THF soluble component, weight average molecular weight (Mw), ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn), Z average molecular weight (M
Table 1 shows the measurement results of the ratio (Mz / Mn) of z) to the number average molecular weight (Mn) and the particle size, and the evaluation results of the odor. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Comparative Example 4 300 parts by weight of deionized water and 0.2 part by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) were placed in a 4-liter glass flask. Was added. Then, 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.3 part of divinylbenzene
In a monomer mixture consisting of 15 parts by weight, 3 parts by weight of benzoyl peroxide as a polymerization initiator were dissolved and charged into a glass flask with stirring. After raising the temperature to 85 ° C. and performing suspension polymerization for 4 hours, the temperature was raised to 103 ° C. and 480 minutes, 50% by weight of water based on the amount of water at the end of the polymerization was distilled out of the system via a condenser. did. Thereafter, the mixture was cooled to room temperature, sufficiently washed, dehydrated, and dried to obtain a styrene-acrylic copolymer. Glass transition temperature, softening temperature, THF of the obtained styrene-acrylic copolymer
Insoluble component amount, molecular weight distribution peak of THF soluble component, weight average molecular weight (Mw), ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn), Z average molecular weight (M
Table 1 shows the measurement results of the ratio (Mz / Mn) of z) to the number average molecular weight (Mn) and the particle size, and the evaluation results of the odor. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.) and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

Comparative Example 5 After dissolving 3 parts by weight of benzoyl peroxide as a polymerization initiator in a monomer mixture consisting of 74 parts by weight of styrene, 26 parts by weight of n-butyl acrylate and 0.315 part by weight of divinylbenzene. Partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
270 parts by weight of deionized water in which 2 parts by weight were dissolved was added to obtain a suspension dispersion. In a 4 liter glass flask,
30 parts by weight of deionized water are charged, nitrogen is introduced through a nitrogen inlet tube, and the concentration of dissolved oxygen is set at 1.degree.
Nitrogen was allowed to flow at 3 mg / L (measured using a YSI DO meter manufactured by Nikkaki Co., Ltd.). In this state,
The suspension dispersion was added to the glass flask, the temperature was raised to 85 ° C., and the suspension polymerization was carried out for 9 hours. After that, the temperature was raised to 103 ° C., and the amount of water at the end of the polymerization was reduced via a condenser for 480 minutes. On the other hand, 50% by weight of water was distilled out of the system. afterwards,
Cool to room temperature, wash thoroughly, dehydrate, dry,
A styrene-acrylic copolymer was obtained. Glass transition temperature, softening temperature of the obtained styrene-acrylic copolymer,
THF-insoluble component amount, THF-soluble molecular weight distribution peak, weight average molecular weight (Mw), weight average molecular weight (Mw)
And the ratio of the number average molecular weight (Mn) (Mw / Mn), the ratio of the Z average molecular weight (Mz) and the number average molecular weight (Mn) (Mz / M
Table 1 shows the measurement results of n) and the particle diameter, and the evaluation results of the odor. Table 2 shows the measurement results of the volatile components.

The obtained styrene-acrylic copolymer was used as a binder resin in 93 parts by weight, 4 parts by weight of carbon black (Mitsubishi Kasei's # 40) and a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industries, Ltd.). 1) 1 part by weight and polypropylene wax (660P manufactured by Sanyo Chemical Industries, Ltd.)
2 parts by weight, and about 5 ° C. at 150 ° C. using a twin screw extruder.
Melted and kneaded for minutes. Next, it was pulverized using a jet mill pulverizer and classified to obtain a toner having an average particle diameter of 13 μm. Table 3 shows the evaluation results of the fixing temperature range, image fog, and odor of the obtained toner.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

According to the present invention, a binder for toner having low odor and excellent charge stability can be obtained by reducing the content of volatile components contained in a binder resin, particularly the content of volatile components having a benzene ring. In addition to providing a resin, it is possible to provide a production method capable of efficiently producing such a binder resin for a toner.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Junya Nakamura 4-1-1 Ushikawa-dori, Toyohashi-shi, Aichi F-term (reference) in Toyohashi Works, 2R005 AA01 AB06 AB09 CA04 CA30 EA03 EA07 4J002 BC071 BC081 BC091 BC111 BG041 BG051 BH011 4J015 AA02 BA03 4J100 AB02P AB03P AB04P AB07P AB16Q AL03Q AL04Q AL05Q AL34Q AL62Q AL63Q AL66Q BA02Q BA08Q BC43P CA04 CA23 DA00 DA58 FA03 GC25 GC29 JA09

Claims (7)

[Claims] 1. A styrene-acrylic copolymer or a mixture thereof, wherein the total content of volatile components is 1500 pp.
m or less. 2. The binder resin according to claim 1, wherein the content of the volatile component having a benzene ring is 1400 ppm or less. 3. The binder resin according to claim 1, wherein the content of a volatile component having a benzene ring and having a boiling point of less than 200 ° C. is 500 ppm or less. 4. The binder resin according to claim 1, wherein the content of a volatile component having a benzene ring and having a boiling point of less than 150 ° C. is 300 ppm or less. 5. After the polymerization of the styrene-acrylic copolymer, a heat treatment is performed under pressure at a temperature of 110 ° C. or higher, and volatile components are distilled out of the reaction system and removed. Of producing a binder resin for a toner. 6. The toner according to claim 5, wherein after the heat treatment is performed in a state where the reaction system is sealed, the volatile component is distilled out of the reaction system while gradually releasing the pressurized state. Of binder resin for plastics. 7. The method for producing a binder resin for a toner according to claim 5, wherein the polymerization is carried out using two or more polymerization initiators having different half-life temperatures in combination.