JPH08179551A - Production of noncrosslinking resin binder for toner - Google Patents

Abstract

PURPOSE: To produce a noncrosslinking resin binder contg. a high mol.wt. polymer component and a low mol.wt. polymer component, having a wide mol.wt. distribution and ensuring well-balanced fixability and anti-offsetting property of a toner in a short time. CONSTITUTION: A high mol.wt. polymer component is suspension-polymerized at >=95 deg.C using a monomer for a high mol.wt. polymer contg. 0.001-0.1 pt.wt. multifunctional vinyl monomer and a polymn. initiator and then a low mol. wt. polymer component is suspension-polymerized in the presence of suspended particles of a high mol.wt. polymer to produce the objective noncrosslinking resin binder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a non-crosslinking binder resin for toner used in electrophotography, electrostatic printing, etc. More specifically, it is a high molecular weight polymer having a high molecular weight in a short time. The present invention relates to a method for producing a non-crosslinking binder resin for a toner, which has a wide molecular weight distribution containing a component and a low molecular weight polymer component, and can produce a non-crosslinking binder resin for a toner having a well-balanced fixing property and non-offset property of the toner. It is a thing.

[0002]

2. Description of the Related Art A typical image forming process using electrophotography or electrostatic printing is to uniformly charge a photoconductive insulating layer, expose the insulating layer, and then charge the exposed portion. To form an electrical latent image by dissipating the latent image, and visualized by attaching a fine powder toner having an electric charge to the latent image, the obtained visible image on 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.

As the toner and the binder resin for the toner used in such an electrophotographic method or electrostatic printing method, various performances are required in each of the above steps. For example, in the developing process, the toner and the binder resin for the toner retain the charge amount suitable for the 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 process using the heat roller fixing method, the non-offset property that does not adhere to the heat roller and the fixability on paper must be good. Further, blocking resistance that toner does not block during storage in a copying machine is also required.

Conventionally, as a binder resin for toner,
Styrene-acrylic resins are often used, and linear type resins and crosslinked type resins are used. In a linear type resin, it has been attempted to improve the fixing property and non-offset property of the toner by mixing a high molecular weight polymer and a low molecular weight polymer. But,
In the toner using such a resin, for example, when the fixing property is improved, the melt viscosity of the resin is lowered and the non-offset property of the toner is lowered, and it is difficult to obtain a toner having a good balance between the two. . Therefore, attempts have been made to improve the balance between the fixability and the non-offset property by widening the molecular weight distribution of the binder resin according to the resin production method.

[0005]

Generally, styrene-
The non-crosslinked binder resin made of an acrylic copolymer can be obtained by a polymerization method such as a suspension polymerization method, a solution polymerization method, an emulsion polymerization method or a bulk polymerization method. However, the solution polymerization method is difficult to remove the solvent used, and has problems such as odor and image stability depending on the remaining solvent, and also has a high molecular weight of more than 300,000 in terms of weight average molecular weight. Obtaining a combined component is extremely difficult. Also,
The emulsion polymerization method can obtain a resin having a wide molecular weight distribution with a weight average molecular weight of more than 1,000,000 as a high molecular weight polymer component, but since the emulsifier used remains in the non-crosslinked resin, moisture resistance is improved. It has the problem of being inferior. Further, the bulk polymerization method is difficult to control heat generation and is extremely inferior in productivity. On the other hand, the suspension polymerization method does not have the problem of odor due to the residual solvent because it does not use a solvent, and it is easy to control heat generation, and the amount of the polymerization dispersant used is small and does not impair the moisture resistance. And is suitable for producing a non-crosslinked resin for toner.

However, in the conventional suspension polymerization method, 1
When a compound having one t-butylperoxide group in the molecule is used as a polymerization initiator, in order to obtain a high molecular weight polymer component having a weight average molecular weight of more than 300,000, a long time Polymerization had to be carried out.
Further, a method of increasing the reaction rate of suspension polymerization by using a high-temperature decomposable polymerization initiator having a 10-hour half-life temperature of higher than 90 ° C. is used, but the reaction time of 5 to 6 hours is still used. I needed it. Furthermore, the reaction rate can be increased and the reaction time can be shortened in a short time by increasing the amount of the polymerization initiator used, but the molecular weight of the resin obtained decreases with the increase of the polymerization initiator. . Therefore, an object of the present invention is to include a high molecular weight polymer component having a high molecular weight and a low molecular weight polymer component, a wide molecular weight distribution, a toner non-crosslinking system having a well-balanced fixing property and non-offset property. It is to manufacture the binder resin in a short time.

[0007]

In view of such circumstances, the inventors of the present invention have made earnest studies on a method for producing a non-crosslinking binder resin for toner, and as a result, by using a specific amount of a polyfunctional monomer, The inventors have found that a non-crosslinking binder resin for toner having a good balance of toner fixing property and non-offset property can be produced in a short time, and have reached the present invention. That is, the method for producing a non-crosslinking binder resin for a toner of the present invention uses a monomer for a high molecular weight polymer containing 0.001 to 0.1 part by weight of a polyfunctional vinyl monomer and a polymerization initiator, The method is characterized in that after suspension polymerizing a high molecular weight polymer component at 95 ° C. or higher, suspension polymerizing a low molecular weight polymer component in the presence of suspended particles of the high molecular weight polymer.

The non-crosslinking binder resin for toner obtained by the present invention is a mixture of a high molecular weight polymer component and a low molecular weight polymer component uniformly, and any polymer can be copolymerized with a styrenic monomer or another. In particular, it is a polymer or copolymer made of a vinyl monomer or the like, and a styrene-acrylic copolymer is particularly preferable. In the present invention, examples of the styrene-based monomer used for polymerizing the high molecular weight polymer component and the low molecular weight polymer component include 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
-Hexyl styrene, pn-octyl styrene, p-
n-nonyl styrene, pn-densyl styrene, p-
n-dodecyl styrene, p-phenyl styrene, 3,4
-Diclosyl styrene and the like are mentioned, and among them, styrene is preferable. These styrene-based monomers can be used alone or in combination of two or more.

Other copolymerizable vinyl monomers include ethyl acrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate. , Unsaturated carboxylic acids such as methacrylic acid, ethyl methacrylic acid, methyl methacrylic acid, n-butyl methacrylic acid, isobutyl methacrylic acid, propyl methacrylic acid, 2-ethylhexyl methacrylic acid and stearyl methacrylic acid Examples thereof include esters, unsaturated dicarboxylic acid diesters such as dimethyl maleate, diethyl maleate, butyl maleate, dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

Further, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and cinnamic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate and fumaric acid. A carboxylic acid-containing vinyl monomer such as an unsaturated monocarboxylic acid monoester such as monomethyl, monoethyl fumarate or monobutyl fumarate may also be used in combination. The copolymerization ratio of these monomers is not particularly limited, but it is preferable to set the glass transition temperature of the obtained resin to a range of 50 ° C. or higher. This is because when the glass transition temperature of the resin is lower than 50 ° C, the storage stability may be extremely lowered when the resin is made into a toner, and more preferably in the range of 55 to 70 ° C.

The present invention is directed to polymerizing a high molecular weight polymer component by suspension polymerization and polymerizing a low molecular weight polymer component by suspension polymerization in the presence of suspended particles of the high molecular weight polymer. It is intended to produce a non-crosslinking binder resin for toner in which a coalescing component and a low molecular weight polymer component are uniformly mixed. The suspension polymerization of the high molecular weight polymer component is performed by adding the polyfunctional vinyl monomer together with the high molecular weight polymer monomer as described above to 0.0 to 100 parts by weight of the total monomer.
It is important to use in the range of 01 to 0.1 parts by weight. This is because the amount of polyfunctional vinyl monomer used is 0.00
When the amount is less than 1 part by weight, the effect of adding the polyfunctional vinyl monomer is lost, and when the amount is more than 0.1 part by weight, the low molecular weight polymer component and the high molecular weight polymer component of the resin are not uniformly mixed. And more preferably 0.0
It is in the range of 02 to 0.5 parts by weight. In the present invention, the polyfunctional vinyl monomer is not used as a crosslinking agent, and the obtained binder resin is a non-crosslinked binder resin containing no gel component.

Examples of polyfunctional vinyl monomers used include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, ethylene glycol di (meth) acrylate, triethylene glycol di (meth).
Acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, bisphenol A derivative-based di (meth) acrylate, etc. These may be used alone or in combination of two or more. Among them, divinylbenzene and 1,3-butylene glycol di (meth) acrylate are particularly preferable.

As the polymerization initiator used for suspension polymerization of the high molecular weight polymer component, a compound having three or more t-butylperoxide groups in one molecule or a 10-hour half-life temperature of 90 to 140 ° C. A radical polymerization initiator having one functional group in one molecule of the above can be used, and a compound having three or more t-butylperoxide groups in one molecule can be used as a toner having good fixing property and durability. It is preferable in that the balance with the offset property can be further improved and the polymerization can be carried out in a shorter time.

Specific examples of the polymerization initiator include, for example, 1
Examples of the compound having 3 or more t-butylperoxide groups in the molecule include 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane. Further, as the radical polymerization initiator having one functional group in one molecule having a 10-hour half-life temperature of 90 to 140 ° C., t-butylperoxylaurate, t-butylperoxy 3,5,5- Trimethylhexanoate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxyacetate, t-butylperoxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, diisopropylbenzene hydroperoxide, di- -T-butyl peroxide, p-methane hydroperoxide, 2-
Organic peroxides such as (carbamoylazo) isobutyronitrile, 2,2-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, or azo compounds Is mentioned. These polymerization initiators can be used alone or in combination of two or more kinds. The amount of the polymerization initiator used may be a very small amount as compared with the amount of the polymerization initiator used in the conventional suspension polymerization, and 0.001 to 0.5 parts by weight based on 100 parts by weight of all the monomers. It is preferably used in the range of 0.002 parts by weight, more preferably 0.002 to 0.1 parts by weight. This is because when the amount of the polymerization initiator used is less than 0.001 part by weight, it tends to take a long time to reach a predetermined polymerization reaction rate, and when it exceeds 0.5 part by weight, the high molecular weight polymer is obtained. This is because the molecular weight of the component tends not to be sufficiently high.

In the present invention, the polyfunctional vinyl monomer and the polymerization initiator as described above are used, and the temperature is 9
By polymerizing the high molecular weight polymer component by suspension polymerization at a high temperature of 5 ° C. or higher, preferably 100 ° C. or higher, the polymerization initiator is efficiently consumed, and the weight average molecular weight is 3 × 10 ⁵ or more. 1 high molecular weight polymer component
It can be obtained in a short time of about 3 hours.
This is because if the polymerization temperature is lower than 95 ° C., it takes a long time to reach a predetermined polymerization reaction rate. The high molecular weight polymer component polymerized by suspension polymerization preferably has a weight average molecular weight (Mw) of 1 × 10 ^{5 to} 1.5 × 10 ⁶ . This is the weight average molecular weight (M
If w) is less than 1 × 10 ⁵ , the offset resistance as a toner tends to decrease, and conversely, if it exceeds 1.5 × 10 ⁶ , the fixability as a toner tends to decrease. , And more preferably 3 × 10 ⁵ to 8 × 10 ⁵ .

In the present invention, the low molecular weight polymer component is polymerized by suspension polymerization in the presence of the suspension polymerized high molecular weight polymer component. Suspension polymerization of low molecular weight polymer components
It is not particularly limited, and for example, when the polymerization reaction rate of the high molecular weight polymer reaches about 10 to 90%, the polymerization initiator for the low molecular weight polymer is water or the monomer for the low molecular weight polymer. It is preferable to start the polymerization by dissolving it in and adding it. When the low molecular weight polymer monomer is added, it is preferable to add such an amount that the content of the low molecular weight polymer component of the obtained resin is in the range of 50 to 90% by weight.

The polymerization initiator used for suspension polymerization of the low molecular weight polymer component is not particularly limited,
Commonly used radically polymerizable peroxides and azo compounds can be used, and examples thereof include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, acetyl peroxide and isobutyryl peroxide. Oxide, octanonyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-toluoyl peroxide, t-butylperoxyacetate, t-butylperoxide Oxyisobutyrate,
t-butyl peroxypiperate, t-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, t-butyl peroxy 2-ethylhexanoate,
t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxy lylate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl cavonate, azobisisobutyl nitrile, 2,
2-azobis- (2,4-dimethylvaleronitrile) and the like can be mentioned, but among them, octanonyl peroxide and decanoyl peroxide are preferable from the viewpoint of the sustainability of the polymerization activity for the monomers and the fact that the polymerization is completed in a relatively short time. Peroxide, lauroyl peroxide, benzoyl peroxide and m-trioyl peroxide are preferred. These polymerization initiators can be used alone or in combination of two or more kinds,
The monomer is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.5 to 100 parts by weight.
It is in the range of 10 parts by weight.

The low molecular weight polymer component polymerized by suspension polymerization preferably has a weight average molecular weight of 3 × 10 ³ to 2 × 10 ⁵ . This is because when the weight average molecular weight is less than 3 × 10 ³ , the mechanical strength of the resin is lowered and the toner tends to be in an excessively pulverized state when electrification occurs, and fogging tends to occur in the image. This is because if it exceeds 10 ⁵ , the fixability as a toner tends to be lowered, and the range of 6 × 10 ³ to 1 × 10 ⁵ is more preferable. In the present invention, the ratio of the high molecular weight polymer component and the low molecular weight polymer component is not particularly limited, but the high molecular weight polymer component is preferably contained in the range of 10 to 50% by weight. . This is because if the high molecular weight polymer component is less than 10% by weight, the non-offset property as a toner tends to be poor, and conversely if it exceeds 50% by weight, the fixability as a toner tends to be poor. .

In the present invention, the suspension polymerization is preferably carried out in an amount of 1 to 10 times, more preferably 2 to 4 times, that of the monomer together with a dispersant, a polymerization initiator and, if necessary, a dispersion aid. Agent or chain transfer agent is added, the temperature is raised to a predetermined polymerization temperature, and heating is continued until a predetermined polymerization rate is reached.

Examples of the dispersion stabilizer used in suspension polymerization include polyvinyl alcohol, alkali metal salts of homopolymers or copolymers of (meth) acrylic acid, carboxytyl cellulose, gelatin, starch, barium sulfate,
Calcium sulfate, calcium carbonate, magnesium carbonate,
Examples thereof include calcium phosphate and the like. Among them, polyvinyl alcohol is preferable, and partially saponified polyvinyl alcohol in which an acetic acid group and a hydroxyl group are present in a block manner is particularly preferable. These dispersants are based on 100 parts by weight of water.
It is preferably used in the range of 0.01 to 5 parts by weight.
This is because when the amount of the dispersant used is less than 0.01 part by weight, the stability of suspension polymerization is lowered and the polymer tends to solidify due to the aggregation of the produced particles, and conversely exceeds 5 parts by weight. This is because the environmental dependency of the toner, particularly the humidity resistance tends to decrease, and the range of 0.05 to 2 parts by weight is more preferable. Also, if necessary, together with these dispersants, sodium chloride, potassium chloride, sodium sulfate,
A dispersion aid such as potassium sulfate can also be used in combination. Further, in order to adjust the molecular weight, n-octyl mercaptan, n-dodecyl mercaptan, t-
A chain transfer agent such as dodecyl mercaptan, 2-ethylhexyl thioglycolate, or α-methylstyrene dimer may be used. The binder resin for a toner thus obtained has a softening temperature of 110 to 170 ° C. and a glass transition temperature of 40 to 80 ° C. and has a toner fixing property, non-offset property, storage stability, and fluidity. It is preferable in terms of sex.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, the glass transition temperature was determined by the DSC method (heating rate 10 ° C./min) after the sample was heated to 100 ° C. and melt-quenched. For the softening temperature, a flow tester (CFT-500 manufactured by Shimadzu Corporation) having a nozzle of 1 mmφ × 10 mm was used, and a load of 30 was used.
Under the conditions of Kgf and a temperature rising rate of 3 ° C./min, the temperature when ½ of the sample amount flows out is shown. Weight average molecular weight and molecular weight distribution, tetrahydrofuran as a solvent,
It was measured using gel permeation chromatography (HCL-8020 manufactured by Tosoh Corporation), and determined by polystyrene conversion.

The fixing property was determined by using a fixing tester capable of freely changing the fixing temperature and fixing speed of 130 mm / sec.
When the pressure was 40 kg, cellophane tape was attached to the fixed toner image, and the change in image density before and after peeling when the cellophane tape was peeled off was visually observed and evaluated according to the following criteria. ◯: Small change in image density X: Significant change in image density

The non-offset property is obtained by using a fixing tester capable of freely changing the fixing temperature and fixing speed of 130 m.
The degree of contamination by the toner of the fixing roller was visually observed at m / sec and a pressure of 40 kg, and evaluated according to the following criteria. ⊚: Almost no pollution x: Significantly pollution

The storage stability was evaluated by visually observing the blocking state after the toner was placed in a hot air dryer kept at about 50 ° C. and left for 50 hours according to the following criteria. ○: Almost no blocking occurs ×: Significant blocking occurs.

Moisture resistance is determined by the amount of charge after leaving it for 20 hours in an environment of temperature 30 ° C. and humidity of 85% and the amount of charge after leaving it for 20 hours in an environment of temperature 10 ° C. and humidity 15%. Then, the presence or absence of the environmental dependency was evaluated according to the following criteria. ○: Almost no environmental dependence ×: Significant environmental dependence

Example 1 41.5 parts by weight of styrene, n-butyl acrylate 8.5
As a polymerization initiator, 2 parts by weight of a monomer mixture is added.
2-bis (4,4-di-t-butylperoxycyclohexyl) propane ("Parkadox 1" manufactured by Kayaku Akzo Co., Ltd.
2 ") 0.02 part by weight, 0.01 part by weight of divinylbenzene as a cross-linking agent, and 200 parts by weight of deionized water and partially saponified polyvinyl alcohol (" Gosenol GH "manufactured by Nippon Synthetic Chemical Industry Co., Ltd. -23 ") 0.2 part by weight in a mixture and stirred. Next, the temperature was raised to 130 ° C. and suspension polymerization of the high molecular weight polymer was performed for 1 hour. The polymerization reaction rate at this time was about 35%. Furthermore, styrene 41.5 was added to the dispersion liquid of the high molecular weight polymer cooled to 40 ° C.
Parts by weight, 8.5 parts by weight of n-butyl acrylate, 6 parts by weight of benzoylperoxide and 1 part by weight of t-butylperoxybenzoate ("Perbutyl Z" manufactured by NOF Corporation) are added, and the mixture is heated to 130 ° C. The temperature was raised and suspension polymerization of the low molecular weight polymer was carried out for 1.5 hours. The polymerization reaction rate at this time is about 100%
Met. After that, cool to room temperature, wash thoroughly with water,
After dehydration and drying, a styrene-acrylic toner binder resin in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed was obtained. Table 2 shows the softening temperature, glass transition temperature, weight average molecular weight and content of the high molecular weight polymer component and the low molecular weight polymer component of the obtained binder resin for toner.

93 parts by weight of the obtained binder resin for toner, 5 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), 1 part by weight of a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industry Co., Ltd.) and polypropylene wax. (Sanyo Kasei Co., Ltd. "660P") 1 part by weight is kneaded for about 5 minutes at 150 ° C. using a twin-screw extruder, pulverized with a jet mill fine pulverizer, and classified to have a particle diameter of 5 to 15 μm. Toner was obtained. Table 2 shows the evaluation results of the fixability, offset resistance, storage stability and moisture resistance of the obtained toner.

Example 2 41.5 parts by weight of styrene, n-butyl acrylate 8.5
As a polymerization initiator, 2 parts by weight of a monomer mixture is added.
2-bis (4,4-di-t-butylperoxycyclohexyl) propane ("Parkadox 1" manufactured by Kayaku Akzo Co., Ltd.
2 ") 0.02 parts by weight, 0.025 parts by weight of divinylbenzene as a cross-linking agent are dissolved, 200 parts by weight of deionized water and partially saponified polyvinyl alcohol (" Gosenol GH "manufactured by Nippon Synthetic Chemical Industry Co., Ltd. -23 ") 0.2 part by weight in a mixture and stirred. Next, the temperature was raised to 130 ° C. and suspension polymerization of the high molecular weight polymer was performed for 1 hour. The polymerization reaction rate at this time was about 35%. Furthermore, styrene 41.5 was added to the dispersion liquid of the high molecular weight polymer cooled to 40 ° C.
Parts by weight, 8.5 parts by weight of n-butyl acrylate, 6 parts by weight of benzoylperoxide and 1 part by weight of t-butylperoxybenzoate ("Perbutyl Z" manufactured by NOF Corporation) are added, and the mixture is heated to 130 ° C. The temperature was raised and suspension polymerization of the low molecular weight polymer was carried out for 1.5 hours. The polymerization reaction rate at this time is about 100%
Met. After that, cool to room temperature, wash thoroughly with water,
After dehydration and drying, a styrene-acrylic toner binder resin in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed was obtained. Table 2 shows the softening temperature, glass transition temperature, weight average molecular weight and content of the high molecular weight polymer component and the low molecular weight polymer component of the obtained binder resin for toner.

93 parts by weight of the obtained binder resin for toner, 5 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), 1 part by weight of a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industry Co., Ltd.) and polypropylene wax. (Sanyo Kasei Co., Ltd. "660P") 1 part by weight is kneaded for about 5 minutes at 150 ° C. using a twin-screw extruder, pulverized with a jet mill fine pulverizer, and classified to have a particle diameter of 5 to 15 μm. Toner was obtained. Table 2 shows the evaluation results of the fixability, offset resistance, storage stability and moisture resistance of the obtained toner.

Example 3 41.5 parts by weight of styrene, n-butyl acrylate 8.5
To the monomer mixture consisting of parts by weight, t-as a polymerization initiator
Butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF CORPORATION) 0.03 parts by weight and 0.01 parts by weight of divinylbenzene as a cross-linking agent were dissolved, and 200 parts by weight of deionized water and partially saponified polyvinyl alcohol ( 0.2 g by weight of "Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and stirred. Next, the temperature was raised to 130 ° C. and suspension polymerization of the high molecular weight polymer was performed for 2 hours. The polymerization reaction rate at this time was about 66%. Further, in a dispersion liquid of a high molecular weight polymer cooled to 40 ° C., styrene 41.
5 parts by weight, 8.5 parts by weight of n-butyl acrylate, 6 parts by weight of benzoylperoxide and 1 part by weight of t-butylperoxybenzoate (“Perbutyl Z” manufactured by NOF CORPORATION) were added, and the mixture was heated to 130 ° C. The temperature was raised to 1.5 and suspension polymerization of the low molecular weight polymer was performed for 1.5 hours. The polymerization reaction rate at this time is about 99%
Met. After that, cool to room temperature, wash thoroughly with water,
After dehydration and drying, a styrene-acrylic toner binder resin in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed was obtained. Table 2 shows the softening temperature, glass transition temperature, weight average molecular weight and content of the high molecular weight polymer component and the low molecular weight polymer component of the obtained binder resin for toner.

93 parts by weight of the obtained binder resin for toner, 5 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei), 1 part by weight of a charge control agent ("Bontron S-34" manufactured by Orient Chemical Co., Ltd.) and polyprolylene. 1 part by weight of wax (“660P” manufactured by Sanyo Kasei Co., Ltd.) was kneaded with a twin-screw extruder at 150 ° C. for about 5 minutes, pulverized with a jet mill fine pulverizer, and classified to have a particle diameter of 5 A toner of 15 μm was obtained. Table 2 shows the evaluation results of the fixability, offset resistance, storage stability and moisture resistance of the obtained toner.

Example 4 41.5 parts by weight of styrene, n-butyl acrylate 8.5
To the monomer mixture consisting of parts by weight, t-as a polymerization initiator
0.03 parts by weight of butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF CORPORATION) and 0.025 parts by weight of divinylbenzene as a crosslinking agent were dissolved, and 200 parts by weight of deionized water and partially saponified polyvinyl alcohol ( 0.2 g by weight of "Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and stirred. Next, the temperature was raised to 130 ° C. and suspension polymerization of the high molecular weight polymer was performed for 2 hours. The polymerization reaction rate at this time was about 50%. Further, styrene 4 was added to the dispersion liquid of the high molecular weight polymer cooled to 40 ° C.
1.5 parts by weight, 8.5 parts by weight of n-butyl acrylate, 6 parts by weight of benzoylperoxide and 1 part by weight of t-butylperoxybenzoate ("Perbutyl Z" manufactured by NOF CORPORATION) were added, The temperature was raised to 130 ° C. and suspension polymerization of the low molecular weight polymer was performed for 1.5 hours. The polymerization reaction rate at this time is about 1
00%. Then, it was cooled to room temperature, sufficiently washed with water, dehydrated and dried to obtain a styrene-acrylic toner binder resin in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed. Table 2 shows the softening temperature, glass transition temperature, weight average molecular weight and content of the high molecular weight polymer component and the low molecular weight polymer component of the obtained binder resin for toner.

93 parts by weight of the obtained binder resin for toner, 5 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei), 1 part by weight of a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industry Co., Ltd.) and polypropylene wax. (Sanyo Kasei Co., Ltd. "660P") 1 part by weight is kneaded for about 5 minutes at 150 ° C. using a twin-screw extruder, pulverized with a jet mill fine pulverizer, and classified to have a particle diameter of 5 to 15 μm. Toner was obtained. Table 2 shows the evaluation results of the fixability, offset resistance, storage stability and moisture resistance of the obtained toner.

Comparative Example 1 41.5 parts by weight of styrene, n-butyl acrylate 8.5
To the monomer mixture consisting of parts by weight, t-as a polymerization initiator
Dissolve 0.03 part by weight of butyl peroxybenzoate (“Perbutyl Z” manufactured by NOF CORPORATION), and add 200 parts of deionized water.
The mixture is added to a mixture of 0.2 parts by weight of partially saponified polyvinyl alcohol ("Gosenol GH-23" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and stirred. Next, the temperature was raised to 130 ° C. and suspension polymerization of the high molecular weight polymer was performed for 2 hours.
The polymerization reaction rate at this time was about 50%. Furthermore, 40
41.5 parts by weight of styrene, 8.5 parts by weight of n-butyl acrylate, in a dispersion liquid of the high molecular weight polymer cooled to ℃,
6 parts by weight of benzoylperoxide and 1 part by weight of t-butylperoxybenzoate (“Perbutyl Z” manufactured by NOF CORPORATION) were added, and the temperature was raised to 130 ° C. for 1.5 hours to suspend the low molecular weight polymer. Suspension polymerization was performed. The polymerization reaction rate at this time was about 100%. Then, it was cooled to room temperature, sufficiently washed with water, dehydrated and dried to obtain a styrene-acrylic toner binder resin in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed. Table 2 shows the softening temperature, glass transition temperature, weight average molecular weight and content of the high molecular weight polymer component and the low molecular weight polymer component of the obtained binder resin for toner.

93 parts by weight of the obtained binder resin for toner, 5 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), 1 part by weight of a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industry Co., Ltd.) and polyprolylene. 1 part by weight of wax (“660P” manufactured by Sanyo Kasei Co., Ltd.) was kneaded with a twin-screw extruder at 150 ° C. for about 5 minutes, pulverized with a jet mill fine pulverizer, and classified to have a particle diameter of 5 A toner of 15 μm was obtained. Table 2 shows the evaluation results of the fixability, offset resistance, storage stability and moisture resistance of the obtained toner.

Comparative Example 2 41.5 parts by weight of styrene, n-butyl acrylate 8.5
As a polymerization initiator, 2 parts by weight of a monomer mixture is added.
2-bis (4,4-di-t-butylperoxycyclohexyl) propane ("Parkadox 1" manufactured by Kayaku Akzo Co., Ltd.
2 ") 0.02 parts by weight, 0.2 parts by weight of divinylbenzene as a cross-linking agent are dissolved, 200 parts by weight of deionized water and partially saponified polyvinyl alcohol (" Gosenol GH "manufactured by Nippon Synthetic Chemical Industry Co., Ltd. -23 ") 0.2 part by weight in a mixture and stirred. Next, the temperature was raised to 130 ° C. and suspension polymerization of the high molecular weight polymer was performed for 2 hours. The polymerization reaction rate at this time was about 35%. Further, 41.5 parts by weight of styrene, 8.5 parts by weight of n-butyl acrylate, 6 parts by weight of benzoylperoxide and 6 parts by weight of t-butylperoxybenzoene were added to the dispersion liquid of the high molecular weight polymer cooled to 40 ° C.
1 part by weight of "Perbutyl Z" (manufactured by Nippon Oil & Fats Co., Ltd.) was added, and the temperature was raised to 130 ° C to carry out suspension polymerization of the low molecular weight polymer for 1.5 hours. The polymerization reaction rate at this time was about 100%. Then, it was cooled to room temperature, sufficiently washed with water, dehydrated and dried to obtain a styrene-acrylic toner binder resin in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed. Table 2 shows the softening temperature, glass transition temperature, weight average molecular weight and content of the high molecular weight polymer component and the low molecular weight polymer component of the obtained binder resin for toner.

93 parts by weight of the obtained binder resin for toner, 5 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), 1 part by weight of a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industry Co., Ltd.) and polypropylene wax. (Sanyo Kasei Co., Ltd. "660P") 1 part by weight is kneaded for about 5 minutes at 150 ° C. using a twin-screw extruder, pulverized with a jet mill fine pulverizer, and classified to have a particle diameter of 5 to 15 μm. Toner was obtained. Table 2 shows the evaluation results of the fixability, offset resistance, storage stability and moisture resistance of the obtained toner.

Comparative Example 3 41.5 parts by weight of styrene, n-butyl acrylate 8.5
As a polymerization initiator, 2 parts by weight of a monomer mixture is added.
2-bis (4,4-di-t-butylperoxycyclohexyl) propane ("Parkadox 1" manufactured by Kayaku Akzo Co., Ltd.
2 ") 0.02 part by weight, 0.01 part by weight of divinylbenzene as a cross-linking agent, and 200 parts by weight of deionized water and partially saponified polyvinyl alcohol (" Gosenol GH "manufactured by Nippon Synthetic Chemical Industry Co., Ltd. -23 ") 0.2 part by weight in a mixture and stirred. Then, raise the temperature to 90 ° C and
Suspension polymerization of the high molecular weight polymer was carried out for a period of time. The polymerization reaction rate at this time was about 35%. Furthermore, 41.5 parts by weight of styrene, 8.5 parts by weight of n-butyl acrylate, 6 parts by weight of benzoylperoxide and t-butylperoxybenzoate (in a dispersion of a high molecular weight polymer cooled to 40 ° C.). 1 part by weight of Nippon Oil & Fats Co., Ltd. "Perbutyl Z" was added, and the temperature was raised to 130 ° C to carry out suspension polymerization of the low molecular weight polymer for 1.5 hours. The polymerization reaction rate at this time was about 100%. Then, it was cooled to room temperature, sufficiently washed with water, dehydrated and dried to obtain a styrene-acrylic toner binder resin in which a high molecular weight polymer component and a low molecular weight polymer component were uniformly mixed. Table 2 shows the softening temperature, glass transition temperature, weight average molecular weight and content of the high molecular weight polymer component and the low molecular weight polymer component of the obtained binder resin for toner.

93 parts by weight of the obtained binder resin for toner, 5 parts by weight of carbon black (# 40 manufactured by Mitsubishi Kasei Co., Ltd.), 1 part by weight of a charge control agent ("Bontron S-34" manufactured by Orient Chemical Industry Co., Ltd.) and polypropylene wax. (Sanyo Kasei Co., Ltd. "660P") 1 part by weight is kneaded for about 5 minutes at 150 ° C. using a twin-screw extruder, pulverized with a jet mill fine pulverizer, and classified to have a particle diameter of 5 to 15 μm. Toner was obtained. Table 2 shows the evaluation results of the fixability, offset resistance, storage stability and moisture resistance of the obtained toner.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

The method for producing a non-crosslinking resin for a toner of the present invention comprises carrying out suspension polymerization of a high molecular weight polymer component using a specific amount of a polyfunctional vinyl monomer to obtain a high molecular weight polymer component. And a low molecular weight polymer component and having a wide molecular weight distribution and a well-balanced toner fixing property and non-offset property can be produced in a short time.

Front Page Continuation (72) Inventor Yoko Harada 2 1-4-1, Ushikawa-dori, Toyohashi City, Aichi Sanryo Rayon Co., Ltd. Toyohashi Plant

Claims (1)

[Claims] 1. A polyfunctional vinyl monomer in an amount of 0.001 to
Using 0.1 part by weight of a monomer for a high molecular weight polymer and a polymerization initiator, the high molecular weight polymer component was subjected to suspension polymerization at a temperature of 95 ° C. or higher, and then a suspension particle of the high molecular weight polymer was obtained. A method for producing a non-crosslinking binder resin for toner, which comprises subjecting a low molecular weight polymer component to suspension polymerization in the presence of the same.