JPH05173366A - Resin for toenr ensuring high image quality - Google Patents

Abstract

PURPOSE:To provide a resin forming a toner ensuring high image quality, excellent in fixability, anti-offsetting property, blocking resistance and electrostatic chargeability at the time of kick-off and having such satisfactory image characteristics as to give a fog-free clear image. CONSTITUTION:This resin for a toner ensuring high image quality is a styrene- acrylic copolymer having <=20mgKOH/g acid value, <=1,000ppm residual monomer and/or residual solvent content, 50-68 deg.C glass transition temp. and 110-145 deg.C softening temp. The copolymer consists of 15-40wt.% high mol.wt. polymer having 3mu10<5>-1.5X10-wt. average mol.wt. and 0.5-20mgKOH/g acid value (AV) and 60-85wt.% low mol. wt. polymer having 3X10<3>-6X10<4>wt. average mol. wt. and 0.5-20mgK0H/g acid value (AV). In the copolymer, the ratio of AVH to AVL is 0.025-40.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for high image quality toner which is excellent in non-offset properties, fixing properties, blocking resistance and image characteristics used in electrophotographic copying machines and printers.

[0002]

2. Description of the Related Art Copiers and printers that use electrophotography are designed for high-speed printing and high quality image characteristics.
The toner used for this purpose or the resin for toner is required to have excellent fixability, non-offset property, and image quality characteristics.

Generally, as a toner resin used in a high speed type copying machine or printer, a linear type styrene-acrylic resin is used as a mixture of a high molecular weight polymer and a low molecular weight polymer. .. Conventionally, the fixability and non-offset property of the resin for toner have been improved by controlling the molecular weight and content of the high molecular weight polymer and the low molecular weight polymer and considering the balance between the high molecular weight polymer and the low molecular weight polymer. It was Regarding the image characteristics, the pulverizability of the resin is controlled by the mixing ratio of the high molecular weight polymer and the low molecular weight polymer, and the toner and the resin for the toner are prevented from being excessively pulverized at the time of printing, resulting in a clear image without fog. There was a way to get an image.

[0004]

However, when polymers having different molecular weights are mixed, the balance between the fixability and the non-offset property may be impaired, and the balance between the fixability and the non-offset property is not sufficient. It wasn't something. Further, as the printing speed increases, the toner and the carrier are violently mixed in the charge generation step, and the toner and the resin for the toner are often over-pulverized, so that the image characteristics are not sufficiently improved.

Regarding the image characteristics, attention has been paid to the charging step which is a step prior to image formation, and attempts have been made to improve the rising charge by introducing an acid monomer as a method for obtaining a more stable charge. However, the acid value of the resin was increased by the introduction of the acid monomer, and due to the environmental stability, particularly the influence of humidity, stable charging could not be obtained. Further, a method of reducing the residual monomer and residual solvent contained in the resin to prevent image fogging has been attempted, but it has been difficult to obtain a clear image only by reducing the residual monomer. Therefore, an object of the present invention is to provide a resin for toner which is excellent in the balance between the fixing property and the non-offset property, and is also excellent in the image characteristics and the blocking resistance.

[0006]

In view of such circumstances, the inventors of the present invention have made earnest studies on a resin for toner, and as a result, have found that the molecular weight and the mixing ratio of the high molecular weight polymer and the low molecular weight polymer of the toner resin are high. By controlling the acid value and its ratio, and balancing the content of residual monomer and residual solvent, glass transition temperature, softening temperature and acid value, excellent fixability, non-offset property, image characteristics and blocking resistance, The present invention has been accomplished by finding that a resin for high-quality toner having good charging characteristics such as rising charging can be obtained.

That is, the resin for high quality toner of the present invention has a high weight average molecular weight of 3 × 10 ^{5 to} 1.5 × 10 ⁶ and an acid value (AV ^H ) of 0.5 to 20 mgKOH / g. A low molecular weight polymer 60 having a molecular weight polymer of 15 to 40% by weight, a weight average molecular weight of 3 × 10 ^{3 to} 6 × 10 ⁴ , and an acid value (AV ^L ) of 0.5 to 20 mgKOH / g.
Acid value 20 mgKOH / g or less of styrene consisting of 85 wt% - an acrylic copolymer, AV ^H / AV
^L is 0.025-40, residual monomer and / or residual solvent is 1000 ppm or less, glass transition temperature is 50-
It is characterized by having a temperature of 68 ° C. and a softening temperature of 110 to 145 ° C.

The styrene-acrylic copolymer used in the resin for toner of the present invention is a copolymer of a styrene monomer and a radically polymerizable polymerizable vinyl monomer containing an acrylic monomer. The monomer used is not particularly limited, but examples of the styrene-based monomer include styrene, o-methylstyrene, m-
Methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn- Octyl styrene, pn-nonyl styrene, pn-densyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, 3,4-diclosyl styrene and the like can be mentioned. One kind or two or more kinds can be used.

Further, as the polymerizable vinyl monomer,
For example, acrylic acid, ethyl acrylate, methyl acrylate, n-butyl acrylate, t-butyl acrylate,
2-ethylhexyl acrylate, isobutyl acrylate, propyl acrylate, dodecyl acrylate, lauryl acrylate, stearyl acrylate, phenyl acrylate, alkyl acrylate, glycidyl acrylate, 2-hydroxymethyl acrylate, 2-hydroxy acrylate Ethyl, benzyl acrylate, methacrylic acid, ethyl methacrylate, methyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, propyl methacrylate. , Dodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, phenyl methacrylate, alkyl methacrylate, glycidyl methacrylate, 2-hydroxymethyl methacrylate, methacrylic acid Acrylic monomers such as 2-hydroxyethyl phosphate, benzyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, maleic acid, butyl maleate, methyl maleate, dimethyl maleate, fumaric acid, fumaric acid Butyl, dibutyl fumarate, diisobutyl fumarate, dimethyl fumarate, unsaturated dibasic acids such as diethyl fumarate, monomers obtained by adding ε-caprolactone and an acrylic monomer, bisphenol A derivative acrylic monomers, and the like, One or two of these
More than one species can be used.

Further, in the present invention, a chain transfer agent may be used to adjust the molecular weight. Examples of the chain transfer agent include α-methylstyrene dimer, n-dodecyl mercaptan, 2-ethylhexyl thioglycolate, and n-octyl mercaptan.

The resin for toner of the present invention obtained from the above components has a weight average molecular weight of 3 × 10 ^{5 to} 1.5.
A high molecular weight polymer 15 to 40 wt% is a × 10 ^6, a weight average molecular weight is a low molecular weight polymer 60 to 85 wt% which is ^{3 × 10 3 ~6 × 10 4} . When the weight average molecular weight and the mixing ratio of the high molecular weight polymer and the low molecular weight polymer are in the above ranges, respectively, the balance between fixing property and non-offset property is excellent. Preferably, the weight average molecular weight is 4
High molecular weight polymer 20 to 35 having a size of × 10 ^{5 to} 9 × 10 ^5.
It is a resin for toner, which comprises 65% to 80% by weight of a low molecular weight polymer having a weight average molecular weight of 4 × 10 ^{3 to} 5 × 10 ⁴ .

In the resin for toner of the present invention, the high molecular weight polymer has an acid value (AV ^H ) of 0.5 to 20 mgKOH.
/ G, the acid value (AV ^L ) of the low molecular weight polymer is 0.5 to 20
mg KOH / g, and AV ^H / AV ^L is 0.025 to
40 and the acid value of the resin is 20 mgKOH /
g or less. Resins for toners satisfying these acid values have excellent moisture resistance, good dispersibility of pigments, charge control agents, additives such as waxes used at the time of toner formation, stable chargeability of toner, A clear image that is not affected by the environment can be obtained. Preferably, the high molecular weight polymer has an acid value (AV ^H ) of 0.5 to 15 mgKOH / g, and the low molecular weight polymer has an acid value (AV ^L ) of 0.5 to 15 mgKOH / g.
AV ^H / AV ^L is 0.025 to 30, and the acid value of the resin is in the range of 15 mgKOH / g or less.

That is, the ratio of the acid value of the high molecular weight polymer to the acid value of the low molecular weight polymer (AV ^H / AV ^L ) is a value that takes into consideration the balance of the acid values of both polymers in relation to the image characteristics. , AV ^H / AV ^L is less than 0.025, the acid value of the low molecular weight polymer is large, and it is difficult to obtain a stable image due to poor moisture resistance. Conversely, when it exceeds 40, the acid value of the high molecular weight polymer is high. Is large, it is difficult to obtain a stable image due to poor moisture resistance,
This is because the grindability of the resin is also poor. In addition, the acid value of the high molecular weight polymer and the low molecular weight polymer is 0.5 mgKOH /
If it is less than g, it is difficult to produce a resin, and conversely, 20 mg
When it exceeds KOH / g, it is difficult to obtain a stable image because of poor moisture resistance. Furthermore, the acid value of the resin is 2
This is because when the amount exceeds 0 mgKOH / g, the moisture resistance is poor and it is difficult to obtain a stable image.

In the resin for toner of the present invention, the residual monomer and / or residual solvent content is 1000 ppm or less, preferably 800 ppm or less. This is because the residual monomer and / or residual solvent is 1000
This is because if the content exceeds ppm, the image will be fogged and a clear image cannot be obtained.

In the toner resin of the present invention satisfying the above-mentioned acid value, residual monomer and / or residual solvent ranges, in order to obtain a negatively charged toner, 2-hexylhexyl acrylate is obtained as a monomer and a positively charged toner is obtained. It is preferable to use diethylaminoethyl methacrylate for the purpose from the viewpoint of charging characteristics such as rising charging. 2-Hethylhexyl acrylate is 5 to 30% by weight
When the content of 2-hexylhexyl acrylate is less than 5% by weight, the toner is weakly negatively charged, and when it exceeds 30% by weight, the glass transition temperature of the resin is lowered and the blocking resistance is poor. This is because. Further, diethylaminoethyl methacrylate is 0.1 to 5
It is preferably used in the range of wt%, more preferably 1 to 4 wt%. This is because when the amount of diethylaminoethyl methacrylate is less than 0.1% by weight, the positive chargeability of the toner is weak, and when it exceeds 5% by weight, the moisture resistance is poor.

The glass transition temperature of the resin for toner of the present invention is in the range of 50 to 68 ° C., preferably 54 to 68 ° C.
It is in the range of 66 ° C. This is because by setting the glass transition temperature of the resin for toner to the above range, the blocking resistance can be improved without impairing the fixability, and if the glass transition temperature is less than 50 ° C, the blocking resistance is insufficient. This is because the storability of the toner is poor, and when it exceeds 68 ° C., the fixability is poor.

Further, in the present invention, the softening temperature of the resin for toner is 110 to 1 from the viewpoint of the fixing property of the toner.
It is in the range of 45 ° C, preferably in the range of 120 to 140 ° C. This is because when the softening temperature is lower than 110 ° C., the non-offset property is poor, and when it exceeds 145 ° C., the fixability is poor.

The method for producing the toner resin of the present invention is not particularly limited, and polymers having respective molecular weight distributions may be mixed and melt-kneaded by an extruder, a kneader, a mixer or the like, It may be produced by a polymerization method such as a suspension polymerization method, a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, or a combination thereof. When a resin is obtained by combining the respective polymerization methods, emulsion-suspension polymerization, bulk-suspension polymerization, solution-suspension polymerization, suspension-suspension polymerization, bulk-solution polymerization, solution-solution polymerization, bulk A combination of bulk polymerizations is preferred.

Further, the treatment of the residual monomer or the residual solvent is preferably carried out after the polymerization in a step of heat treatment at 90 ° C. or higher and / or a distillation step. In particular, when heat treatment is performed, it is preferable to use an initiator for treating residual monomers, and when a distillation step is performed, 10
It is preferably performed at 0 ° C. or higher.

Further, for the polymerization of the toner resin, one of radical polymerization catalysts such as peroxide initiators and azo initiators is used.
One kind or two or more kinds can be used. Examples of the radical polymerization catalyst include potassium persulfate, benzoyl peroxide, t-butylperoxybenzoate, and 2,2.
-Azobis (2-methylbutyronitrile), 1,1-azobis (cyclohexane-1-carbonitrile) and the like.

[0021]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, the weight average molecular weight is a value measured by gel permeation chromatography and tetrahydrofuran is used as a solvent, and HCL-802 manufactured by Tosoh Corporation is used.
It was measured by 0 and calculated by polystyrene conversion. The acid value was determined by a titration method using KOH in a toluene solvent. The glass transition temperature (Tg) was measured at a temperature rising rate of 10 ° C./min by a differential calorimeter after melt quenching the sample at 100 ° C. As for the softening temperature, a flow tester CFT-500 manufactured by Shimadzu Corporation was used and a load of 30 was used.
Kgf, heating rate 3 ° C./min, nozzle 1.0 mmφ × 10
The temperature was measured under the condition of mm, and the temperature when the sample flowed out by 1/2 was measured, and this was defined as the softening temperature. The contents of residual monomer and residual solvent were determined by gas chromatography.

The fixing property and the non-offset property are obtained by using a copying machine for negatively charged toner or positively charged toner, which can freely change the copying speed, and set the printing speed to 5
It was evaluated by setting it to 00 mm / sec. Image characteristics are as follows: Use a copier for negatively charged toner or positively charged toner that can freely change the copying speed, set the printing speed to 500 mm / sec, and set the temperature at which the toner is sufficiently fixed. 5000 copies were made and evaluated by the presence or absence of fog phenomenon in the obtained image.

The rising chargeability was determined by measuring the charge amount with a blow-off measuring device after stirring and mixing the carrier and toner with a ball mill, and measuring the time until the charge amount was stabilized.

Blocking resistance is 1 g of toner at 50 ° C.
Evaluation was made based on the aggregation state of the toner after standing for 50 hours in the hot air dryer kept at.

Production Example 1 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with 6000 parts by weight of deionized water and 5 parts by weight of a reactive emulsifier of an allyl alcohol derivative, and then 780 parts by weight of styrene. A mixed solution of 200 parts by weight of 2-ethylhexyl acrylate, 20 parts by weight of methacrylic acid and 2.5 parts by weight of potassium persulfate was added. Then, N ₂ gas was introduced into the reaction vessel, N ₂ substitution was performed for about 1 hour, and the stirring rotation speed was changed to 15
While maintaining at 0 rpm, the reaction system was heated to 72 ° C. and emulsion polymerization was performed for about 3 hours to obtain an emulsion. Next, the temperature of the reaction system was raised to 100 ° C., and 1200 cc of a mixed liquid of the residual monomer and deionized water was flown out. Then, the temperature was lowered and the emulsion was salted out to obtain Resin 1. Resin 1 obtained
Had an acid value of 11.3 mgKOH / g and a weight average molecular weight of 7.5 × 10 ⁵ .

Preparation Example 2 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with 6000 parts by weight of deionized water and 5 parts by weight of a reactive emulsifier of an allyl alcohol derivative, and then 795 parts by weight of styrene. , 200 parts by weight of 2-ethylhexyl acrylate, 5 parts by weight of methacrylic acid and 3 parts by weight of potassium persulfate were added. Then, N ₂ gas was introduced into the reaction vessel, N ₂ substitution was performed for about 1 hour, and the stirring rotation speed was 150 rp.
m, and the reaction system is heated to 75 ° C to carry out emulsion polymerization to about 3
An emulsion was obtained over a period of time. Then, the reaction system is set to 100
Liquid mixture 12 of residual monomer and deionized water
00 cc was drained. Then, the temperature was lowered and the emulsion was salted out to obtain Resin 2. The resulting resin 2 has an acid value of 3.2 mgKOH / g and a weight average molecular weight of 4.5.
It was × 10 ⁵ .

Production Example 3 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with 6000 parts by weight of deionized water and 5 parts by weight of a reactive emulsifier of an allyl alcohol derivative, and then 770 parts by weight of styrene. A mixed solution of 200 parts by weight of 2-ethylhexyl acrylate, 30 parts by weight of methacrylic acid and 2 parts by weight of potassium persulfate was added. After that, N ₂ gas was introduced into the reaction vessel, N ₂ substitution was performed for about 1 hour, and the stirring speed was 150 r.
The reaction system was kept at pm and the temperature of the reaction system was raised to 68 ° C. to carry out emulsion polymerization for about 3 hours to obtain an emulsion. Then, the reaction system is set to 10
Mixture 1 of residual monomer and deionized water heated to 0 ° C
200 cc was drained. Then, the temperature was lowered and the emulsion was salted out to obtain Resin 3. The resin 3 obtained is
The acid value was 18.2 mgKOH / g and the weight average molecular weight was 1.05 × 10 ⁶ .

Preparation Example 4 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with 6000 parts by weight of deionized water and 5 parts by weight of a reactive emulsifier of an allyl alcohol derivative, and then 795 parts by weight of styrene. , 200 parts by weight of n-butyl acrylate, 5 parts by weight of methacrylic acid and 2.5 parts by weight of potassium persulfate were added. Thereafter, about 1 hour N ₂ substituted N ₂ gas was introduced into the reaction vessel, holding the stirring rotational speed to 150 rpm, the reaction system to obtain an emulsion subjected to heated emulsion polymerization for about 3 hours to 72 ° C. .. Then, the temperature of the reaction system is raised to 100 ° C., and a mixed solution 1200 of the residual monomer and deionized water is prepared.
cc was drained. Then, the temperature was lowered and the emulsion was salted out to obtain Resin 4. The resulting resin 4 had an acid value of 3.3 mgKOH / g and a weight average molecular weight of 7.5 × 1.
It was 0 ⁵ .

Production Example 5 A mixture of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol was placed in a reaction vessel equipped with a thermometer, a stirrer and a distillation column, and then 780 parts by weight of styrene and acrylic acid were added. A mixed solution of 200 parts by weight of 2-ethylhexyl, 20 parts by weight of methacrylic acid and 10 parts by weight of α-methylstyrene dimer was added, and the stirring rotation speed was kept at 350 rpm to obtain 80 parts by weight of benzoyl peroxide and t-butylperoxy. 10 parts by weight of benzoate was added. Then, the reaction vessel was kept sealed and the temperature of the reaction system was raised to 130 ° C. in about 30 minutes to carry out suspension polymerization for about 2 hours. Next, the temperature of the reaction system was lowered to 100 ° C., the reaction system was returned to normal pressure, and about 400 cc of residual monomer was allowed to flow out of the reaction system together with deionized water. Then, the reaction system was maintained at 90 ° C., and 15 parts by weight of sodium hydroxide was added to the reaction system to about 30
Alkaline treatment was performed for a minute. The reaction system was cooled to room temperature to obtain Resin 5. The obtained resin 5 has an acid value of 12.9 m.
The weight average molecular weight was 9 × 10 ³ in gKOH / g.

Production Example 6 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with a mixed solution of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol, and then 795 parts by weight of styrene and acrylic acid. A mixed solution of 200 parts by weight of 2-ethylhexyl, 5 parts by weight of methacrylic acid and 15 parts by weight of α-methylstyrene dimer was added, and the stirring rotation speed was kept at 350 rpm to obtain 80 parts by weight of benzoyl peroxide and t-butylperoxy. 10 parts by weight of benzoate was added. Then, the reaction vessel was kept sealed and the temperature of the reaction system was raised to 130 ° C. in about 30 minutes to carry out suspension polymerization for about 2 hours. Then
The temperature of the reaction system was lowered to 100 ° C., the reaction system was returned to normal pressure, and about 400 cc of residual monomer was allowed to flow out of the reaction system together with deionized water. Then, the reaction system was maintained at 90 ° C., 15 parts by weight of sodium hydroxide was added, and alkali treatment was performed for about 30 minutes. The reaction system was cooled to room temperature to obtain Resin 6. The obtained resin 6 has an acid value of 2.9 mgKO.
The weight average molecular weight was 4.5 × 10 ³ at H / g.

Production Example 7 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with a mixed solution of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol, and then 770 parts by weight of styrene and acrylic acid. A mixed solution of 200 parts by weight of 2-ethylhexyl, 30 parts by weight of methacrylic acid and 5 parts by weight of α-methylstyrene dimer was added, and the stirring rotation speed was kept at 350 rpm to obtain 80 parts by weight of benzoyl peroxide and t-butylperoxy. 10 parts by weight of benzoate was added. Then, the reaction vessel was kept at normal pressure, the temperature of the reaction system was raised to 88 ° C. in about 30 minutes, and suspension polymerization was carried out for about 2 hours. Next, the temperature of the reaction system is raised to 100 ° C., and the residual monomer is about 400 c.
c was made to flow out of the reaction system together with deionized water. Then, the reaction system was maintained at 90 ° C., 15 parts by weight of sodium hydroxide was added, and alkali treatment was performed for about 30 minutes. The reaction system was cooled to room temperature to obtain Resin 7. The resulting Resin 7 had an acid value of 18.9 mgKOH / g and a weight average molecular weight of 1.75 × 10 ⁴ .

Production Example 8 A reaction vessel equipped with a thermometer, a stirrer, and a distillation column was charged with a mixed solution of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol, and then 795 parts by weight of styrene and acrylic acid. A mixture of 170 parts by weight of n-butyl, 5 parts by weight of methacrylic acid and 30 parts by weight of diethylaminoethyl methacrylate was added, and the stirring speed was kept at 350 rpm to obtain 2,2-azobis (2-methylbutyronitrile). ) 70
Part by weight was added. Then, the reaction vessel was kept at atmospheric pressure, the temperature of the reaction system was raised to 78 ° C. in about 30 minutes, and suspension polymerization was carried out for about 2 hours. Then, the temperature of the reaction system is set to 100.
The temperature was raised to 0 ° C., and about 400 cc of residual monomer was allowed to flow out of the reaction system together with deionized water. Then, the reaction system was cooled to room temperature to obtain Resin 8. The resulting resin 8 has an acid value of 2.9 mgKOH / g and a weight average molecular weight of 2.85.
It was × 10 ⁴ .

Production Example 9 A reaction vessel equipped with a thermometer, a stirrer, and a distillation column was charged with a mixed solution of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol, and then 795 parts by weight of styrene and acrylic acid. A mixture of 190 parts by weight of n-butyl, 5 parts by weight of methacrylic acid and 10 parts by weight of diethylaminoethyl methacrylate was added, and the stirring speed was kept at 350 rpm to obtain 2,2-azobis (2-methylbutyronitrile). ) 80
Parts by weight and 10 parts by weight of 1,1-azobis (cyclohexane-1-carbonitrile) were added. Then, keep the reaction vessel in a sealed state and raise the temperature of the reaction system up to 100 ° C by about 3
The temperature was raised in 0 minutes and suspension polymerization was carried out for about 2 hours. Next, while maintaining the temperature of the reaction system at 100 ° C., about 400 cc of residual monomer was allowed to flow out of the reaction system together with deionized water. Then, the reaction system was cooled to room temperature to obtain Resin 9. The resulting Resin 9 had an acid value of 2.5 mgKOH / g and a weight average molecular weight of 8.5 × 10 ³ .

Production Example 10 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with a mixed solution of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol, and then 790 parts by weight of styrene and acrylic acid. A mixture of 150 parts by weight of n-butyl, 5 parts by weight of methacrylic acid and 50 parts by weight of diethylaminoethyl methacrylate was added, and the stirring speed was kept at 350 rpm to obtain 2,2-azobis (2-methylbutyronitrile). ) 50
Part by weight was added. Then, the reaction vessel was kept at atmospheric pressure, the temperature of the reaction system was raised to 78 ° C. in about 30 minutes, and suspension polymerization was carried out for about 2 hours. Then, the temperature of the reaction system is set to 100.
The temperature was raised to 0 ° C., and about 400 cc of residual monomer was allowed to flow out of the reaction system together with deionized water. Then, the reaction system was cooled to room temperature to obtain Resin 10. The resulting resin 10 is
The acid value is 2.1 mgKOH / g and the weight average molecular weight is 5.
It was 55 × 10 ⁴ .

Production Example 11 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with 6000 parts by weight of deionized water and 5 parts by weight of a reactive emulsifier of an allyl alcohol derivative, and then 800 parts by weight of styrene. , 200 parts by weight of n-butyl acrylate and 2.5 parts by weight of potassium persulfate were added. Thereafter, the reaction vessel N ₂ gas was subjected to introduction for about 1 hour N ₂ substitutions, and retains the stirring rotational speed to 150 rpm, the reaction system to obtain an emulsion subjected to heated emulsion polymerization for about 3 hours to 72 ° C.. Next, the temperature of the reaction system was raised to 100 ° C., and 1200 cc of a mixed liquid of the residual monomer and deionized water was flown out. afterwards,
The temperature was lowered and the emulsion was salted out to obtain Resin 11.
The obtained resin 11 has an acid value of 0.5 mgKOH / g
The weight average molecular weight was 7 × 10 ⁵ .

Production Example 12 A reaction vessel equipped with a thermometer, a stirrer, and a distillation column was charged with a mixed solution of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol, and then 800 parts by weight of styrene and acrylic acid. A mixed solution of 200 parts by weight of n-butyl and 10 parts by weight of α-methylstyrene dimer was added, and the stirring speed was set to 3
80 parts by weight of benzoyl peroxide and t
10 parts by weight of butyl peroxybenzoate were added. After that, the reaction vessel is kept sealed and the temperature of the reaction system is raised to 130 ° C. in about 30 minutes to carry out suspension polymerization in about 2 minutes.
Went on time. Next, the temperature of the reaction system is lowered to 100 ° C., the reaction system is returned to normal pressure, and the residual monomer is about 400 cc.
Was allowed to flow out of the reaction system together with deionized water. afterwards,
The reaction system was maintained at 90 ° C., 15 parts by weight of sodium hydroxide was added, and alkali treatment was performed for about 30 minutes. The reaction system was cooled to room temperature to obtain Resin 12. Resin 1 obtained
No. 2 had an acid value of 0.5 mgKOH / g and a weight average molecular weight of 8.7 × 10 ³ .

Production Example 13 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with 6000 parts by weight of deionized water and 5 parts by weight of a reactive emulsifier of an allyl alcohol derivative, and then 660 parts by weight of styrene. A mixed solution of 300 parts by weight of n-butyl acrylate, 40 parts by weight of methacrylic acid and 2.5 parts by weight of potassium persulfate was added. Then, N ₂ gas was introduced into the reaction vessel, N ₂ substitution was performed for about 1 hour, and the stirring rotation speed was 150 rpm.
The reaction system was heated to 72 ° C. and emulsion polymerization was performed for about 3 hours to obtain an emulsion. Next, the reaction system is heated to 100 ° C.
Temperature rises to 120 and mixed liquid of residual monomer and deionized water 120
0 cc was drained. Then, the temperature was lowered and the emulsion was salted out to obtain Resin 13. The obtained resin 13 is
The acid value was 26.5 mgKOH / g and the weight average molecular weight was 7.5 × 10 ⁵ .

Production Example 14 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with a mixed solution of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol, and then 660 parts by weight of styrene and acrylic acid. A mixed solution of 300 parts by weight of n-butyl, 40 parts by weight of methacrylic acid and 10 parts by weight of α-methylstyrene dimer was charged, and the stirring rotation speed was kept at 350 rpm, and 80 parts by weight of benzoyl peroxide and t-butylperoxy were added. 10 parts by weight of benzoate was added. Then, the reaction vessel was kept sealed and the temperature of the reaction system was raised to 130 ° C. in about 30 minutes to carry out suspension polymerization for about 2 hours. Next, the temperature of the reaction system was lowered to 100 ° C., the reaction system was returned to normal pressure, and about 400 cc of residual monomer was allowed to flow out of the reaction system together with deionized water. Then, the reaction system was maintained at 90 ° C., 15 parts by weight of sodium hydroxide was added, and alkali treatment was performed for about 30 minutes. The reaction system was cooled to room temperature to obtain Resin 14. The resulting resin 14 had an acid value of 26.4 mg KO.
The weight average molecular weight was 9 × 10 ³ at H / g.

Production Example 15 A reaction vessel equipped with a thermometer, a stirrer and a distillation column was charged with 6000 parts by weight of deionized water and 5 parts by weight of a reactive emulsifier of an allyl alcohol derivative, and then 795 parts by weight of styrene. , 200 parts by weight of n-butyl acrylate, 5 parts by weight of methacrylic acid and 2.5 parts by weight of potassium persulfate were added. Thereafter, about 1 hour N ₂ substituted N ₂ gas was introduced into the reaction vessel, holding the stirring rotational speed to 150 rpm, the reaction system to obtain an emulsion subjected to heated emulsion polymerization for about 3 hours to 72 ° C. .. Next, the temperature of the reaction system was lowered and the emulsion was salted out to obtain Resin 15. The resulting Resin 15 had an acid value of 3.3 mgKOH / g and a weight average molecular weight of 7.5 × 10 ⁵ .

Production Example 16 A mixture of 2000 parts by weight of deionized water and 4.5 parts by weight of polyvinyl alcohol was placed in a reaction vessel equipped with a thermometer, a stirrer and a distillation column, and then 795 parts by weight of styrene and acrylic acid were added. A mixture of 190 parts by weight of n-butyl, 5 parts by weight of methacrylic acid and 10 parts by weight of diethylaminoethyl methacrylate was added, and the stirring speed was kept at 350 rpm to obtain 2,2-azobis (2-methylbutyronitrile). ) 80
Parts by weight and 10 parts by weight of 1,1-azobis (cyclohexane-1-carbonitrile) were added. Then, keep the reaction vessel in a sealed state and raise the temperature of the reaction system up to 100 ° C by about 3
The temperature was raised in 0 minutes and suspension polymerization was carried out for about 2 hours. Then, the temperature of the reaction system was lowered to room temperature to obtain Resin 16. The resulting resin 16 had an acid value of 2.5 mgKOH / g and a weight average molecular weight of 8.5 × 10 ³ .

Example 1 20 parts by weight of Resin 1 obtained in Production Example 1 and 80 parts by weight of Resin 5 obtained in Production Example 5 were used at 180 ° C. using a mixer.
To obtain a resin for toner. The obtained resin for toner has a glass transition temperature of 64 ° C. and a softening temperature of 13
5 ℃, acid value 12.5mgKOH / g, AV ^H / AV ^L
Was 0.88. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 9.1 × 10 3. Furthermore, the amount of residual monomers was 50 ppm or less.

On the other hand, 92 parts by weight of the obtained resin for toner, 5 parts by weight of carbon black, and 3 parts by weight of low-molecular-weight polypropylene wax were mixed, and mixed with a twin-screw extruder to prepare 1
The toner was manufactured by kneading at 50 ° C., cooling and then finely pulverizing and classifying. The toner properties of the obtained toner were evaluated using a copier for negative charging.
Both the non-offset property and the blocking resistance were excellent. In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 5 minutes.

Example 2 A toner resin was obtained under the same conditions as in Example 1 except that 38 parts by weight of Resin 2 obtained in Production Example 2 and 62 parts by weight of Resin 5 obtained in Production Example 5 were used. It was The obtained resin for toner has a glass transition temperature of 66 ° C. and a softening temperature of 138.
C., the acid value was 9.2 mg KOH / g, and the AV ^H / AV ^L was 0.24. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, and the weight average molecular weight of the high molecular weight region is 3.9 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 9 × 10 ³ . Furthermore, the amount of residual monomers was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, the fixability, non-offset property, and blocking resistance were excellent.
In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 3 minutes.

Example 3 A toner resin was obtained under the same conditions as in Example 1 except that 30 parts by weight of Resin 2 obtained in Production Example 2 and 70 parts by weight of Resin 7 obtained in Production Example 7 were used. It was The obtained resin for toner has a glass transition temperature of 62 ° C. and a softening temperature of 143.
℃, acid value 14.19mgKOH / g, AV ^H / AV ^L
Was 0.174. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, and the weight average molecular weight of the high molecular weight region is 3.91 × 10 ^5, which is the weight average molecular weight of the low molecular weight region. Was 1.7 × 10 ⁴ . further,
The amount of residual monomer was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, both the non-offset property and the blocking resistance were excellent. The fixability was slightly inferior, but it was not a problem in practical use. In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 6 minutes.

Example 4 A toner resin was obtained under the same conditions as in Example 1 except that 17 parts by weight of Resin 3 obtained in Production Example 3 and 83 parts by weight of Resin 6 obtained in Production Example 6 were used. It was The obtained resin for toner has a glass transition temperature of 57 ° C. and a softening temperature of 121.
C., the acid value was 7.3 mg KOH / g, and AV ^H / AV ^L was 6.48. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the high molecular weight region has a weight average molecular weight of 9 × 10 ⁵ , and the low molecular weight region has a weight average molecular weight of 4 It was 0.6 × 10 ³ . Furthermore, the amount of residual monomers was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, the fixability, non-offset property, and blocking resistance were excellent.
In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 3 minutes.

Example 5 Example 1 was repeated except that 17 parts by weight of Resin 11 obtained in Production Example 11 and 83 parts by weight of Resin 7 obtained in Production Example 7 were used.
A resin for toner was obtained under the same conditions as above. The obtained resin for toner has a glass transition temperature of 58 ° C. and a softening temperature of 12
3 ℃, acid value 15.7mgKOH / g, AV ^H / AV ^L
Was 0.03. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, and the weight average molecular weight of the high molecular weight region is 6.1 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 1.76 × 10 ⁴ . Furthermore, the amount of residual monomers was 50 ppm or less.

The toner resin thus obtained was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, the fixability, non-offset property, and blocking resistance were excellent.
In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 6 minutes.

Example 6 35 parts by weight of Resin 3 obtained in Production Example 3 and Production Example 12
Example 1 except that 65 parts by weight of the resin 12 obtained in 1. was used.
A resin for toner was obtained under the same conditions as above. The obtained resin for toner has a glass transition temperature of 60 ° C. and a softening temperature of 13
4 ° C., an acid value of ^{6.9mgKOH / g, AV H / AV} L was 37.6. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 9 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is 8 It was 0.6 × 10 ³ . Furthermore, the amount of residual monomers was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, the fixability, non-offset property, and blocking resistance were excellent.
In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 3 minutes.

Example 7 17 parts by weight of Resin 3 obtained in Production Example 3 and Production Example 12
Example 1 except that 83 parts by weight of the resin 12 obtained in 1. was used.
A resin for toner was obtained under the same conditions as above. The obtained resin for toner has a glass transition temperature of 55 ° C. and a softening temperature of 11
At 8 ° C., the acid value was 2.4 mg KOH / g and AV ^H / AV ^L was 22.6. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 8.6 × 10 ³ . Furthermore, the amount of residual monomers was about 55 ppm.

The toner resin thus obtained was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, the fixability, non-offset property, and blocking resistance were excellent.
In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 3 minutes.

Example 8 A toner resin was obtained under the same conditions as in Example 1 except that 30 parts by weight of the resin 4 obtained in Production Example 4 and 70 parts by weight of the resin 8 obtained in Production Example 8 were used. It was The obtained resin for toner has a glass transition temperature of 58 ° C. and a softening temperature of 131.
° C., an acid value of ^{3.1mgKOH / g, AV H / AV} L was 1.14. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.85 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 2.86 × 10 ⁴ . Furthermore, the amount of residual monomers was about 300 ppm.

The toner resin thus obtained was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for positive charging. As a result, the fixability, non-offset property, and blocking resistance were excellent. In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was positively large and the charge amount was stable and good in 3 minutes.

Example 9 A toner resin was obtained under the same conditions as in Example 1 except that 30 parts by weight of Resin 4 obtained in Production Example 4 and 70 parts by weight of Resin 9 obtained in Production Example 9 were used. It was The obtained resin for toner has a glass transition temperature of 53 ° C. and a softening temperature of 132.
C., the acid value was 2.7 mg KOH / g, and AV ^H / AV ^L was 1.32. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 8.7 × 10 ³ . Further, the amount of residual monomer was about 800 ppm.

The toner resin thus obtained was made into a toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for positive charging. As a result, the fixing property and the non-offset property were excellent. Regarding the blocking resistance, although a slight blocking phenomenon was observed, there was no problem in practical use. In terms of image characteristics, a clear image free from fog was obtained. Further, the rising chargeability was positively large and the charge amount was stable and good in 6 minutes.

Example 10 30 parts by weight of Resin 4 obtained in Production Example 4 and Production Example 10
A resin for toner was obtained under the same conditions as in Example 1 except that 70 parts by weight of the resin 10 obtained in 1. was used. The obtained resin for toner has a glass transition temperature of 62 ° C. and a softening temperature of 1
42 ℃, acid value 2.1mgKOH / g, AV ^H / AV ^L
Was 1.57. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 5.6 × 10 ⁴ . further,
The amount of residual monomer was about 100 ppm.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for positive charging. As a result, the anti-offset property and the blocking resistance were excellent. The fixability was slightly inferior, but there was no problem in practical use. Also,
In terms of image characteristics, a clear image without fog was obtained. Further, the rising chargeability was positively large and the charge amount was stable and good in 3 minutes.

Comparative Example 1 A toner resin was obtained under the same conditions as in Example 1 except that 30 parts by weight of the resin 13 obtained in Production Example 13 and 70 parts by weight of the resin 14 obtained in Production Example 14 were used. It was The obtained resin for toner has a glass transition temperature of 43 ° C., a softening temperature of 132 ° C., an acid value of 26.1 mg KOH / g, AV ^H /
AV ^L was 1.00. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 9.1 × 10 ³ . Furthermore, the amount of residual monomers was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for positive charging and negative charging. As a result, the fixability and the non-offset property were excellent. Blocking resistance was poor because many blocking phenomena were observed. Further, in terms of image characteristics, although some fog occurred, there was no problem in practical use. Further, the positive charging property was weak both positively and negatively, and the charge amount was not stable and continued to increase, which was poor.

Comparative Example 2 A toner resin was obtained under the same conditions as in Example 1 except that 30 parts by weight of the resin 13 obtained in Production Example 13 and 70 parts by weight of the resin 12 obtained in Production Example 12 were used. It was The obtained resin for toner has a glass transition temperature of 54 ° C., a softening temperature of 133 ° C., an acid value of 8.3 mgKOH / g, AV ^H / A.
V ^L was 53.0. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 8.8 × 10 ³ . further,
The amount of residual monomer was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for positive charging and negative charging. As a result, the fixability, non-offset property and blocking resistance were excellent. Further, in terms of image characteristics, although some fog occurred, there was no problem in practical use. further,
With respect to the rising chargeability, both positive and negative charges were weak, and the charge amount was not stable and continued to increase, which was poor.

Comparative Example 3 A toner resin was obtained under the same conditions as in Example 1 except that 30 parts by weight of the resin 11 obtained in Production Example 11 and 70 parts by weight of the resin 14 obtained in Production Example 14 were used. It was The obtained resin for toner has a glass transition temperature of 60 ° C., a softening temperature of 135 ° C., an acid value of 18.6 mgKOH / g, AV ^H /
The AV ^L was 0.02. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 9 × 10 ³ . Furthermore, the amount of residual monomers was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for positive charging and negative charging. As a result, the fixability, non-offset property and blocking resistance were excellent. Further, in terms of image characteristics, although some fog occurred, there was no problem in practical use. further,
With respect to the rising chargeability, both positive and negative charges were weak, and the charge amount was not stable and continued to increase, which was poor.

Comparative Example 4 A toner resin was obtained under the same conditions as in Example 1 except that 5 parts by weight of Resin 3 obtained in Production Example 3 and 95 parts by weight of Resin 6 obtained in Production Example 6 were used. It was The obtained resin for toner has a glass transition temperature of 48 ° C. and a softening temperature of 105.
° C., an acid value of ^{3.7mmgKOH / g, AV H / AV} L was 6.48. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the high molecular weight region has a weight average molecular weight of 9 × 10 ⁵ , and the low molecular weight region has a weight average molecular weight of 4 It was 0.6 × 10 ³ . Furthermore, the amount of residual monomers was 50 ppm or less.

The toner resin thus obtained was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, the fixability was excellent, but the non-offset property was poor. Blocking resistance was poor because many blocking phenomena were observed. In terms of image characteristics, a clear image without fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 7 minutes.

Comparative Example 5 A toner resin was obtained under the same conditions as in Example 1 except that 50 parts by weight of Resin 3 obtained in Production Example 3 and 50 parts by weight of Resin 6 obtained in Production Example 6 were used. It was The obtained resin for toner has a glass transition temperature of 64 ° C. and a softening temperature of 148.
At 0 ° C., the acid value was 10.9 mgKOH / g, and the AV ^H / AV ^L was 6.48. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the high molecular weight region has a weight average molecular weight of 9 × 10 ⁵ , and the low molecular weight region has a weight average molecular weight of 4 It was 0.6 × 10 ³ . Furthermore, the amount of residual monomers was 50 ppm or less.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for negative charging. As a result, the anti-offset property and the blocking resistance were excellent, but the fixability was poor. In terms of image characteristics, a clear image without fog was obtained. Further, the rising chargeability was negatively large and the charge amount was stable and good in 7 minutes.

Comparative Example 6 A toner resin was obtained under the same conditions as in Example 1 except that 30 parts by weight of the resin 15 obtained in Production Example 15 and 70 parts by weight of the resin 16 obtained in Production Example 16 were used. It was The obtained resin for toner has a glass transition temperature of 48 ° C., a softening temperature of 129 ° C., an acid value of 2.7 mgKOH / g, AV ^H / A.
V ^L was 1.32. Further, in the molecular weight distribution by gel permeation chromatography, there are two peaks in the high molecular weight region and the low molecular weight region, the weight average molecular weight of the high molecular weight region is 6.8 × 10 ⁵ , and the weight average molecular weight of the low molecular weight region is Was 8.7 × 10 ³ . further,
The amount of residual monomer was about 1300 ppm.

The obtained toner resin was made into toner by the same method as in Example 1, and the toner characteristics were evaluated using a copying machine for positive charging. As a result, the fixability and the non-offset property were excellent. Blocking resistance was poor because many blocking phenomena were observed. In terms of image characteristics, a clear image without fog was obtained. Further, the rising chargeability was positively large and the charge amount was stable and good in 8 minutes.

As described above, the toner resin of the present invention has a good balance between fixability and non-offset property by controlling the molecular weight and content ratio of the high molecular weight polymer and the low molecular weight polymer, By controlling the acid value of the low molecular weight polymer and the ratio thereof, rising charge can be improved, and by controlling the residual monomer of the resin to be a certain amount or less, a clear image without fog can be obtained. Further, when the softening temperature is within a certain range, the fixability is good, and when the glass transition temperature is within a certain range, the blocking resistance is good.

[0074]

The toner resin of the present invention controls the molecular weight, content ratio, acid value and ratio of the high molecular weight polymer and the low molecular weight polymer to control the residual monomer amount of the resin.
High-quality toner with good image characteristics, which is excellent in fixability, non-offset property, blocking resistance, rising charge, and can obtain clear images without fogging by setting the softening temperature and glass transition temperature within certain ranges. Can be provided.

Claims (1)

[Claims] 1. A weight average molecular weight of 3 × 10 ^{5 to} 1.5 ×
10 ⁶ and an acid value (AV ^H ) of 0.5 to 20 mg KO
H / g of high molecular weight polymer 15 to 40% by weight, weight average molecular weight of 3 × 10 ^{3 to} 6 × 10 ⁴ , and acid value (A
^VL ) is 0.5 to 20 mgKOH / g, and a low molecular weight polymer is 60 to 85% by weight, and an acid value is 20 mgKOH /
a styrene-acrylic copolymer having a weight ratio of g or less, which is AV
^H / AV ^L is 0.025 to 40, the residual monomers and /
Alternatively, a resin for high-quality toner, which has a residual solvent content of 1000 ppm or less, a glass transition temperature of 50 to 68 ° C., and a softening temperature of 110 to 145 ° C.