JPH05323663A - Binder resin for positively chargeable toner - Google Patents

Abstract

PURPOSE:To obtain a binder resin for a toner excellent in positive chargeability as well as fixability, anti-offsetting property and blocking resistance, ensuring a stable amt. of positive charges and causing no environmental pollution. CONSTITUTION:This binder resin for a positively chargeable toner is a polymer contg. acrylic ester and/or methacrylic ester (A) having an ether group, other acrylic ester and/or methacrylic ester (B) and styrene (C) while satisfying inequalities 50wt.%<=C/(A+B+C)X100<=90wt.%, 10wt.%<=(A+B)/(A+B+C)X100<=50 wt.% and 3wt.%<=A/(A+B)X100<=90wt.%. This resin binder has 40-68 deg.C glass transition temp., 80-180 deg.C softening temp. and <=20mg KOH/g acid value.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a toner which is excellent in non-offset property, fixing property and blocking resistance used in electrophotographic method, electrostatic printing method, etc. A binder resin for use is provided.

[0002]

2. Description of the Related Art Toners and binder resins for toners used in electrophotographic copying machines, printers and the like are required to have the following properties. Blocking resistance and the like are listed, and secondly, charging characteristics that affect image formation are listed.

Regarding the fixability, it is of utmost importance to lower the fixing temperature due to the increase in the printing speed, and as the binder resin for toner, one having good melt fluidity has been used. Regarding the non-offset property, it is important that the toner does not offset to the roller even in a relatively high temperature region, and as the binder resin for toner, one having a high elastic force has been used. Regarding blocking resistance, it is important that the toner does not block even if the temperature during storage of the toner is high, and as the binder resin for toner, one having a relatively high glass transition temperature (Tg) has been used.

Furthermore, the charging characteristics that have the greatest influence on image formation are important, and the problem of charge amount and charge stability (moisture resistance)
It is roughly divided into. Regarding the problem of the charge amount, it is necessary to determine the charge amount of the toner and the binder resin for the toner by the photoconductor such as a copying machine or a printer, and the charge amount of the binder resin for the toner depends on the monomer and the molecular structure used. I've been in control. Regarding the charge stability, it is necessary that the charge amount does not change with time during printing and that the charge amount of the toner does not decrease at high humidity, and as a binder resin for toner, this is prevented by the resin manufacturing method. I've been

The charging of the toner and the binder resin for the toner includes a negative charging type and a positive charging type. For a negative charging type toner, the charge amount is adjusted by a negative charging type resin and a negative charging type charge control agent. Has been done. Further, the positively chargeable toner also uses a positively chargeable resin and a charge control agent like the negatively chargeable toner, but the control of the charge amount of the positively chargeable toner has various problems, Various studies have been conducted on a positively chargeable binder resin for toner.

[0006]

In order to obtain a positively chargeable binder resin, an amine type or amide type monomer is generally used. However, when an amine type or amide type monomer is used, Requires that an azo-based polymerization initiator be used in the synthesis of the binder resin, and the reaction conditions and characteristic values of the resin may differ when compared with the case where a peroxide-based polymerization initiator is used. However, there is a problem in that the moisture resistance becomes poor and the charging stability becomes poor, and the thermal characteristics of the toner are different, resulting in poor toner color development. Furthermore, azobisisobutyronitrile, which is generally used as an azo-based polymerization initiator, has a problem of environmental pollution because a toxic substance having a CN group is generated as a decomposition by-product.

SUMMARY OF THE INVENTION An object of the present invention is to provide a binder resin for toner which is excellent in non-offset property, fixing property and anti-blocking property and has excellent positive charging property without environmental pollution.

[0008]

In view of the above situation, the inventors of the present invention have made extensive studies as to a resin for toner, and as a result, they have excellent non-offset property, fixing property, blocking resistance property, and excellent positive charging property. And a binder resin for a toner of the present invention having no environmental pollution is found. That is, the binder resin for a positively chargeable toner of the present invention comprises an acrylic acid ester component and / or a methacrylic acid ester component (A) having an ether group and an acrylic acid ester component and / or a methacrylic acid ester component other than the A component ( B) and a polymer component containing a styrene component (C), the blending amounts of A component, B component and C component satisfy the following relational expressions (1) to (3), and the glass transition temperature is 40 to 68 ° C, softening temperature of 80-
It is characterized by having an acid value of 20 mgKOH / g or less at 180 ° C.

50% by weight ≦ C / (A + B + C) × 100 ≦ 90% by weight (1) 10% by weight ≦ (A + B) / (A + B + C) × 100 ≦ 50% by weight (2) 3% by weight ≦ A / (A + B) × 100 ≦ 90% by weight (3) Examples of the acrylate ester component or methacrylic acid ester component having an ether group, which is the component A of the resin of the present invention, include 2-ethoxyethyl acrylate, 2-methoxyethyl acrylate, and acrylic acid. 2-Budoxyethyl, 2-ethoxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-budoxyethyl methacrylate and the like can be mentioned, with 2-ethoxyethyl methacrylate being particularly preferred. In the present invention, the acrylic ester component or methacrylic ester component having these ether groups may be used alone,
You may mix and use 2 or more types.

The acrylic acid ester component or methacrylic acid ester component which is the component B of the present invention is a component other than the acrylic acid ester component or methacrylic acid ester component having an ether group. Examples of the acrylate component include acrylic acid, ethyl acrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, and lauryl acrylate. Among them, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferable.
Examples of the methacrylic acid ester component include methacrylic acid, ethyl methacrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, Examples thereof include glycidyl methacrylate, cyclohexyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, and the like. Among them, methacrylic acid, methyl methacrylate, and n-butyl methacrylate are particularly preferable. Such an acrylic acid ester component or a methacrylic acid ester component can improve the positive chargeability of the toner, and can easily obtain a synergistic effect with the acrylic acid ester component or the methacrylic acid ester component having an ether group. is there.

Further, the styrene component which is the component C of the present invention includes, for example, styrene, O-methylstyrene,
m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Examples thereof include p-tert butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, and α-methyl styrene. Among them, styrene, p-methylstyrene and α-methylstyrene are particularly preferable. By using such a styrene component,
It is possible to improve the moisture resistance of the toner.

In the present invention, it is important that the blending amounts of the above-mentioned components A, B and C are in the relations of the following formulas (1) to (3). Within this range, excellent positive charging property is obtained. And a binder resin having moisture resistance is obtained.

50% by weight ≦ C / (A + B + C) × 100 ≦ 90% by weight (1) 10% by weight ≦ (A + B) / (A + B + C) × 100 ≦ 50% by weight (2) 3% by weight ≦ A / (A + B) × 100 ≦ 90% by weight (3) Formula (1) indicates that the C component is contained in the whole polymer component in the range of 50 to 90% by weight, preferably in the range of 55 to 85% by weight. Is. This is because the resin whose C component is in this region has excellent moisture resistance of the toner and does not impair the positive charging property.

The formula (2) includes components A and B, that is, components having an ether group, and the total amount of acrylic acid ester component and / or methacrylic acid ester component is 10 to 50% by weight based on the total amount of polymer components. It is shown that the content is in the range, and preferably in the range of 15 to 45% by weight. This is because the resin in this region can improve the positive charging property without impairing the moisture resistance.

The formula (3) is a ratio of the A component to the A component and the B component, that is, an acrylic group having an ether group to the whole acrylic acid ester component and / or a methacrylic acid ester component including a component having an ether group. It is shown that the acid ester component and / or the methacrylic acid ester component is in the range of 3 to 90% by weight, and preferably in the range of 5 to 85% by weight. this is,
This is because the resin in this region is excellent in positive charging property.

In the binder resin of the present invention, the glass transition temperature needs to be in the range of 40 to 68 ° C, preferably 50 to 65 ° C. this is,
This is because if the glass transition temperature is lower than 40 ° C., the blocking resistance of the toner is poor, and if it exceeds 68 ° C., the fixing property of the toner is poor. In the binder resin of the present invention, the softening temperature needs to be in the range of 80 to 180 ° C, preferably 90 to 170 ° C. This is because when the softening temperature is lower than 80 ° C., the non-offset property of the toner is poor, and when it exceeds 180 ° C., the fixing property of the toner is poor. Furthermore, in the binder resin of the present invention, it is necessary that the acid value is 20 mgKOH / g or less, preferably 15 mgKOH.
/ G or less. This has an acid value of 20 mg KOH
This is because the moisture resistance of the toner is inferior when it exceeds / g.

Further, in the binder resin of the present invention, by controlling the molecular weight of the THF-soluble component, it is more effective for the positive charging property. That is, the weight average molecular weight is 3,000 to 80,000,
The number average molecular weight is preferably in the range of 1,000 to 45,000, and by controlling in this molecular weight range, excellent positive charging property is exhibited. This is because a resin having a weight average molecular weight of less than 3,000 tends to have a low glass transition temperature and poor blocking resistance, and a resin having a weight average molecular weight of more than 80,000 has a poor positive charging property. More preferably, the weight-average molecular weight is 5,
It is in the range of 000 to 70,000. Further, a resin having a number average molecular weight of less than 1,000 tends to have a low glass transition temperature and is inferior in blocking resistance, and conversely 45,000.
This is because the resin exceeding 0 has a poor positive charging property, and is more preferably in the range of 2,000 to 40,000.

A chain transfer agent component may be used as a softening temperature and molecular weight adjusting agent in the binder resin of the present invention. Examples of the chain transfer agent component include α-methylstyrene dimer, n-dodecyl mercaptan and thioglycol. Examples thereof include acid esters and n-octyl mercaptan, and of these, α-methylstyrene dimer and thioglycolic acid ester are particularly preferable. The molecular structure of the binder resin of the present invention has a cross-linking structure, a non-cross-linking structure having one or more peaks in the ultrahigh molecular weight region and low molecular weight region in the molecular weight distribution, and one or more peaks in the molecular weight distribution And the like, but can be appropriately selected in consideration of the fixing property and non-offset property of the toner.

The binder resin having a crosslinked structure is
It contains 1 to 75% of a component (gel fraction) insoluble in a solvent such as tetrahydrofuran or chloroform. The monomer giving the crosslinked structure is not particularly limited as long as it forms the crosslinked structure in the reaction,
For example, divinylbenzene, aromatic divinyl compounds such as divinylnaphthalene, ethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butylene glycol diacrylate, Examples thereof include trimethylol propane triacrylate, tetramethylol methane triacrylate, tetramethylol methane tetraacrylate, acrylates of bisphenol A derivative type, and the like in which acrylic acid of these compounds is changed to methacrylic acid.

The non-crosslinked binder resin having one or more peaks in the ultrahigh molecular weight and one in the extremely low molecular weight in the molecular weight distribution has a molecular weight of 3 in the molecular weight distribution.
A binder resin having one or more peaks in the ultrahigh molecular region of 10 ^{5 to} 2 × 10 ⁶ and one or more peaks in the low molecular weight region of 3 × 10 ³ to 8 × 10 ⁴ is preferable. Further, the binder resin having one or more peaks in the molecular weight distribution is a binder resin having a non-crosslinking structure having one or more peaks in the molecular weight distribution, in addition to the above-mentioned non-crosslinking structure.

The binder resin of the present invention can be used alone as a binder resin for toner,
Normally used styrene / acrylic, styrene /
Binder resins such as butadiene type and polyester type,
Alternatively, they can be used in combination with a mixture thereof. Examples of the method for producing the binder resin of the present invention include bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization and the like, and two or more of these polymerization methods may be combined. These manufacturing methods are preferably selected according to the required characteristics of the toner.

The polymerization initiator used in the production of the binder resin of the present invention is not particularly limited as long as it can be used in ordinary radical polymerization, but in order to achieve the object of the present invention, a peroxide type initiator is used. The polymerization initiator of is particularly preferable. Examples of peroxide-based polymerization initiators include benzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxy 2-ethylhexanoate, t-butylperoxybenzoate and t-butylperoxy. Examples thereof include isopropyl carbonate and di-t-butyldiperoxyisophthalate, which may be used alone or in combination of two or more kinds.
Among them, benzoyl peroxide and t-butyl peroxybenzoate are particularly preferable. Furthermore, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4′-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) 3,3,3 5-trimethylcyclohexane, 1,1-azobis (cyclohexane-1-
Carbonitrile), 2,2'-azobis (2,4,4-
The effect of positive charging can also be obtained by using an azo-based polymerization initiator such as trimethylpentane).

When the binder resin of the present invention is produced by emulsion polymerization or suspension polymerization, ordinary emulsifiers and dispersants can be used. As the emulsifier and the dispersant, polyvinyl alcohol, a sodium polyacrylate-based dispersant,
Examples include polyether-based dispersants and ethylene oxide-based dispersants. Furthermore, as a dispersion aid, sodium sulfate, sodium carbonate, hydrogen peroxide solution, which are usually used,
Boric acid or the like can be used.

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, the glass transition temperature (Tg) was determined by heating the sample to 100 ° C. and melt quenching,
It was measured by a differential calorimeter at a temperature rising rate of 10 ° C./min. The softening temperature was measured under the conditions of a load of 30 Kgf and a heating rate of 3 ° C./min using a flow tester CFT-500 manufactured by Shimadzu Corporation having a nozzle of 1.0 mmφ × 10 mm, and 1/2 of the sample flowed out. The temperature at that time was defined as the softening temperature. The acid value was determined by a titration method using KOH in a toluene solvent.

The molecular weight was determined by polystyrene conversion using gel permeation chromatography HCL-8020 (manufactured by Toso Corporation). The gel fraction was measured when 0.5 g of the sample was put in 50 ml of tetrahydrofuran, heated and dissolved at 60 ° C. for 3 hours, filtered through a glass filter covered with Celite # 545, and sufficiently dried at 80 ° C. using a vacuum dryer. The weight is divided by the initial weight. The positive charging property is obtained by weighing 0.45 part by weight of the toner and 10 parts by weight of the carrier for positive charging in a polyethylene container of 50 cc and heating at 20
After leaving it for about 24 hours in an environment of ℃ and humidity of 60%, 0.2 parts by weight of a mixture which was stirred and mixed with a ball mill stirrer at a speed of about 200 rpm for about 30 minutes was weighed, and a blow-off electrostatic charge measuring device (Toshiba Chemical Co., Ltd. The charge amount was measured by using TB-500 manufactured by KK, and the sign was reversed to calculate the charge amount per 1 g of the toner. As a result, it was evaluated according to the following criteria.

⊚: Charge amount of 25 μC / g or more ◯: Charge amount of 20 to 24 μC / g Δ: Charge amount of 14 to 20 μC / g ×: Charge amount of less than 14 μC / g Moisture resistance is the same as that of positive charge property. The charge amount after standing for about 24 hours in an environment of temperature 35 ° C. and humidity 85% is calculated, and the difference is obtained from the amount of charge after standing for about 24 hours in the environment of temperature 20 ° C. and humidity 60%. It was evaluated according to the standard.

⊚: less than 2 μC / g ◯: less than 2 to 3 μC / g Δ: less than 3 to 4 μC / g x: 4 μC / g or more The fixing property is a fixing tester capable of freely changing temperature and speed. The fixing temperature was measured by using and the result was evaluated according to the following criteria.

⊚: Less than 120 ° C. ∘: 120 to 139 ° C. Δ: 140 to 149 ° C. ×: 150 ° C. or more The non-offset property is offset by using a fixing tester capable of freely changing temperature and speed. The generated temperature was measured and the result was evaluated according to the following criteria.

⊚: 170 ° C. or higher ○: 155 to 169 ° C. Δ: 140 to 154 ° C. ×: less than 140 ° C. As for blocking resistance, about 10 g of the toner was put in a 200 cc glass container and kept at about 40 ° C. in a hot air dryer. After standing for about 120 hours in a glass container, the aggregation state of the toner when the taken out glass container was turned upside down was evaluated according to the following criteria.

⊚: The toner is uniformly dispersed. ◯: The toner is uniformly dispersed by tapping twice. Δ: The toner is uniformly dispersed by tapping 4 times. X: The toner is not aggregated and dispersed. In the evaluation of moisture resistance, fixability, non-offset property and blocking resistance, ⊚ to Δ are practically usable.

Manufacturing Method of Dispersant A In a reaction vessel equipped with a stirrer, a thermometer, and a gas introduction tube, 900 parts by weight of deionized water, 25 parts by weight of methyl methacrylate,
75 parts by weight of 3-sodium sulfopropyl methacrylate was charged, and N ₂ gas was blown for about 30 minutes to expel the air in the reaction system. Next, the mixture was heated from the outside with stirring in a hot water bath to raise the temperature to 60 ° C., and 0.5 part by weight of ammonium persulfate was added. Stirring was continued at the same temperature for about 3 hours to obtain a polymer liquid (solid content: 3.3%) having a bluish white appearance and a viscosity of 340 centipoise (25 ° C.).

Examples 1 to 4 220 parts by weight of deionized water, 0.60 parts by weight of sodium polyacrylate (solid content 3.3%), 2.42 parts by weight of dispersant A, and 0.55 parts by weight of sodium sulfate were mixed. Agitator,
Charge into a reaction vessel equipped with a distillation column and a thermometer, then mix and add the amounts of the monomers and additives shown in the composition of Table 1, keep the stirring speed at 300 rpm, and start the polymerization of the amount shown in Table 1. The agent was added. Then, the reaction vessel is heated from the outside in a hot water bath and the temperature in the reaction system is adjusted to 92
The temperature was raised to ° C and suspension polymerization was started. After the suspension polymerization was carried out for about 6 hours, the temperature in the reaction system was raised to about 100 ° C., and about 44 parts by weight of residual monomer and deionized water in the reaction system were allowed to flow out of the reaction system. The residual monomer of the polymer was reduced. Then, the temperature in the reaction system was adjusted to about 90 ° C., 0.5 part by weight of sodium hydroxide was added, and alkali treatment was performed for about 30 minutes while maintaining the temperature at 90 ° C. Then, the temperature in the reaction system was lowered to room temperature, the resin was taken out from the reaction vessel, washed with deionized water for about 5 minutes, and then dried with a hot air dryer at 50 ° C. for about 48 hours to obtain a resin. The characteristic values of the obtained resin are shown in Table 2.

Next, 90 parts by weight of the obtained resin, 5 parts by weight of carbon black and 5 parts by weight of low molecular weight polypropylene wax were mixed for about 20 minutes, and melt-kneaded for about 20 minutes with a mixer. The melt-kneading temperature was 10 ° C. higher than the softening temperature of the resin. Then, the kneaded product was indirectly cooled with water and coarsely pulverized, and then finely pulverized with a jet mill fine pulverizer and adjusted with a classifier to finally obtain a toner having an area average particle size of 10 to 11 μm. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Also, using a fixing tester having a fixing roller coated with silicone oil, the printing speed was set to 2
Table 2 shows the evaluation results of the fixability and offset resistance of the toner obtained at 0 mm / sec.

As shown in Table 2, the toner of Example 1 is
It showed positive chargeability and had a good charge level. The toners of Examples 2 and 4 showed positive chargeability and had an excellent charge level. Further, the toner of Example 3 showed a positive charging property and the charge amount was a little low, but it was at a practical level. Furthermore, the toners of Examples 1 to 4 showed excellent humidity resistance with little attenuation of the charge amount. Regarding fixability, Examples 1 to 1
The toner of No. 3 was good, and the toner of Example 4 showed excellent fixability. Regarding the non-offset property, the toners of Examples 1 to 3 were excellent, and the toner of Example 4 was good. Regarding blocking resistance, Example 1,
The toners 3 and 4 were good, and the toner of Example 2 showed excellent blocking resistance.

Examples 5 to 6 The same conditions as in Examples 1 to 4 except that the monomers, additives and polymerization initiators shown in Table 1 were used except for the step of flowing out deionized water and residual monomers at 100 ° C. The resin was obtained in Table 1 and the resin properties of each resin are shown in Table 2.
Further, the resins obtained under the same conditions as in Examples 1 to 4 were made into toner. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Further, the fixing property and the offset resistance were evaluated at a printing speed of 20 mm / sec using a fixing tester in which the roller surface was coated with silicone oil, and the results are shown in Table 2.

As shown in Table 2, the positive charging property is as follows.
The toners of Examples 5 and 6 showed a positive charging property and had an excellent charging level. Further, the toners of Examples 5 and 6 both showed excellent moisture resistance and fixability. Regarding the non-offset property and blocking resistance, the toner of Example 5 was good, and the toner of Example 6 was slightly inferior, but usable.

Examples 7 to 8 except that the suspension polymerization temperature was set to 88 ° C., and the monomers, additives and polymerization initiators shown in the composition of Table 1 were used except for the step of flowing out deionized water and residual monomer at 100 ° C. Is Example 1
Resin was obtained under the same conditions as ~ 4. The characteristic values of the obtained resin are shown in Table 2. Further, the resins obtained under the same conditions as in Examples 1 to 4 were made into toner. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Also, using a fixing tester in which silicone oil is applied to the roller surface, a printing speed of 20 mm /
The fixing property and anti-offset property were evaluated by sec, and the results are shown in Table 2.

As shown in Table 2, the positive charging property is as follows.
The toner of Example 7 had positive chargeability and good charge level, and the toner of Example 8 had positive chargeability and slightly lower charge level, but it was practical. Further, the toners of Examples 7 and 8 both showed excellent moisture resistance. Regarding the fixability, the toners of Examples 7 and 8 were slightly inferior, but were practically applicable. The toners of Examples 7 and 8 were excellent in non-offset property and anti-blocking property.

Example 9 Examples 1 to 4 except that the suspension polymerization temperature was 140 ° C. and the monomers, additives and polymerization initiators shown in the composition of Table 1 were used.
A resin was obtained under the same conditions as above. The characteristic values of the obtained resin are shown in Table 2. Further, the obtained resin was used in Examples 1 to 4
Toner was formed under the same conditions as above. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Table 2 shows the evaluation results of the fixability and anti-offset property of the toner obtained at a printing speed of 20 mm / sec using a fixing tester in which silicone oil was applied to the roller surface. As shown in Table 2, positive chargeability was exhibited and the charge level was excellent. Further, it was excellent in moisture resistance and fixability. The non-offset property was good, and the blocking resistance was slightly inferior, but it was practical.

Examples 10 to 11 Resins were obtained under the same conditions as in Examples 1 to 4 except that the monomers, additives and polymerization initiators shown in Table 3 were used. The characteristic values of the obtained resin are shown in Table 4. further,
The resins obtained under the same conditions as in Examples 1 to 4 were made into toner. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Further, the fixing property and the offset resistance were evaluated at a printing speed of 3000 mm / sec using a fixing tester, and the results are shown in Table 4.

As shown in Table 4, Examples 10 and 11
The toner of No. 3 showed positive chargeability and the charge level was excellent. Further, the toners of Examples 10 and 11 both showed excellent moisture resistance. Regarding the fixability, the toner of Example 10 was good, and the toner of Example 11 was slightly inferior, but it was also practical. The toners of Examples 10 and 11 were excellent in non-offset property and blocking resistance.

Comparative Example 1 A resin was obtained in the same manner as in Examples 1 to 4 except that the monomers, additives and polymerization initiators having the compositions shown in Table 1 were used. The characteristic values of the obtained resin are shown in Table 2. Further, the obtained resin was made into a toner under the same conditions as in Examples 1 to 4. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Table 2 shows the evaluation results of the fixability and anti-offset property of the toner obtained at a printing speed of 20 mm / sec using a fixing tester in which silicone oil was applied to the roller surface. As shown in Table 2, the chargeability was inferior and the charge level was not satisfactory.

Comparative Example 2 A resin was obtained in the same manner as in Examples 7 to 8 except that the monomers, additives and polymerization initiators having the compositions shown in Table 1 were used. The characteristic values of the obtained resin are shown in Table 2. Further, the obtained resin was made into a toner under the same conditions as in Examples 1 to 4. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Table 2 shows the evaluation results of the fixability and anti-offset property of the toner obtained at a printing speed of 20 mm / sec using a fixing tester in which silicone oil was applied to the roller surface. As shown in Table 2, it was inferior in moisture resistance and blocking resistance and could not be used.

Comparative Example 3 A resin was obtained in the same manner as in Examples 1 to 4 except that the monomers, additives and polymerization initiators having the compositions shown in Table 1 were used. The characteristic values of the obtained resin are shown in Table 2. Further, the obtained resin was made into a toner under the same conditions as in Examples 1 to 4. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Table 2 shows the evaluation results of the fixability and anti-offset property of the toner obtained at a printing speed of 20 mm / sec using a fixing tester in which silicone oil was applied to the roller surface. As shown in Table 2, the chargeability was inferior and the charge level was not satisfactory.

Comparative Example 4 A resin was obtained in the same manner as in Example 9 except that the polymerization temperature was 145 ° C. and the monomers, additives and polymerization initiators having the compositions shown in Table 1 were used. The characteristic values of the obtained resin are shown in Table 2. Further, the obtained resin was used in Examples 1 to 1.
Toner was formed under the same conditions as in No. 4. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Also, using a fixing tester in which silicone oil is applied to the roller surface, the printing speed is 20 mm / sec.
The fixability and anti-offset property were evaluated with and the results are shown in Table 2.
It was shown to. As shown in Table 2, the moisture resistance, the non-offset property, and the blocking resistance were poor and it was impossible to put into practical use.

Comparative Example 5 A resin was obtained in the same manner as in Examples 1 to 4 except that the monomers, additives and polymerization initiators having the compositions shown in Table 1 were used. The characteristic values of the obtained resin are shown in Table 2. Further, the obtained resin was made into a toner under the same conditions as in Examples 1 to 4. Table 2 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Table 2 shows the evaluation results of the fixability and offset resistance of the toner obtained at a printing speed of 20 mm / sec using a fixing tester in which silicone oil was applied to the roller surface.
As shown in Table 2, it was inferior in moisture resistance and fixability and was not practical.

Comparative Example 6 Resins were obtained in the same manner as in Examples 10 to 11 except that the monomers, additives and polymerization initiators having the compositions shown in Table 3 were used. The characteristic values of the obtained resin are shown in Table 4. Further, the obtained resin was made into a toner under the same conditions as in Examples 10-11. Table 4 shows the evaluation results of the positive chargeability, moisture resistance and blocking resistance of the obtained toner. Also,
Table 4 shows the evaluation results of the fixability and offset resistance of the toner obtained at a printing speed of 300 mm / sec using a fixing tester. As shown in Table 4, the fixability was poor and it was not practical.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

[Table 3]

[0051]

[Table 4]

Example 12 120 parts by weight of deionized water and 4.85 parts by weight of dispersant A were mixed and charged into a reaction vessel, the monomers shown in the emulsion polymerization composition of Table 5 were charged, and N ₂ gas was introduced with stirring. Then, bubbling was performed for about 1 hour. After that, the N ₂ gas was stopped, the amount of potassium persulfate shown in Table 5 was added, the N ₂ gas was caused to flow, the stirring speed was kept at 150 rpm, and the temperature in the reaction system was raised to 70 ° C. over about 30 minutes. Then, emulsion polymerization was performed for 6 hours. After that, the N ₂ gas was stopped and the temperature in the reaction system was changed to 40 ° C.
Cooled to 80 parts by weight of deionized water, dispersant A4.85
Parts by weight, 9.70 parts by weight of sodium polyacrylate, and 8.0 parts by weight of sodium sulfate are mixed and charged into a reaction vessel,
The monomers shown in the suspension composition of Table 5 were mixed and added. Next, the stirring speed was set to 300 rpm and the temperature in the reaction system was set to 4
The emulsion and the monomer were impregnated at 0 ° C. for about 1 hour. Then, the amount of polymerization initiator shown in Table 3 was added,
The temperature in the reaction system was raised to 90 ° C. and suspension polymerization was carried out for about 3 hours. After the suspension polymerization was completed, a resin was obtained under the same conditions as in Examples 1 to 4. The characteristic values of the obtained resin are shown in Table 6.

Further, the obtained resin was used in Examples 10 to 1.
Toner was formed under the same conditions as in 1. Table 6 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Also, the printing speed of the fixing tester is 300 mm / s.
Table 6 shows the evaluation results of the fixability and offset resistance of the obtained toner as ec. As shown in Table 6, positive chargeability was exhibited, the charge level was good, and the moisture resistance was also good. Further, the fixing property and the non-offset property were excellent, and the blocking resistance was also good.

Example 13 180 parts by weight of deionized water used in emulsion polymerization, 7.3 parts by weight of dispersant A, 70 parts by weight of deionized water used in suspension polymerization, polyvinyl alcohol (saponification degree) 80
%), Sodium sulfate 7 parts by weight, the suspension polymerization temperature was 88 ° C., and the composition, additives and initiators shown in Table 5 were used under the same conditions as in Example 12 except for using the resin. Got The characteristic values of the obtained resin are shown in Table 6. Further, the obtained resin was made into a toner under the same conditions as in Examples 10-11. Table 6 shows the evaluation results of the positive chargeability, moisture resistance and blocking resistance of the obtained toner. Also,
Table 6 shows the evaluation results of the fixability and anti-offset property of the obtained toner when the printing speed of the fixing tester was 300 mm / sec. As shown in Table 6, the charge level was positive and the charge level was excellent, and the moisture resistance was slightly inferior, but it was at a practical level. Further, it was excellent in fixing property, non-offset property and blocking resistance.

Example 14 The reaction vessel was sealed and the suspension polymerization temperature was 140 ° C.
A resin was obtained under the same conditions as in Example 12, except that the composition, additives and polymerization initiator shown in Table 5 were used. The characteristic values of the obtained resin are shown in Table 6. Further, the obtained resin was made into a toner under the same conditions as in Examples 10-11. Table 6 shows the evaluation results of the positive charging property, moisture resistance and blocking resistance of the obtained toner. Table 6 shows the evaluation results of the fixability and anti-offset property of the obtained toner when the printing speed of the fixing tester was 300 mm / sec. Table 6
As shown in (1), the charge level was positive and the charge level was excellent, and the moisture resistance was good. Further, the fixing property and the non-offset property were excellent, and the blocking resistance was good.

[0056]

[Table 5]

[0057]

[Table 6]

The symbols in Table 1, Table 3 and Table 5 represent the following components, respectively. St: Styrene nBA: n-Butyl acrylate MAA: Methacrylic acid MMA: Methyl methacrylate nBMA: n-Butyl methacrylate ET: 2-Ethoxyethyl methacrylate DVB: Divinylbenzene DE: Diethylaminoethyl methacrylate BDMA: Dimethacrylic acid 1 , 3-butylene glycol MSD: α-methylstyrene dimer BPO: benzoyl peroxide tBP: t-butylperoxybenzoate V-59: 2,2′-azobis (2-methylbutyronitrile) AIBN: azobisisobutyrate Ronitrile KPS: Potassium persulfate

[0059]

The toner using the binder resin of the present invention is excellent in fixability, non-offset property, blocking resistance, excellent positive chargeability, and has a stable charge amount. Further, the binder resin of the present invention does not use azobisisobutyronitrile, which has a problem of toxicity,
Further, by using the peroxide type polymerization initiator, a toner having a good positive charging property can be obtained and there is no environmental pollution.

Claims (3)

[Claims] 1. An acrylic ester component and / or a methacrylic ester component (A) having an ether group.
And an acrylic acid ester component and / or a methacrylic acid ester component (B) other than the A component, and a polymer component containing a styrene component (C), and the blending amounts of the A component, the B component and the C component are as follows: A binder resin for a positively chargeable toner, which satisfies the requirements (1) to (3), has a glass transition temperature of 40 to 68 ° C., a softening temperature of 80 to 180 ° C., and an acid value of 20 mgKOH / g or less. .. 50% by weight C / (A + B + C) × 100 ≦ 90% by weight (1) 10% by weight ≦ (A + B) / (A + B + C) × 100 ≦ 50% by weight (2) 3% by weight ≦ A / (A + B) × 100 ≦ 90% by weight (3) 2. A weight average molecular weight of 3,000 to 80,0.
The binder resin for a positively chargeable toner according to claim 1, wherein the binder resin has a number average molecular weight of 00 and a number average molecular weight of 1,000 to 45,000. 3. At least one peroxide type polymerization initiator is used.
3. The binder resin for positively chargeable toner according to claim 1, wherein at least one kind is used.