JP5983980B2 - Method for producing polyester resin for toner, polyester resin for toner, method for producing toner, and toner - Google Patents

Description

  The present invention relates to a polyester resin suitable for a toner used for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording method, electrostatic printing method and the like.

  In the method of obtaining an image by the electrophotographic printing method and the electrostatic charge developing method, the electrostatic charge image formed on the photosensitive member is developed with toner charged in advance by friction and then fixed. As for the fixing method, there are a heat roller method in which a toner image obtained by development is fixed using a pressurized and heated roller, and a non-contact fixing method in which fixing is performed using an electric oven or flash beam light. In order to pass through these processes without any problem, the toner needs to maintain a stable charge amount first, and then needs to have good fixability to paper. In addition, the apparatus has a fixing unit which is a heating body, and the temperature in the apparatus rises, so that it is necessary that the toner does not block. Further, even during continuous printing, it is necessary that the apparatus is not soiled or fogged on the printing surface, that is, the durability of the toner is required.

  Further, in the heat roller system, the temperature of the fixing unit has been lowered from the viewpoint of energy saving, and the toner has been strongly required to have a capability of fixing onto a paper at a lower temperature, that is, a low temperature fixability. In addition, as the apparatus becomes more compact, a roller that does not apply a release agent has been used, and there is an increasing demand for toner to be peelable from the heat roller, that is, non-offset.

  The binder resin for toner has a great influence on the toner characteristics as described above, and polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyamide resin, and the like are known. In particular, a polyester resin which is excellent in fixing property at a low temperature and has a good performance balance has attracted attention. A polyester resin generally tends to have a low hot offset resistance, and a technique for improving the hot offset resistance as a toner by imparting elasticity by imparting a gel to the resin is widely known.

  On the other hand, examples of a method for producing a toner using a polyester resin include a pulverization method and a chemical method. The pulverization method is a method for obtaining a toner by melting and kneading a polyester resin, a pigment (colorant), a release agent, and the like, and finely pulverizing and classifying the obtained kneaded material with a pulverizer or the like. Widely used.

  In recent years, it has been desired to reduce the particle size of toner in order to achieve high image quality. However, in the pulverization method, energy and time required for pulverization increase, the manufacturing process becomes complicated, and the yield increases. Since it falls, there existed a problem which manufacturing cost increased. Therefore, a chemical method that can reduce the particle diameter more efficiently is drawing attention.

As a method for producing a toner using a polyester resin by a chemical method, for example, an aqueous medium obtained by dissolving or dispersing a material containing a polyester resin and other toner compound in an organic solvent in which the polyester resin can be dissolved is used. After dispersing and granulating, the organic solvent is removed, and the resulting particles are separated, washed and dried to obtain toner particles, or a polyester emulsion is produced to disperse the toner formulation in water. Examples of the method include a method of obtaining toner particles by aggregating and granulating in water together with a liquid, and separating, washing, and drying the obtained particles. Examples of a method for producing a polyester emulsion include a method of dissolving a polyester resin in an organic solvent in which the polyester resin can be dissolved, finely dispersing the solution in water, and then removing the solvent.
As described above, in the process of producing a chemical toner using a polyester resin, an organic solvent is used. However, when a polyester resin having insufficient solvent solubility is used, the processability is deteriorated or the toner particles obtained are obtained. The heat characteristics of the toner, the mixing state of the toner compound, and the like are not uniform, which adversely affects the toner performance. For this reason, it is important for the polyester resin that the solvent solubility is good.
As a polyester resin for a chemical toner, for example, Patent Document 1 describes a polyester resin for a chemical toner that has a good fixability and hot offset resistance, in which a linear polyester and a crosslinked polyester are blended.
JP 2002-148866 A

  However, in the technique of Patent Document 1, the crosslinked polyester resin contains a THF-insoluble component (gel), and the solubility in an organic solvent, which is an important performance as a resin for a chemical toner, is insufficient.

  An object of the present invention is to obtain a polyester resin that has good solubility in an organic solvent used for toner production in a chemical method, and that can provide a toner with good low-temperature fixability and hot offset resistance.

The gist of the present invention is a method for producing a polyester resin for a toner, wherein polyhydric alcohol and polyhydric alcohol containing 8 to 25 mol% of trivalent or higher polycarboxylic acid in 100 mol% of polyhydric carboxylic acid are polycondensed. In the method for producing a polyester resin for toner, the polycondensation is terminated in the range where the softening temperature value of the polyester resin satisfies the formula (1).
115-0.2X <softening temperature <136-0.8X Formula (1)
(X is the number of moles of trivalent or higher polyvalent carboxylic acid in 100 moles of polyvalent carboxylic acid)

  The polyester resin obtained by the production method of the present invention has good solubility in an organic solvent, and a toner excellent in low-temperature fixability and hot offset resistance can be obtained by a chemical method.

In the present invention, there is provided a method for producing a polyester resin for a toner in which polycondensation of a polyhydric carboxylic acid and a polyhydric alcohol containing 8 to 25 mol% of a trivalent or higher polycarboxylic acid in 100 mol% of the polycarboxylic acid. Thus, the polycondensation is terminated in the range where the softening temperature value of the polyester resin satisfies the formula (1).
115-0.2X <softening temperature <136-0.8X Formula (1)
(X is the number of moles of trivalent or higher polyvalent carboxylic acid in 100 moles of polyvalent carboxylic acid)
When 8 mol% or more of a trivalent or higher polyvalent carboxylic acid is contained in 100 mol% of the polyvalent carboxylic acid, the low temperature fixability of the toner using the polyester resin obtained is improved. Moreover, when it is 25 mol% or less, the solubility to the solvent of the resin obtained and hot offset resistance become favorable.

  Examples of the trivalent or higher carboxylic acid component that can be used in the method for producing a polyester resin of the present invention include trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, and 2,5,7-naphthalenetricarboxylic acid. Acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, or esters or acid anhydrides thereof. Or two or more types can be used in combination. Trimellitic acid or its acid anhydride is preferable in terms of handling properties and cost.

  Moreover, a well-known raw material can be used suitably as polyhydric carboxylic acid. Examples of divalent carboxylic acids include terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, and esters or acid anhydrides thereof. Dicarboxylic acid component: Aliphatic dicarboxylic acid components such as phthalic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, or esters or acid anhydrides thereof. As the aromatic dicarboxylic acid, terephthalic acid and isophthalic acid are preferable in terms of handling properties and cost.

  The amount of the aromatic dicarboxylic acid used is not particularly limited, but is preferably 70 mol% or more in 100 mol% of the polyvalent carboxylic acid. When the amount of the aromatic dicarboxylic acid used is 70 mol% or more, the storage stability of the toner and the resin strength tend to be improved. As for the lower limit of the usage-amount of aromatic dicarboxylic acid, 75 mol% or more is more preferable.

Furthermore, in the present invention, the polycondensation is terminated in the range where the softening temperature of the polyester resin satisfies the following formula (1).
115-0.2X <softening temperature <136-0.8X Formula (1)
(X is the number of moles of trivalent or higher polyvalent carboxylic acid in 100 moles of polyvalent carboxylic acid)
By terminating the polycondensation when the softening temperature exceeds 115-0.2X (° C.), the hot offset resistance of the toner using the resulting resin is improved, and when the softening temperature is lower than 136-0.8X, By terminating the condensation, the solvent solubility of the toner using the resulting resin is improved and the fixability is improved.

  As a method for terminating the polycondensation at a desired softening temperature, for example, in advance, the relationship between the torque value applied to the stirring blade in the polycondensation in the composition and the softening temperature of the obtained resin is grasped, and the desired torque value is determined. Examples include a method of terminating the polymerization when indicated. Also, when the polymerization is completed, the stirring of the reaction apparatus is stopped, the inside of the apparatus is brought to normal pressure, and the reaction product is taken out from the lower part of the apparatus by maintaining the normal pressure or pressurizing the inside of the apparatus with nitrogen and cooling to 100 ° C. or lower. To do.

  In the present invention, polycondensation may be performed by a known method. For example, polycondensation with a polyhydric carboxylic acid and a polyhydric alcohol is performed at normal pressure or under pressure, followed by polycondensation under vacuum. Condensation can be performed.

  The temperature of the esterification reaction or transesterification reaction is more preferably 255 ° C. or higher from the viewpoint of improving productivity. The upper limit of the temperature is preferably 280 ° C. or lower. This is because when the esterification reaction or transesterification reaction temperature is 280 ° C. or lower, decomposition of the resin and by-products of volatile components that cause odor tend to be suppressed, and 270 ° C. or lower is more preferable.

  The polycondensation temperature is preferably 200 ° C to 260 ° C. When the temperature of the polycondensation reaction is 200 ° C. or higher, productivity tends to be good, 210 ° C. or higher is more preferable, and 220 ° C. or higher is particularly preferable. Further, when the temperature of the polycondensation reaction is 260 ° C. or lower, the decomposition of the resin and the by-product of volatile components that cause odor tend to be suppressed, and 250 ° C. or lower is more preferable.

  Regarding the degree of vacuum in the polycondensation, the higher the vacuum, the higher the reaction rate. Therefore, it is important to adjust the degree of vacuum by introducing nitrogen into the reaction system as necessary to adjust the reaction rate.

  The polycondensation catalyst may be a known one used in the production of polyester resins, such as titanium tetraalkoxide, dibutyltin oxide, stannous oxide, tin 2-ethylhexanoate, tin acetate, zinc acetate, tin disulfide, Antimony trioxide, germanium dioxide, or the like can be used.

  In the present invention, known polyhydric alcohols can be used as appropriate, and aliphatic diols, aromatic diols, and the like can be used.

  Aliphatic diols include ethylene glycol, neopentyl glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,4-cyclohexanedimethanol, isosorbide and the like. Can be mentioned.

  As the aromatic diol, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, or those having different number of added moles of ethylene oxide, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, or its propylene oxide having a different number of added moles, polyoxypropylene (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-Hydroxyphenyl) propane or its propylene oxide, ethylene oxide having different number of moles to be added.

  These can be used alone or in combination of two or more, and can also be used in combination of aliphatic diol and aromatic diol.

  In addition to these diols, trihydric or higher polyhydric alcohols can also be used as the polyhydric alcohol. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolpropane, 1,3,5-trihydroxymethyl Examples include benzene. These can be used alone or in combination of two or more. Among these, pentaerythritol and trimethylolpropane are particularly preferable in terms of handling properties and cost.

  Although the usage-amount of aliphatic diol is not specifically limited, 10 mol% or more is preferable with respect to 100 mol% of polyhydric carboxylic acid. When the amount of aliphatic diol used is 10 mol% or more, the degree of polymerization tends to increase and the non-offset property of the toner tends to be good, and long-time condensation polymerization can be performed without using a large amount of polymerization catalyst. Even if it is not carried out, the polymerization degree tends to be increased, which is preferable in terms of cost and environment.

  Moreover, the usage-amount of a polyhydric alcohol has preferable 100 mol part-150 mol part with respect to 100 mol part of polyhydric carboxylic acid. When the amount is 100 mol parts or more with respect to 100 mol parts of the polyvalent carboxylic acid, the reactivity becomes good, so that the reaction time is shortened, the productivity is improved, and the residual monomer in the resin can be reduced. It is in. Further, when the amount of polyhydric alcohol used is 150 mol parts or less, the chargeability of the resin tends to be good. The lower limit of the amount of polyhydric alcohol used is preferably 101 mol parts or more, and the upper limit is preferably 145 mol parts or less.

  Next, the polyester resin obtained by the method for producing a polyester resin of the present invention will be described.

The polyester resin of the present invention preferably has an ethyl acetate insoluble content of less than 0.1% by mass.
When the ethyl acetate insoluble content is less than 0.1% by mass, the solubility in an organic solvent, which is an important performance as a resin for a chemical toner, is improved. The content of ethyl acetate insolubles is preferably less than 0.05% by mass, most preferably 0% by mass.

The ethyl acetate insoluble matter is measured by the following method. About 0.5 g of sample is precisely weighed in an Erlenmeyer flask (Ag), 50 ml of ethyl acetate is added to the flask, and heated and dissolved in a water bath at 70 ° C. for 3 hours. Next, the solution was filtered while suctioning through a 1GP100 glass filter (Bg) that had been thoroughly packed with Celite 545 (manufactured by Kishida Chemical Co., Ltd.) and thoroughly dried. After sufficiently removing the ethyl acetate-soluble component remaining therein, the glass filter remaining with the insoluble component is dried again and the weight is measured (Cg), and the ethyl acetate-insoluble component is calculated according to the following formula.
Ethyl acetate insoluble matter (% by mass) = (C−B) / A × 100
Further, the glass transition temperature (hereinafter referred to as Tg) of the polyester resin of the present invention is preferably 50 to 65 ° C. When Tg is 50 ° C. or higher, the toner has a tendency to improve blocking resistance, and when Tg is 65 ° C. or lower, the toner has a tendency to improve fixability. As for the lower limit of Tg, 52 degreeC or more is more preferable.

  The glass transition temperature (Tg) can be measured using a differential scanning calorimeter (DSC).

  Further, the polyester resin of the present invention preferably has a storage elastic modulus (G ′) at 100 ° C. of 70000 Pa or less. This is because the low-temperature fixability of the obtained toner tends to be good when it is 70000 Pa or less, and more preferably 60000 Pa or less.

  The polyester resin of the present invention preferably has a storage elastic modulus (G ′) at 140 ° C. of 100 Pa or more. This is because, when the pressure is 100 Pa or more, the resulting toner tends to have good hot offset resistance, and more preferably 300 Pa or less.

The storage elastic modulus (G ′) is measured under the following conditions.
Plate: 25 mmφ parallel plate, thickness: 1 mm, frequency: 1 Hz, strain: 1%
Measurement temperature range: 80 ° C. to 150 ° C. Rate of temperature increase: 3 ° C./min Further, the acid value (AV) of the polyester resin of the present invention is preferably 20 mgKOH / g or less. When the acid value is 20 mgKOH / g or less, the image density of the toner tends to be stable. The upper limit of the acid value of the polyester resin is more preferably 15 mgKOH / g or less.

  Next, a toner using the polyester resin of the present invention will be described.

  The polyester resin of the present invention uses a pulverization method in which a polyester resin, a pigment (colorant), a release agent, and the like are melt-kneaded, and the obtained kneaded material is finely pulverized and classified by a pulverizer or the like, and an organic solvent is used. It can be suitably used in the production of chemical toners.

  As a method for producing a toner using an organic solvent, for example, a material containing a polyester resin and other toner compound is dissolved or dispersed in an organic solvent in which the polyester resin can be dissolved, and the liquid contains a dispersion stabilizer. After dispersing in an aqueous medium and granulating, the organic solvent is removed, the obtained particles are separated, washed and dried to obtain toner particles, the polyester resin is dissolved in an organic solvent, After emulsifying the liquid in an aqueous medium, the organic solvent is removed, and the polyester emulsion is combined with an aqueous medium in which other toner formulations are dispersed, and the particles are aggregated and thermally fused to obtain particles. Examples thereof include a method of obtaining toner particles by separating, washing and drying.

  The organic solvent can be appropriately selected and used in consideration of affinity with water and ease of solvent removal later. Specific examples of preferable organic solvents include, for example, hexane, cyclohexane, toluene, xylene, benzene, carbon tetrachloride, 1,1-dichloroethane, 1,1,1-trichloroethane, trichloroethylene, chloroform, methyl acetate, ethyl acetate, acetic acid. Examples thereof include butyl, methyl ethyl ketone, tetrahydrofuran, and isopropanol, and these can be used alone or in combination of two or more.

  The polyester resin of the present invention can be used in combination with other resins as the main component of the toner binder. When using a resin other than the polyester resin of the present invention, for example, a polyester resin other than the polyester resin of the present invention, a styrene acrylic resin, a cyclic olefin resin, a methacrylic acid resin, an epoxy resin, and the like can be appropriately selected and used. These resins can be used alone or in combination of two or more.

  The colorants used in the toner are carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo And disazo dyes, condensed azo dyes or pigments. These dyes and pigments can be used alone or in admixture of two or more. In the case of a full color toner, yellow includes benzidine yellow, monoazo dyes and dyes, condensed azo dyes and the like, magenta includes quinacridone, rhodamine dyes and monoazo dyes, and cyan includes phthalocyanine blue and the like.

  The content of the colorant is preferably 2 to 10% by mass in the toner from the viewpoint of the color tone, image density, and thermal characteristics of the toner.

  Examples of the charge control agent include a quaternary ammonium salt as a positive charge control agent and a basic or electron donating organic substance, and as a negative charge control agent, a metal chelate, a metal-containing dye, an acid or electron withdrawing property. Organic materials and the like. In the case of color toners, it is important that the charge control agent is colorless or light color and does not cause any color tone problems on the toner. Examples include metal salts, metal complexes, amides of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, etc. A compound, a phenol compound, a naphthol compound, etc. are mentioned. Furthermore, a vinyl polymer having a styrene, acrylic acid, methacrylic acid or sulfonic acid group may be used as the charge control agent.

  The content of the charge control agent is preferably 0.5 to 5% by mass in the toner. When the content of the charge control agent is 0.5% by mass or more, the charge amount of the toner tends to be a sufficient level, and when the content is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent is suppressed. It tends to be.

  As the release agent (wax), synthetic ester wax, carnauba wax, rice wax, montan wax, beeswax, polypropylene wax, polyethylene wax, paraffin wax, fatty acid amide, silicone wax, etc. may be used as appropriate. It can be used alone or in combination of two or more.

  The content of the wax to be blended at the time of forming the toner is preferably 0.3 to 15% by mass in the toner because it affects the releasing effect, fixing property, storage property, color developing property and the like of the toner. The lower limit value of the wax content is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. Further, the upper limit value of the wax content is more preferably 13% by mass or less, and particularly preferably 10% by mass or less.

  Furthermore, as other additives, fluidity improvers such as fine powder silica, alumina, titania, inorganic fine powders such as magnetite, ferrite, cerium oxide, strontium titanate, conductive titania, resistance such as styrene resin, acrylic resin, etc. Regulators, lubricants, etc. are used as internal or external additives.

  The content of these additives is preferably 0.05 to 10% by mass in the toner. When the content of these additives is 0.05% by mass or more, a toner performance-modifying effect tends to be sufficiently obtained, and when it is 10% by mass or less, the image stability of the toner tends to be good. is there.

  Examples of the present invention are shown below. Also, the resin analysis and evaluation methods and toner evaluation methods shown in this example are as follows.

<Analytical evaluation method of resin>
(1) Softening temperature When measured using a flow tester CFT-500 manufactured by Shimadzu Corporation with a nozzle of 1 mmφ × 10 mm under a constant temperature increase with a load of 294 N (30 Kgf) and a temperature increase rate of 3 ° C./min. The temperature at which 1/2 of 1.0 g of sample flowed out was determined.

(2) Glass transition temperature (Tg)
The temperature at the intersection of the base line of the chart and the tangent line of the endothermic curve near the glass transition temperature when measured at a heating rate of 5 ° C./min using a differential differential calorimeter DSC-60 manufactured by Shimadzu Corporation Asked.

(3) About 0.2 g of acid value sample is precisely weighed in a Erlenmeyer flask with branches (A (g)), 10 ml of benzyl alcohol is added, and the resin is dissolved by heating in a nitrogen atmosphere for 15 minutes with a heater at 230 ° C. did. After allowing to cool to room temperature, 10 ml of benzyl alcohol, 20 ml of chloroform and several drops of phenolphthalein were added, and titrated with a 0.02 N KOH solution (titrate = B (ml), titer of KOH solution = p). A blank measurement was performed in the same manner (titer amount = C (ml)), and calculation was performed according to the following formula.
Acid value (mgKOH / g) = (BC) × 0.02 × 56.11 × p ÷ A
(4) Storage elastic modulus (G ')
Using AR2000ex manufactured by TA Instruments, set a sample with a thickness of 1 mm between 25 mmφ parallel plates, and measure from 80 ° C to 150 ° C at a frequency of 1 Hz and a strain of 1% at a rate of temperature rise of 3 ° C / min. The storage elastic modulus at 100 ° C. and 140 ° C. was determined.

<Toner evaluation method>
(1) About 0.5 g of ethyl acetate insoluble polyester resin was precisely weighed in an Erlenmeyer flask (Ag), 50 ml of ethyl acetate was added to the flask, and heated and dissolved in a 70 ° C. water bath for 3 hours. The solution was filtered while sucking through a 1GP100 glass filter (Bg) that was tightly packed with Celite 545 and thoroughly dried, and the ethyl acetate-soluble matter remaining in the glass filter was sufficiently removed using acetone. Then, the glass filter in which the insoluble matter remained was dried again and weighed (Cg), and the ethyl acetate insoluble matter was calculated according to the following formula.
Ethyl acetate insoluble matter (% by mass) = (C−B) / A × 100
(2) Toner concentration of 0.5 mg / cm2 as a test pattern using a printer having a fixing roller not coated with low-temperature fixing silicone oil and capable of changing the roller temperature with the roller speed set to 100 mm / s A solid image having a length of 4.5 cm and a width of 15 cm was prepared and the fixing roller was set at a temperature of 145 ° C. and fixed. The test pattern image was recorded by measuring the image density with a Macbeth image densitometer.

Next, the density measurement portion is vertically folded, and a protective paper is placed on the folded portion, and then a 1 kg weight is slid five times on the folded portion to make a crease, followed by a mountain fold at the same fold and the protective paper is placed Then, a 1 kg weight was slid to the bent part 5 times. The test paper was stretched, cellophane tape (Nitto Denko CS System No. 29) was affixed to the bent part, traced 5 times, and then slowly peeled off, and the image density was measured with a Macbeth image densitometer. The same measurement was performed at three locations, and the respective fixing rates were calculated from the image densities before and after the test by the following formula, and evaluated based on the following criteria based on the average fixing rates at the three locations.
Fixing rate = image density after test / image density before test × 100 (%)
◎ (Very good): Fixing rate of 85% or more ○ (Good): Fixing rate of 75% or more and less than 85% x (Inferior): Fixation rate of less than 75% or an offset phenomenon occurs at 145 ° C. and cannot be measured ( 3) Toner concentration of 0.5 mg / cm ² as a test pattern using a printer having a fixing roller not coated with hot offset-resistant silicone oil and capable of changing the roller temperature set to a roller speed of 30 mm / s When printing a solid image of 4.5 cm in length and 15 cm in width at every roller temperature of 5 ° C., the minimum temperature when the toner moves to the fixing roller due to the hot offset phenomenon during fixing is defined as the hot offset generation temperature. Hot offset resistance was judged using the criteria.
◎ (Very good): Hot offset generation temperature is 200 ° C or higher ○ (Good): Hot offset generation temperature is 180 ° C or higher and lower than 200 ° C ○ △ (available): Hot offset generation temperature is 170 ° C or higher and lower than 180 ° C × (Inferior): Hot offset occurrence temperature is less than 170 ° C. (Example 1)
Polyhydric carboxylic acid, polyhydric alcohol and other components having the charge composition shown in Table 1 and 1500 ppm of antimony trioxide with respect to the polyvalent carboxylic acid were charged into a reaction vessel equipped with a distillation column. Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction.

  Next, the temperature in the reaction system is lowered and maintained at 235 ° C., the pressure in the reaction vessel is reduced over about 40 minutes, the degree of vacuum is 133 Pa (abs), and condensation polymerization is performed while distilling the diol component from the reaction system. It was. Condensation polymerization was carried out until the viscosity of the reaction system increased with the reaction, the degree of vacuum was reduced with increasing viscosity, and the torque of the stirring blades reached a value indicating a desired softening temperature satisfying the formula (1). Stirring was stopped when the torque of the stirring blade showed a predetermined torque, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reaction product was taken out over about 40 minutes to obtain a polyester resin. The characteristic values and evaluation results of the obtained resin are shown in Table 1.

  Next, the obtained polyester resin was used to form a toner. Tonerization includes 93 parts by weight of polyester resin, 3 parts by weight of quinacridone pigment (HOSTAPARM PIN E, CI No .: Pigment Red 122 manufactured by Clariant), 3 parts by weight of Carnauba Wax No. 1 (manufactured by Toyo Adre), 1 part by mass of a negatively chargeable charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) was mixed with a Henschel mixer for 5 minutes.

  Next, the obtained mixture was melt-kneaded with a biaxial kneader. The melt kneading was performed by setting the internal temperature to the softening temperature of the resin. After kneading, the toner soul was obtained by cooling, finely pulverized to 10 μm or less with a jet mill fine pulverizer, and fine particles of 3 μm or less were cut with a classifier to adjust the particle size. To 100 parts by mass of the obtained fine powder, 0.25 part by mass of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added and mixed by a Henschel mixer to obtain a toner. Table 1 shows the evaluation results of the obtained toner. There was no ethyl acetate insoluble component, compatibility as a resin for chemical toners, and the resulting toner had good low-temperature fixability and hot offset resistance.

(Example 2 to Example 4)
A polyester resin was obtained in the same manner as in Example 1 except that the charged composition and the softening temperature at the end of polymerization were changed as shown in Table 1. The characteristic values and evaluation results of the obtained resin are shown in Table 1. There was no ethyl acetate insoluble component, compatibility as a resin for chemical toners, and the resulting toner had good low-temperature fixability and hot offset resistance.

(Comparative Examples 1-7)
A polyester resin was obtained in the same manner as in Example 1 except that the charged composition and the softening temperature at the end of polymerization were changed as shown in Table 1. The characteristic values and evaluation results of the obtained resin are shown in Table 1. Next, toner was obtained in the same manner as in Example 1, and toner evaluation was performed. The evaluation results are shown in Table 1.

Diol A: Polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propanediol Diol B: Polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) Propanediol

Claims (2)

A method for producing a polyester resin for a toner, comprising polycondensation of a polyvalent carboxylic acid containing 8 to 20 mol% of a trivalent or higher polyvalent carboxylic acid and a polyhydric alcohol in 100 mol% of the polyvalent carboxylic acid, The polyhydric alcohol contains 22 mol% or more aliphatic diol with respect to 100 mol% of the polyvalent carboxylic acid, and the polycondensation is terminated in the range where the softening temperature value of the polyester resin satisfies the formula (1). And a glass transition temperature of 52 ° C. to 65 ° C., an acid value of 11.3 mgKOH / g to 15 mgKOH / g, and the polyvalent carboxylic acid containing isophthalic acid and terephthalic acid. .
115-0.2X <softening temperature <136-0.8X Formula (1)
(X is the number of moles of trivalent or higher polyvalent carboxylic acid in 100 moles of polyvalent carboxylic acid)   A toner production method comprising a step of dissolving a polyester resin for toner obtained by the method according to claim 1 in an organic solvent.