JP2011232665A - Method for producing polyester resin composition for toner, polyester resin composition for toner, and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester resin composition with a low environmental load capable of providing toner which includes a plant-derived raw material component and has excellent fixability and hot-offset resistance, and toner using the polyester resin composition.SOLUTION: A polyester resin composition for toner mixing phytosterol and a polyester resin which polycondenses a monomer mixture including a polyhydric alcohol with plant-derived 1, 3-propanediol and a polycarboxylic acid is produced. The polyester resin for toner obtained by the production method and toner including the polyester resin for toner are provided.

Description

  The present invention relates to a method for producing a polyester resin composition for a toner that is suitably used for developing an electrostatic charge image or a magnetic latent image, particularly in electrophotography, electrostatic recording method, electrostatic printing method, etc. The present invention relates to a polyester resin composition for toner and a 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 must first maintain a stable charge amount, and then must 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, 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 a polyester resin with a 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 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 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. Insufficient hot offset resistance.
In Patent Document 2, the binder resin does not contain phytosterol but is mixed into the toner as a color eraser, and the amount of the natural product-derived substance introduced is about 0.5% by mass, which is an environmental burden. The effect on reduction was insufficient.

  The gist of the present invention is a polyester resin composition for toner containing a polyester resin obtained by polycondensation of a monomer mixture containing a polyhydric alcohol containing 1,3-propanediol derived from a plant and a polycarboxylic acid, and phytosterol. is there.

By using the binder resin composition for toner of the present invention, it is possible to provide a toner having a low environmental load, a fixing property and a wide non-offset temperature range.

In the present invention, first, a polyhydric alcohol containing a plant-derived 1,3-propanediol and a monomer mixture containing a polycarboxylic acid are polycondensed.
By including 1,3-propanediol derived from plant raw materials as a polyhydric alcohol in the monomer mixture, the environmental burden can be reduced. 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.
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.

Examples of the polyvalent carboxylic acid contained in the monomer mixture include divalent carboxylic acids such as terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, and dibutyl isophthalate. 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 acids thereof Aliphatic dicarboxylic acid components such as 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, 1,2,7,8 Include octane-tetracarboxylic acid or tri- or higher carboxylic acids, such as their esters or acid anhydrides, may be suitably used alone or in combination of two or more. These may be plant-derived substances or petroleum-derived substances.
Polyhydric alcohols other than plant raw material-derived 1,3-propanediol contained in the monomer mixture include ethylene glycol, neopentyl glycol, polyethylene glycol, 1,2-propanediol, and 1,3-propane. Diol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,4-cyclohexanedimethanol, aliphatic diols such as 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 -Hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxy Siethylene- (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 , 2-methyl-1,2,4-butanetriol, trimethylolpropane, trihydric or higher alcohol components such as 1,3,5-trihydroxymethylbenzene, etc., and the range not impairing the effects of the present invention Thus, they can be used alone or in combination of two or more. These may be plant-derived substances or petroleum-derived substances.
In the case of using a trivalent or higher carboxylic acid and / or a trivalent or higher alcohol, the total amount of the polyvalent carboxylic acid is preferably 0.5 to 30 mol%. 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 this invention, isosorbide can also be used as a copolymerization component as a raw material derived from a plant raw material. Examples of isosorbide include Polysorb-P (registered trademark) (Roquette).
In the present invention, a polycondensation reaction of a monomer mixture containing the polyvalent carboxylic acid and the polyhydric alcohol is performed. Examples of the polycondensation method include a method in which the polyvalent carboxylic acid and the polyhydric alcohol are introduced into a reaction vessel and polymerized through an esterification reaction or a transesterification reaction and a condensation polymerization reaction. Polyester resin 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, and magnesium acetate 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, it is also possible to perform polymerization by adding a release agent component together with the above components within a range not impairing the effects of the present invention. By adding a release agent component and polymerizing, the toner fixing property and wax dispersibility tend to be improved. 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 present invention preferably has a 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, it is preferable that the acid value of the polyester resin of this invention is 2-25 mgKOH / g. When the acid value is 2 mgKOH / g or more, the reactivity of the resin tends to be improved, and when the acid value is 25 mgKOH / g or less, the toner image density tends to be stable. The upper limit of the acid value of the polyester resin is more preferably 20 mgKOH / g or less, and particularly preferably 15 mgKOH / g or less.
In the present invention, it is necessary to mix the polyester resin and phytosterol. By mixing phytosterol, the ratio of plant-derived raw materials can be increased, and a polyester resin composition excellent in low-temperature fixability and hot offset resistance as a toner can be provided.
From the viewpoint of reducing the environmental burden and from the viewpoint of low-temperature fixability and hot offset resistance of the toner, the phytosterol content is preferably 1% by mass or more based on the total components of the polyester resin composition. More preferably, it is 2% by mass or more. Moreover, it exists in the tendency for the storage stability of a polyester resin composition to become favorable because content of a phytosterol shall be 20 mass% or less.
Moreover, the phytosterol used by this invention is a general term for the sterols contained in a plant, and is cyclic alcohols, such as (beta) -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 a mixture of two or more. As phytosterols, phytosterols derived from soybeans manufactured by Tama Seikagaku are available.
The method for mixing the polyester resin and the phytosterol is not particularly limited, and the polyester resin and the phytosterol are dry-blended with a Henschel mixer, etc., melt-kneaded with a twin screw extruder, a single screw extruder, a batch kneader, an open roll, or the like. Examples thereof include a method of dissolving or finely dispersing a polyester resin and phytosterol in an organic solvent and then removing the solvent.

  The polyester resin composition 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 material 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.
The ratio of plant-derived substances in all toners is preferably 10% by mass or more, and more preferably 15% by mass or more.

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
(Low temperature fixability)
Using a printer that has a fixing roller not coated with silicone oil and can change the roller temperature with the roller speed set to 30 mm / s, the test pattern has a toner concentration of 0.5 mg / cm2 and a length of 4.5 cm. X A solid image having a width of 15 cm was prepared, and the temperature of the fixing roller was set to 95 ° C. and fixed on the test paper. For this test pattern image, the image density was measured with a Macbeth image densitometer.

The density measurement part of the test paper was vertically folded, and the protective paper was placed on the folding part, and a 1 kg weight was slid five times on the folded part to make a crease, and then the protective paper was put on the same crease as a mountain fold. A 1 kg weight was slid from the top to the bent part 5 times. 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. 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 (%)
○ (Good): Fixing rate of 70% or more × (Inferior): Fixing rate of less than 70% or Offset phenomenon occurs at 95 ° C (non-offset temperature range)
Using a printer that has a fixing roller not coated with silicone oil and can change the roller temperature set at a roller speed of 100 mm / s, the test pattern has a toner concentration of 0.5 mg / cm ^{2 and} a length of 4.5 cm. × When a solid image of 15 cm in width is created and fixed at every 5 ° C roller temperature, the minimum temperature at which the toner does not transfer to the fixing roller due to the offset phenomenon due to insufficient melting of the toner is fixed by the non-offset lower limit temperature and the hot offset phenomenon The maximum temperature at which toner does not transfer to the roller was defined as the non-offset upper limit temperature, and the non-offset upper limit temperature (° C.) − The non-offset lower limit temperature (° C.) was evaluated as the non-offset temperature range according to the following criteria.
◎ (Very good): Non-offset temperature range is 70 ° C or higher ○ + (Good): Non-offset temperature range is 65 ° C or higher and lower than 70 ° C ○ (Good): Non-offset temperature range is 60 ° C or higher and lower than 65 ° C ○-(available): Non-offset temperature range of 55 ° C or higher and less than 60 ° C x (Inferior): Non-offset temperature range of less than 55 ° C (ratio of plant-derived substances)
The ratio of plant-derived substances in the toner was calculated based on the toner blending ratio and evaluated according to the following criteria. The ratio of plant-derived substances in the polyester resin was based on the ratio of plant-derived substances in all raw materials.
○ (Good): The toner has a ratio of plant-derived substances in the toner of 15% by mass or more, and considers reduction of environmental burden.
X (defect): The toner has a plant-derived material ratio of less than 15% by mass, and has no or little consideration for reducing environmental burden.
(Synthesis Example 1)
1500 ppm of antimony trioxide with respect to the polyvalent carboxylic acid, polyhydric alcohol, and all acid components shown in Table 1 was 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.
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.

(Synthesis Example 2)
A polyester resin 2 was obtained in the same manner as in Synthesis Example 1, except that the charged composition was changed as shown in Table 1. Table 2 shows the physical property values of the obtained polyester resin.

ジオールＡ：ポリオキシプロピレン−（２．３）−２，２−ビス（４−ヒドロキシフェニル）プロパンジオール
ジオールＢ：ポリオキシエチレン−（２．０）−２，２−ビス（４−ヒドロキシフェニル）プロパンジオール

（ポリエステル樹脂組成物１）
表２に示す比率で、ポリエステル樹脂１およびフィトステロールをヘンシェルミキサーで５分間混合し、ポリエステル樹脂組成物１を得た。得られたポリエステル樹脂組成物１の物性値を表２に示す。
（ポリエステル樹脂組成物２）
表２に示す比率でポリエステル樹脂１およびフィトステロールをヘンシェルミキサーで５分間混合したのち、シリンダー温度を１２０℃に設定した二軸押出機にて溶融混練し、ポリエステル樹脂組成物２を得た。得られたポリエステル樹脂組成物２の物性値を表２に示す。
（ポリエステル樹脂組成物３）
ポリエステル樹脂１およびフィトステロールの混合比率を表２に示す比率に変更する以外は、ポリエステル樹脂組成物２と同様の方法で、ポリエステル樹脂組成物３を得た。得られたポリエステル樹脂組成物３の物性値を表２に示す。
（ポリエステル樹脂組成物４）
ポリエステル樹脂１をポリエステル樹脂２に変更する以外は、ポリエステル樹脂組成物２と同様の方法で、ポリエステル樹脂組成物４を得た。得られたポリエステル樹脂組成物４の物性値を表２に示す。

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

(Polyester resin composition 1)
Polyester resin 1 and phytosterol were mixed for 5 minutes with a Henschel mixer at the ratio shown in Table 2 to obtain polyester resin composition 1. The physical property values of the obtained polyester resin composition 1 are shown in Table 2.
(Polyester resin composition 2)
Polyester resin 1 and phytosterol were mixed at a ratio shown in Table 2 for 5 minutes with a Henschel mixer, and then melt-kneaded in a twin-screw extruder set at a cylinder temperature of 120 ° C. to obtain polyester resin composition 2. The physical property values of the obtained polyester resin composition 2 are shown in Table 2.
(Polyester resin composition 3)
A polyester resin composition 3 was obtained in the same manner as the polyester resin composition 2 except that the mixing ratio of the polyester resin 1 and phytosterol was changed to the ratio shown in Table 2. The physical property values of the obtained polyester resin composition 3 are shown in Table 2.
(Polyester resin composition 4)
A polyester resin composition 4 was obtained in the same manner as the polyester resin composition 2 except that the polyester resin 1 was changed to the polyester resin 2. The physical property values of the obtained polyester resin composition 4 are shown in Table 2.

（実施例１）
上記で得られたポリエステル樹脂組成物１を用いて、トナー化を行った。ポリエステル樹脂組成物１を９３質量％、キナクリドン顔料（クラリアント社製ＨＯＳＴＡＰＡＲＭ ＰＩＮＫ Ｅ、Ｃ．Ｉ．番号：Ｐｉｇｍｅｎｔ Ｒｅｄ １２２）を３質量％、カルナバワックス１号（東洋アドレ社製）３質量％、負帯電性の荷電制御剤（日本カーリット社製ＬＲ−１４７）１質量％を、ヘンシェルミキサーで５分間混合した。

Example 1
The polyester resin composition 1 obtained above was used to form a toner. 93% by mass of polyester resin composition 1, 3% by mass of quinacridone pigment (HOSTAPARM PIN E, CI No .: Pigment Red 122 manufactured by Clariant), 3% by mass of carnauba wax No. 1 (manufactured by Toyo Adre), negative 1% by mass of a chargeable charge control agent (LR-147 manufactured by Nippon Carlit Co., Ltd.) was mixed for 5 minutes with a Henschel mixer.

  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% by mass of the obtained fine powder, 0.25% by mass of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added and mixed and adhered by a Henschel mixer to obtain a toner. Table 3 shows the evaluation results of the obtained toner performance.

(Examples 2 and 3, Comparative Examples 1 and 2)
A toner was obtained in the same manner as in Example 1 except that the polyester resin composition 1 was changed as shown in Table 3. Table 3 shows the evaluation results of the obtained toner performance.

比較例１は、フィトステロールを含有しておらず、トナーの低温定着性が不良であった。
比較例２は植物由来の１，３−プロパンジオール環境負荷低減への配慮が不良であった。

Comparative Example 1 did not contain phytosterol, and the low-temperature fixability of the toner was poor.
In Comparative Example 2, consideration for reducing the environmental load of plant-derived 1,3-propanediol was poor.

Claims (2)

A polyester resin composition for toner, comprising a polyester resin obtained by polycondensation of a monomer mixture containing a polyhydric alcohol containing 1,3-propanediol derived from a plant and a polyvalent carboxylic acid, and phytosterol. A toner using the polyester resin composition for toner according to claim 1.