JP2011248341A - Manufacturing method of polyester resin for toner, polyester resin for toner and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a polyester resin, the polyester resin for a toner and the toner using thereof with low environmental loads, capable of providing the toner containing a plant-derived raw material component and having a good fixability, hot-offset resistance and storage stability.SOLUTION: In the manufacturing method of the polyester resin for the toner, condensation polymerization of a monomer mixture including a polyhydric alcohol and a polyvalent carboxylic acid having a plant-derived 1,3-propanediol is performed under the presence of phytosterol, and the toner uses the polyester resin for the toner as a binder resin for the toner.

Description

  The present invention relates to a method for producing a polyester resin for a toner suitably used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc., and a toner obtained by the method The present invention relates to polyester resin and toner.

  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 that is a heating body, and it is necessary that the toner does not block due to a temperature rise in the apparatus. 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, devices are becoming more compact and rollers that do not apply oil are being used, and it is necessary for the toner to maintain its releasability from the heat roller, that is, non-offset properties.
The binder resin for toner has a great influence on the toner characteristics as described above. As the binder resin for toner, polystyrene resin, styrene acrylic resin, polyester resin, epoxy resin, polyamide resin and the like are known, and they are appropriately selected and used depending on required performance and the like.

  On the other hand, in recent years, from the viewpoint of environmental protection such as the suppression of global warming, the conversion from conventional plastics derived from petroleum raw materials to plastics derived from plant raw materials with less environmental impact has been actively promoted. For example, the Japan Bioplastics Association has certified plastic products with a ratio of 25% by weight or more of biomass-derived components in the biomass plastic composition contained in raw materials and products as “biomass plastics”. Authorized for use. As for the toner, use of a plant-derived component is desired, and the binder resin constituting the toner is also desired to contain a constituent unit derived from a plant raw material.

As such a polyester resin with low environmental load, for example, Patent Document 1 proposes a polyester resin obtained by polycondensation of a plant-derived dicarboxylic acid and a diol. Patent Document 2 describes a polyester resin obtained by adding a natural wax such as rice wax during polymerization. Patent Document 3 describes a toner in which phytosterol, which is a plant-derived substance, is mixed as a decoloring agent when forming a toner.
JP 2007-197654 A JP-A-11-295919 JP 2000-56497 A

However, the polyester resin described in Patent Document 1 is not suggested at all for use as a binder resin for toner, and the polyester resin described in the document is required as a binder resin for toner. Storage stability and hot offset resistance are insufficient.
In addition, when natural wax is introduced into the resin as in Patent Document 2, the glass transition temperature of the resulting polyester resin is lowered, so that it is difficult to achieve both storage stability and fixing property of the toner. Furthermore, the polyester resin described in Patent Document 2 has a non-offset temperature range of about 40 ° C., and has a problem that it is not suitable for use where a wider fixing temperature range such as high-speed printing is required. Moreover, the introduction amount of the natural product-derived substance of the polyester resin described in the document was about 5% by mass, and the effect on the reduction of environmental load was insufficient.
In Patent Document 3, the binder resin does not contain phytosterol but is mixed into the toner as a color eraser, and the amount introduced is about 0.5% by mass, low temperature fixability, and hot offset resistance. Was insufficient.

The gist of the present invention is a method for producing a polyester resin for toner by polycondensing a mixture containing phytosterol, a polyhydric alcohol containing plant-derived 1,3-propanediol and a polyvalent carboxylic acid, wherein the phytosterol is the above-mentioned In the method for producing a polyester resin for toner containing 1 to 20% by mass in the mixture.

  By using the polyester resin for toner obtained by the method of the present invention as a binder resin for a toner, it is possible to provide a toner with low environmental load, good fixability and storage stability, and a wide non-offset temperature range. .

The present invention polycondenses a mixture containing phytosterol, a polyhydric alcohol containing plant-derived 1,3-propanediol, and a polyvalent carboxylic acid.

  By mixing phytosterol with a polyester resin at the time of toner formation, the ratio of plant-derived substances in the toner can be increased, but the storage stability as a toner tends to deteriorate. In the present invention, by polycondensing a monomer mixture containing a polyvalent carboxylic acid and a polyhydric alcohol in the presence of phytosterol, the hydroxyl group of the phytosterol is ester-bonded to the polyvalent carboxylic acid component, and the polyester resin is derived from phytosterol. Even when the ratio of the plant-derived substance in the toner is increased, the storage stability as a toner is good.

In this invention, it is necessary to contain 1-20 mass% of phytosterols in the said mixture. By including 1% by mass or more of phytosterol, the ratio of plant-derived substances in the toner is increased, the environmental load is reduced, and the low-temperature fixability and hot offset resistance as a toner are improved. Moreover, the storage stability of a polyester resin becomes favorable because content of a phytosterol shall be 20 mass% or less. More preferably, it is 5-15 mass%.
The phytosterol used in the present invention is a general term for sterols contained in plants, and is a cyclic alcohol such as β-sitosterol, stigmasterol, brassicasterol, and campesterol. Among plants, it is contained in soybeans, rapeseed, cottonseed, tall, red beans, sugar cane and the like. Soy-derived phytosterol is a mixture containing β-sitosterol as a main component and stigmasterol, campesterol, and the like.
The phytosterol may be composed of the above-mentioned cyclic alcohol single component, or may be composed of two or more kinds. As phytosterols, phytosterols derived from soybeans manufactured by Tama Seikagaku are available.
Furthermore, in the present invention, it is necessary that the mixture contains 1,3-propanediol derived from plant raw materials as a polyhydric alcohol. By including 1,3-propanediol derived from plant raw materials, the ratio of plant-derived substances in the toner is increased, the environmental load is reduced, and low-temperature fixability is improved.
From the viewpoint of reducing environmental burden, the content of 1,3-propanediol derived from plant raw materials is preferably 5% by mass or more based on the total components of the polyester resin. More preferably, it is 10 mass% or more.

Plant raw material-derived 1,3-propanediol can be obtained using corn starch or the like as a raw material. For example, Susterra (registered trademark) propanediol (DuPont Co., Ltd.) is available.
Moreover, as polyhydric alcohols other than 1,3-propanediol derived from plant raw materials contained in the mixture, ethylene glycol, neopentyl glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, Aliphatic diols such as 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, isosorbide, polyoxypropylene- (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-hydroxy) Phenyl) propane, polyoxypropylene (2.2) -polyoxy Ethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2)- 2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis Aromatic diols such as (4-hydroxyphenyl) propane, 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-propanetrio , Trivalent or higher alcohol components such as 2-methyl-1,2,4-butanetriol, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, and the like, within a range not impairing the effects of the present invention. , Alone or in combination of two or more. These may be plant-derived substances or petroleum-derived substances.

The polyvalent carboxylic acid contained in the mixture includes divalent terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate and the like. Carboxylic acids or aromatic dicarboxylic acid components such as esters or anhydrides thereof, phthalic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, succinic acid, or esters or Aliphatic dicarboxylic acid components such as acid anhydrides, trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1 , 2,5-hexanetricarboxylic acid, 1,2, , 8-octane tetracarboxylic acid, or the like trivalent or higher carboxylic acids, such as their esters or acid anhydrides and the like, can be appropriately used individually or in combination of two or more. These may be plant-derived substances or petroleum-derived substances.
In addition, when using trivalent or more carboxylic acid and / or trivalent or more alcohol, it is preferable to contain 0.5-30 mol% in polyvalent carboxylic acid whole quantity. When the trivalent or higher carboxylic acid is 0.5 mol% or more, the hot offset resistance as a toner tends to be good, and when it is 30 mol% or less, the storage stability tends to be good.

Furthermore, in the present invention, by using isosorbide derived from plant raw materials as a copolymerization component, it is possible to prevent a decrease in storage stability and to increase the ratio of plant-derived substances in all raw materials and to reduce the environmental burden. Examples of the isosorbide derived from plant materials include Polysorb-P (registered trademark) (manufactured by Roquette).
In the present invention, the polycondensation of the mixture may be performed by a known method. For example, a method of introducing the mixture into a reaction vessel and performing polycondensation through an esterification reaction or a transesterification reaction may be mentioned. In the polycondensation, for example, a polymerization catalyst such as titanium tetraalkoxide, titanium oxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, magnesium acetate or the like can be used.

  The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C to 280 ° C. When the polymerization temperature is 180 ° C. or higher, the productivity tends to be good, and when it is 280 ° C. or lower, the decomposition of the resin and the by-product of volatile components that cause odor tend to be suppressed. The lower limit of the polymerization temperature is more preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher. The upper limit of the polymerization temperature is more preferably 270 ° C. or less.

In the present invention, if necessary, a release agent component can be added to the above mixture and polycondensed within a range not impairing the effects of the present invention. Addition of a release agent component and polycondensation tend to improve toner fixability and wax dispersibility. As the release agent component, the same waxes that can be used as a toner composition described later can be used as appropriate, for example, carnauba wax, rice wax, beeswax, synthetic ester wax, paraffin wax, various polyolefin waxes or modified products thereof, Examples thereof include fatty acid amides and silicone waxes.
The polyester resin for toner obtained by the production method of the present invention preferably has a glass transition temperature (Tg) of 52 ° C to 75 ° C. When Tg is 48 ° C. or higher, toner storage stability tends to be good, and when it is 75 ° C. or lower, toner fixability tends to be good. As for the lower limit of Tg, 54 degreeC or more is more preferable. The upper limit is more preferably 72 ° C. or lower.

  The softening temperature of the polyester resin of the present invention is preferably 110 to 160 ° C. When the softening temperature is 110 ° C. or higher, the hot offset resistance of the toner tends to be good, and when it is 160 ° C. or lower, the toner fixability tends to be good.

Furthermore, the acid value of the polyester resin of the present invention is preferably 25 mgKOH / g or less. When the acid value is 25 mgKOH / g or less, the image density of the toner tends to be stable.
The polyester resin for toner obtained by the method of the present invention can be suitably used as a binder resin for toner. A toner can be obtained by blending the polyester resin for toner of the present invention with a colorant, a charge control agent, a release agent, a flow modifier, a magnetic substance, and the like.

  The colorant is not particularly limited, but carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow, rhodamine dye, 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 not particularly limited, but is preferably 2 to 10% by mass in the toner from the viewpoint of the toner color tone, image density, and thermal characteristics.

  The charge control agent is not particularly limited, and examples of the positive charge control agent include quaternary ammonium salts and basic or electron-donating organic substances. Negative charge control agents include metal chelates, metal-containing dyes, and acidic substances. Or an electron withdrawing organic substance etc. are mentioned. 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 of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, metal complexes, amides 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 not particularly limited, but 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.

  The release agent is not particularly limited, and carnauba wax, rice wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester type in consideration of toner releasability, storage stability, fixability, color developability, etc. Wax, paraffin wax, fatty acid amide, silicone wax and the like can be appropriately selected and used. These can be used alone or in combination of two or more.

  The melting point of the release agent is not particularly limited, and can be appropriately selected and used in consideration of the toner performance. The content of the release agent is not particularly limited, but is preferably 0.3 to 15% by mass in the toner because it affects the toner performance. The lower limit of the content of the release agent is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. Further, the upper limit value of the content of the release agent is more preferably 13% by mass or less, and particularly preferably 12% by mass or less.

  Additives such as flow modifiers are not particularly limited, but fine powder silica, alumina, titania and other fluidity improvers, magnetite, ferrite, cerium oxide, strontium titanate, conductive titania and other inorganic fine powders , Resistance adjusters such as styrene resin and acrylic resin, and lubricants, and these are used as an internal additive or an external additive.

  The content of these additives is not particularly limited, but 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.

  Further, as the binder resin, a binder resin other than the polyester resin obtained by the production method of the present invention may be used within a range not impairing the effects of the present invention. For example, a polyester other than the polyester resin obtained by the production method of the present invention. A resin, a styrene resin, a styrene-acrylic resin, a cyclic olefin resin, a methacrylic acid resin, an epoxy resin, and the like can be given, and these can be used alone or in admixture of two or more.

  The toner of the present invention can be used as any one of a magnetic one-component developer, a non-magnetic one-component developer, and a two-component developer.

  When used as a magnetic one-component developer, it contains a magnetic substance, and as a magnetic substance, in addition to a ferromagnetic alloy containing ferrite, magnetite, iron, cobalt, nickel, etc., it does not contain a compound or a ferromagnetic element. Examples thereof include alloys that exhibit ferromagnetism by appropriate heat treatment, such as so-called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum and manganese-copper-tin, and chromium dioxide.

  The content of the magnetic substance is not particularly limited, but is preferably 3 to 70% by mass in the toner because it greatly affects the pulverizability of the toner. When the content of the magnetic material is 3% by mass or more, the charge amount of the toner tends to be at a sufficient level, and when it is 70% by mass or less, the fixability and grindability of the toner tend to be good. The lower limit of the content of the magnetic substance is more preferably 3% by mass or more, and particularly preferably 3% by mass or more. Further, the upper limit of the content of the magnetic material is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

  When used as a two-component developer, it is used in combination with a carrier. As the carrier, magnetic substances such as iron powder, magnetite powder and ferrite powder, those whose surfaces are coated with a resin coating, magnetic carriers and the like can be used. As the coating resin for the resin coating carrier, it is possible to use styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluorine resin, a mixture of these resins, etc. it can.

  The method for producing the toner of the present invention is not particularly limited, but after mixing the binder resin and the compound described above, the mixture is melt-kneaded with a twin screw extruder or the like, coarsely pulverized, finely pulverized, and classified. A method of manufacturing by externally adding inorganic particles (grinding method), dissolving and dispersing the binder resin and compound described above in a solvent, granulating in an aqueous medium, removing the solvent, washing, Examples thereof include a method (chemical method) in which toner particles are obtained by drying and externally added with inorganic particles as necessary.

Examples of the present invention are shown below. The evaluation methods for the resin and toner shown in this example are as follows.

(Glass transition temperature (Tg))
Intersection of the base line on the low temperature side of the chart and the tangent line of the endothermic curve near the glass transition temperature when measured with a differential scanning calorimeter DSC-60 manufactured by Shimadzu Corporation at a heating rate of 5 ° C / min The temperature of was determined.

(Softening temperature (T4mm))
When using a flow tester CFT-500 manufactured by Shimadzu Corporation and measuring with a 1 mmφ × 10 mm nozzle 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 the effluent flowed was determined.
(Acid value)
About 0.2 g of the sample was precisely weighed in a branch Erlenmeyer flask (A (g)), 10 ml of benzyl alcohol was added, and the mixture was heated with a heater at 230 ° C. for 15 minutes in a nitrogen atmosphere to dissolve the resin. After cooling to room temperature, 10 ml of benzyl alcohol, 20 ml of chloroform and a few drops of a phenolphthalein solution were added and titrated with a 0.02N 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
(Storage stability)
5 g of the toner was weighed and put into a sample bottle, which was left in a drier kept at 45 ° C. for about 24 hours, and the degree of toner aggregation was evaluated as an index of blocking resistance. The evaluation criteria were as follows.
◎ (Very good): Disperse just by inverting the sample bottle.
○ (Good): Disperse when the sample bottle is turned upside down and tapped 2 to 5 times.
X (Inferior): The sample bottle is inverted and does not disperse when tapped 5 times.

(Low temperature fixability)
^3. Using a printer having a fixing roller not coated with silicone oil and capable of changing the roller temperature with the roller speed set to 30 mm / s, the test pattern has a vertical toner density of 0.5 mg / cm ² . A solid image of 5 cm × 15 cm wide was prepared, and the temperature of the fixing roller was set to 95 ° C. and fixed on the test paper. The density measurement part of the obtained test paper is vertically folded, and the protective paper is put on the protective paper, and a 1 kg weight is slid to the folding part five times to make a crease, and then the same fold is made into a mountain fold. A 1 kg weight was slid five times on the bent part from above. The test paper was stretched, cellophane tape (Nitto Denko CS System No. 29) was applied to the bent part, traced 5 times, and then slowly peeled off, and the image density was measured with a Macbeth image densitometer RD917. The same measurement was performed at three locations, and the respective fixing rates were calculated from the image density before and after the test by the following formula, and evaluated by the average fixing rates at the three locations.
Fixing rate = image density after test / image density before test × 100 (%)
Fixing rate of 70% or more: Good low-temperature fixability Fixing rate of less than 70% or occurrence of offset phenomenon at 95 ° C .: Insufficient low-temperature fixability (hot offset resistance)
Using a printer that has a fixing roller not coated with silicone oil and that can change the roller temperature set at a roller speed of 100 mm / s, the test pattern has a toner density of 0.5 mg / cm 2 and a length of 4.5 cm × A solid image having a width of 15 cm was prepared, and when the roller temperature was changed every 5 ° C. and fixed, the maximum temperature at which the toner did not transfer to the fixing roller due to the hot offset phenomenon was determined as the offset upper limit temperature, and evaluated according to the following criteria.
○ (Good): Hot offset resistance upper limit temperature is 200 ° C or higher x (Inferior): Hot offset resistance upper limit temperature is less than 200 ° C

(Synthesis Example 1)
Polyhydric carboxylic acid, polyhydric alcohol, phytosterol (manufactured by Tama Seikagaku) shown in Table 1 and 1500 ppm of antimony trioxide with respect to all acid components were charged into a reaction vessel equipped with a distillation column. In addition, the preparation composition of polyhydric carboxylic acid and polyhydric alcohol described in Table 1 is a mole part of each component when the total acid component is 100 mole parts. In addition, phytosterol was added in an amount of 4.6% by mass in the total raw material so that the amount was 5% by mass in 100% by mass of the obtained resin.

Next, the temperature of the reaction system was increased, and the number of revolutions of the stirring blade in the reaction vessel was 120 rpm, and the reaction system was heated to a temperature of 265 ° C. From the middle of the temperature increase, water began to distill from the distillation tower and the esterification reaction started. During the esterification reaction, the temperature at the distillation outlet of the distillation column does not exceed 100 ° C, which is the boiling point of water. Measures were taken to prevent the scattering of volatile substances. The esterification reaction was completed when water was no longer distilled from the reaction system.
Subsequently, the temperature in the reaction system was lowered and maintained at 235 ° C., and the pressure in the reaction vessel was reduced to start a polycondensation reaction. The polycondensation reaction was allowed to proceed while distilling the diol component from the reaction system by reducing the pressure over about 20 minutes to a vacuum of 133 Pa in the reaction vessel. As the reaction proceeds, the viscosity of the reaction system increases, and as the viscosity increases, the degree of vacuum in the reaction system gradually approaches normal pressure due to nitrogen, and the polycondensation reaction proceeds until the stirring blade torque reaches the desired softening temperature. I let you. And stirring was stopped when the predetermined torque was shown, and the reaction system was returned to normal pressure to complete the polycondensation reaction. The inside of the reaction system was pressurized with nitrogen and the reaction product was taken out from the bottom of the reaction vessel to obtain a polyester resin 1. The physical property values of the obtained polyester resin 1 are shown in Table 1.

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

(Synthesis Example 2)
A polyester resin 2 was obtained in the same manner as in Synthesis Example 1 except that polyvalent carboxylic acid, polyhydric alcohol, and phytosterol (manufactured by Tama Seikagaku) were changed as shown in Table 1. In addition, 9.2 mass% was thrown in phytosterol in all the raw materials so that it might become 10 mass% in 100 mass% of resin obtained.

(Synthesis Example 3)
A polyester resin 3 was obtained in the same manner as in Synthesis Example 1 except that polyvalent carboxylic acid, polyhydric alcohol, and phytosterol (manufactured by Tama Seikagaku) were changed as shown in Table 1. In addition, 2.7 mass% was thrown in phytosterol in all the raw materials so that it might become 3 mass% in 100 mass% of resin obtained.

(Synthesis Example 4)
A polyester resin 4 was obtained in the same manner as in Synthesis Example 1 except that polyvalent carboxylic acid, polyhydric alcohol, and phytosterol (manufactured by Tama Seikagaku) were changed as shown in Table 1. In addition, 13.7 mass% of phytosterol was thrown in in all the raw materials so that it might become 14 mass% in 100 mass% of resin obtained.

(Synthesis Example 5)
A polyester resin 6 was obtained in the same manner as in Synthesis Example 1 except that the polyvalent carboxylic acid and polyhydric alcohol were changed as shown in Table 1.

(Synthesis Example 6)
A polyester resin 7 was obtained in the same manner as in Synthesis Example 1 except that polyvalent carboxylic acid, polyhydric alcohol, and phytosterol (manufactured by Tama Seikagaku) were changed as shown in Table 1. In addition, 23.1 mass% of phytosterol was thrown into all the raw materials so that it might become 25 mass% in 100 mass% of resin obtained.

(Synthesis Example 7)
A polyester resin 8 was obtained in the same manner as in Synthesis Example 1 except that polyvalent carboxylic acid, polyhydric alcohol, and phytosterol (manufactured by Tama Seikagaku) were changed as shown in Table 1. Note that 0.46% by mass of phytosterol was added to all raw materials so that the amount of phytosterol was 0.5% by mass in 100% by mass of the obtained resin.

(Synthesis Example 8)
A polyester resin 9 was obtained in the same manner as in Synthesis Example 1 except that polyvalent carboxylic acid, polyhydric alcohol, and phytosterol (manufactured by Tama Seikagaku) were changed as shown in Table 1. In addition, 9.4 mass% was thrown in phytosterol in all the raw materials so that it might become 10 mass% in 100 mass% of resin obtained.

Example 1
Tonerization was performed using the polyester resin 1 described above. 93% by mass of polyester resin 1, 3% by mass of quinacridone pigment (HOSTAARM PINK E, CI No .: Pigment Red 122) manufactured by Clariant, 3% by mass of Carnauba Wax No. 1 (manufactured by Toyo Adre), negative chargeability 1% by mass of a 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 at a preset temperature of the cylinder of 120 ° C. After kneading, the cooled mixture was pulverized to 10 μm or less with a jet mill 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 with a Henschel mixer to obtain a toner. The evaluation results of the obtained toner performance are shown in Table 2.

(Examples 2-4, Comparative Examples 1-3)
A toner was obtained in the same manner as in Example 1 except that the binder resin was changed as shown in Table 2. The evaluation results of the obtained toner performance are shown in Table 2.

(Comparative Example 4)
A toner was obtained in the same manner as in Example 1 except that, instead of the polyester resin 1, a binder resin obtained by dry blending 5:95 parts by mass of polyester resin and 5 parts by mass of phytosterol was used. The plant-derived raw material ratio of the binder resin obtained by blending polyester resin 5:95 parts by mass and phytosterols: 5 parts by mass is 21.5% by mass.

  The evaluation results of the obtained toner performance are shown in Table 2.

In Comparative Example 1, the content of phytosterol was large and the storage stability of the toner was poor.

  In Comparative Example 2, the content of phytosterol was small, and the low-temperature fixability and hot offset resistance of the toner were poor.

  In Comparative Example 3, the plant-derived 1,3-propanediol was not contained, and the low-temperature fixability was insufficient.

  In Comparative Example 4, phytosterol was dry blended during the toner production, and the storage stability and hot offset resistance were poor.

Claims (3)

A method for producing a polyester resin for a toner by polycondensation of a mixture containing phytosterol, a polyhydric alcohol containing 1,3-propanediol derived from a plant and a polycarboxylic acid, wherein A method for producing a polyester resin for toner containing mass%. A polyester resin for toner obtained by the method of claim 1. A toner using the toner polyester resin according to claim 2.