JP5690611B2 - Resin particles and toner for electrophotography - Google Patents

Description

  The present invention relates to a resin particle made of a novel polyester resin and an electrophotographic toner.

  Polyester resins are used in various fields such as fibers, packaging materials, fiber reinforced plastics, paints, adhesives, electrophotographic developers, and the amount of use is also enormous. Therefore, the amount of raw materials derived from fossil resources used for these polyester resins and the amount of carbon dioxide generated when the used polyester resin is incinerated have reached a level that cannot be ignored.

  Under such circumstances, development of polyester resins using raw materials obtained from renewable biomass resources has become active. One of the significance of using these biomass resources is that the plant absorbs carbon dioxide generated during the incineration treatment of the resin using biomass and the resin composition thereof and regenerates the biomass in several years. In other words, it is the realization of so-called carbon neutral that does not substantially affect the amount of carbon dioxide in the environment. However, the most developed polylactic acid-based materials are inferior in water resistance, moisture resistance, chemical resistance, and mechanical properties as compared with conventional polyester resins, and their use is limited at present.

  In the field of electrophotographic toners, which is one of the uses of polyester resins, in recent years, there has been a demand for small-diameter toners having a narrow particle size distribution due to increasing demand for higher image quality. As a method for producing a small-diameter toner having a uniform particle diameter, a production method using a phase inversion phenomenon is known (Patent Document 1). In this method, an aqueous dispersion is added to a resin solution obtained by dissolving a resin in a water-insoluble organic solvent to cause phase inversion and emulsify and disperse to form an O / W type emulsion. / W-type emulsion is performed by applying heat to evaporate the organic solvent and precipitate resin particles. This phase inversion emulsification simplifies the process and makes it possible to obtain resin particles having a uniform particle diameter by a relatively simple operation, which can improve production efficiency and at the same time reduce costs. In addition, compared to pulverization methods and suspension polymerization methods, there are many types of resins that can be used, and the use of the resulting resin particles is expanded.

  Further, a method for producing a small particle toner by a phase inversion emulsification method using a polylactic acid resin as a raw material is known (Patent Document 2).

  Moreover, the manufacturing method of the water dispersion by the phase inversion emulsification method which used the carboxyl group-containing polyester-type resin as a raw material is known (patent document 3).

Japanese Patent Laid-Open No. 4-303849 JP 2008-262179 A JP 2004-204033 A

  However, the technique described in Patent Document 2 has a problem in that polylactic acid polymerized with the same monomer component of D-form or L-form has high crystallinity and therefore has extremely low solubility in an organic solvent. In Patent Document 3, in order to obtain an aqueous dispersion having a narrow particle size distribution, a large excess of neutralizing agent is required with respect to the carboxyl groups in the polyester resin. The current situation is that the load on the environment is large.

  Accordingly, an object of the present invention is to provide resin particles and an electrophotographic toner capable of using recyclable resources as a part of raw materials.

  The inventor of the present invention has completed the present invention as a result of intensive studies to solve the above problems. That is, the gist of the present invention is as follows.

That is, the resin particles of the present invention have the following chemical formula:
Wherein X is aliphatic or aromatic, Y is a purified rosin residue, disproportionated rosin residue, or hydrogenated rosin residue, and n = 0 to 1 A polyester resin which is an essential component of the alcohol component.

  In a preferred embodiment of the resin particles of the present invention, the resin particles have a volume average particle size in the range of 0.01 to 1 μm.

  Further, in a preferred embodiment of the resin particle of the present invention, after adding a neutralizing agent and an aqueous medium to a resin solution in which the polyester resin is dissolved in an organic solvent to cause phase inversion, an O / W type resin is obtained. It is obtained by forming emulsified particles and further removing the organic solvent from the O / W type resin emulsified particle dispersion.

In a preferred embodiment of the resin particle of the present invention, the compound has the following chemical formula [Chemical Formula 2],
A compound having two epoxy groups in one molecule (wherein X is aliphatic or aromatic and n = 0 to 1) is added to a purified rosin, a disproportionate amount It is characterized by being obtained by addition reaction of one or more selected from fluorinated rosin and hydrogenated rosin.

In a preferred embodiment of the resin particle of the present invention, the compound represented by the chemical formula [ Chemical Formula 1] is blended in an amount of 20% by weight or more as a polyester raw material.

  Moreover, in a preferred embodiment of the resin particle of the present invention, the neutralizing agent is contained in an amount of 0.8 to 1.7 times the carboxyl group contained in the polyester resin.

The electrophotographic toner of the present invention is an electrophotographic toner comprising at least a polyester resin and a colorant, and has the following chemical formula:
Wherein X is aliphatic or aromatic, Y is a purified rosin residue, disproportionated rosin residue, or hydrogenated rosin residue, and n = 0 to 1 Is) containing resin particles made of a polyester resin which is an essential component of the alcohol component.

  In the electrophotographic toner of the present invention, the resin particles have an average particle diameter in the range of 0.01 to 1 μm.

  In a preferred embodiment of the electrophotographic toner of the present invention, after adding a neutralizing agent and an aqueous medium to a resin solution obtained by dissolving the polyester resin in an organic solvent to cause phase inversion, an O / W It includes resin particles obtained by forming molded resin emulsified particles and further removing the organic solvent from the O / W resin emulsified particle dispersion.

In a preferred embodiment of the electrophotographic toner of the present invention, the compound has the following chemical formula:
A compound having two epoxy groups in one molecule (wherein X is aliphatic or aromatic and n = 0 to 1) is added to a purified rosin, a disproportionate amount It is characterized by being obtained by addition reaction of one or more selected from fluorinated rosin and hydrogenated rosin.

In a preferred embodiment of the electrophotographic toner of the present invention, the compound represented by the chemical formula [Chemical Formula 3] is blended in an amount of 20% by weight or more as a polyester raw material.

  In a preferred embodiment of the electrophotographic toner of the present invention, the neutralizing agent is contained in an amount of 0.8 to 1.7 times equivalent to the carboxyl group contained in the polyester resin.

  According to the present invention, there are advantageous effects that it is possible to provide resin particles having excellent environmental characteristics and a narrow particle size distribution, and a small particle size toner having a narrow particle size distribution that can cope with high image quality. Further, according to the present invention, in addition to environmental characteristics such as a small amount of waste water in the production process, there is an advantageous effect that resin particles and toner having a narrow particle size distribution can be provided.

The IR (infrared absorption spectrum) chart of the polyester resin obtained in Synthesis Example 1 is shown. The ¹ H-NMR (nuclear magnetic resonance) spectrum of the polyester resin obtained in Synthesis Example 1 is shown. The infrared absorption spectrum of the alcohol compound obtained by the synthesis example 1 is shown. 1 shows the ¹ H-NMR (nuclear magnetic resonance) spectrum of the alcohol compound obtained in Synthesis Example 1.

  The present invention comprises a resin particle and an electrophotographic toner containing the resin particle. The resin particles of the present invention can be used not only for electrophotographic toners but also, for example, aqueous dispersions of the resin particles are useful as binder components in the fields of paints, inks, adhesives, coatings and the like.

First, the polyester resin used in the resin particles and the electrophotographic toner of the present invention will be described. The polyester resin used in the resin particles and the electrophotographic toner of the present invention has the following chemical formula:
Wherein X is aliphatic or aromatic, Y is a purified rosin residue, disproportionated rosin residue, or hydrogenated rosin residue, and n = 0-1. ) Can be an essential component.

In a preferred embodiment of the present invention, the compound represented by the above [Chemical 5] has the following compound [Chemical 6] having two epoxy groups in one molecule,
A compound selected from the group consisting of a purified rosin, a disproportionated rosin, and a hydrogenated rosin on the epoxy group of the compound represented by formula (wherein X is aliphatic or aromatic and n = 0 to 1). The above can be obtained by addition reaction.

  In a preferred embodiment of the resin particle of the present invention, the compound represented by the above [Chemical Formula 5] is blended in an amount of 20% by weight or more as a polyester raw material.

  In the present specification, rosin is a natural resin obtained from pine, and the main components thereof are abietic acid, parastrinic acid, neoabietic acid, pimaric acid, dehydroabietic acid, isopimaric acid, sandaracopimalic acid, It means a resin acid such as dihydroabietic acid and a mixture thereof. Rosin is roughly divided into tall rosin obtained from tall oil obtained as a by-product in the process of producing pulp, gum rosin obtained from raw pine ani, wood rosin obtained from pine stumps, etc. One or more selected from rosin, disproportionated rosin and hydrogenated rosin.

  First, a method for producing a polyester resin constituting the resin particles and the electrophotographic toner of the present invention will be described. One example of a method for producing a polyester resin constituting the present invention comprises a two-stage reaction, and after obtaining the following compound (a) by the first stage reaction, the polyester resin is obtained by the same method as before in the second stage. Is to be manufactured.

  First, the compound (a) ([Chemical Formula 8]) represented by the following chemical formula (2), which is an essential alcohol raw material for the polyester resin of the present invention, will be described. Compound (a) is selected from, for example, purified rosin, disproportionated rosin, and hydrogenated rosin as the epoxy group of the compound having two epoxy groups in one molecule represented by chemical formula (1) ([Chem. 7]) One or more of these can be obtained by addition reaction in the presence of a known catalyst under nitrogen at a temperature of 130 to 185 ° C. until the acid value is less than 5 mg KOH / g.

Chemical formula (1) ([Chem. 7])
(In the formula, X is aliphatic or aromatic, and n = 0 to 1.)

Compound (a) ([Chemical Formula 8])
(In the formula, X is aliphatic or aromatic, Y is a purified rosin, a disproportionated rosin residue, or a hydrogenated rosin residue, and n = 0 to 1.)

  The reaction temperature is not particularly limited, but when the reaction temperature at the first stage is 185 ° C. or higher, the hydroxyl group present in the epoxy compound molecule or the hydroxyl group formed by the reaction of rosin and the unreacted rosin is dehydrated. From the viewpoint that the alcohol used as the raw material of the polyester resin may not be obtained, the first stage reaction temperature is preferably less than 185 ° C.

  Further, from the viewpoint of shortening the reaction time, the reaction can be preferably performed at 130 ° C. or higher. The reaction end point of the first stage is defined by the acid value. However, when the acid value is 5 mgKOH / g or more and the reaction proceeds to the second stage reaction, the unreacted rosin causes a reaction that hinders the formation of the molecular chain, which is the target. There is a possibility that a molecular weight polyester resin cannot be obtained. In addition, when the number n of the compound having two epoxy groups in one molecule represented by the chemical formula (1) is larger than 1, the resulting compound becomes a polyfunctional alcohol, and the polyester resin is branched to increase the viscosity or gel. The target polyester resin may not be obtained. The amount of compound (a) added in the first stage is not particularly limited. The compound (a) produced in the first stage is contained in an amount of 20% or more by weight in the target polyester raw material from the viewpoint that the effect is low in terms of water resistance and physical properties and the effect of reducing the environmental load is low. Is preferred.

The epoxy compound having two epoxy groups in one molecule represented by the chemical formula (1) ([Chem. 7]) is not particularly limited, but phenols having two phenolic hydroxyl groups in one molecule, 1 Alcohols having two hydroxyl groups in the molecule can be produced by epoxidizing with epichlorohydrin by a known method, alone or in combination of two or more. Commercially available epoxy compounds can also be used. Commercially available epoxy compounds include "JER828" manufactured by Mitsubishi Chemical Corporation, "AER260" manufactured by Asahi Kasei Chemicals Corporation, "Epicron 840, 850" manufactured by DIC Corporation, "Epototo 128" manufactured by Tohto Kasei Corporation, and Dow Chemical Company "D.E.R.317", "D.E.R.331", bisphenol A type epoxy compounds such as "Sumiepoxy ESA-011" manufactured by Sumitomo Chemical Co., Ltd., "Epiclon 830S" manufactured by DIC, Mitsubishi Bisphenol F type epoxy compounds such as “Epicoat 807” manufactured by Kagaku Co., Ltd., “Epototo YDF-170” manufactured by Tohto Kasei Co., Ltd., “Araldite XPY306” manufactured by Asahi Kasei Chemicals Co., Ltd., “EBPS-200” manufactured by Nippon Kayaku, Asahi Bisphenol S type such as “EPX-30” manufactured by Denka Kogyo Co., Ltd. and “Epicron EXA1514” manufactured by DIC Co., Ltd. Xyl compounds, bisphenolfluorene type epoxy compounds such as "BPFG" manufactured by Osaka Gas Chemical Company, bixylenol type compounds such as "YL-6056" and "YX-4000" manufactured by Mitsubishi Chemical Corporation, or biphenyl type epoxy compounds, or those , "HBE-100" manufactured by Shin Nippon Chemical Co., Ltd., hydrogenated bisphenol A type epoxy compounds such as "Epototo ST-2004" manufactured by Tohto Kasei Co., Ltd., "Epiclon 152" manufactured by DIC, manufactured by Sakamoto Pharmaceutical Co., Ltd. "SR-BSP", Toto Kasei "Epototo YDB-400", Dow Chemical "DE 542", Asahi Kasei Chemicals "AER8018", Sumitomo Chemical "Sumiepoxy ESB" Brominated bisphenol A type epoxy compounds such as “-400”, trade name “ESN-19” manufactured by Nippon Steel Chemical Co., Ltd. ”, An epoxy compound having a naphthalene skeleton such as a product name“ HP-4032 ”manufactured by DIC, a product name“ Epolite 400E ”,“ Epolite 400P ”,“ Epolite 1600 ”manufactured by Kyoeisha Chemical Co., Ltd., manufactured by Sakamoto Pharmaceutical Co., Ltd. Aliphatic epoxy compounds such as “SR-NPG” and “SR-16HL” are exemplified, but not limited thereto. These can be used alone or in combination of two or more.

  Next, the carboxylic acid, alcohol, and glycolic acid, which are raw materials for the polyester resin used in the second stage reaction, were either thermochemically produced from conventional petroleum, biochemically produced from animal or plant raw materials, or Although it is possible to use compounds produced by thermochemical treatment of compounds produced biochemically from animal and plant materials, they are biochemically produced from animal and plant materials in terms of environmental impact and carbon neutrality, or animal and plant materials. It is preferable to use a compound produced by thermochemical treatment of a compound produced biochemically from the above.

Conventional carboxylic acids thermochemically produced from petroleum include phthalic acid, terephthalic acid, isophthalic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, 5-
Examples thereof include tert-butyl-1,3-benzenedicarboxylic acid and derivatives thereof such as acid anhydrides and lower alkyl esters thereof. Among these, it is particularly preferable to use at least one selected from the group consisting of terephthalic acid, isophthalic acid, and derivatives thereof. The lower alkyl esters of terephthalic acid and isophthalic acid may be used. Examples of lower alkyl esters of terephthalic acid and isophthalic acid include, for example, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, Although there are dibutyl terephthalate, dibutyl isophthalate, and the like, dimethyl terephthalate and dimethyl isophthalate are preferable in terms of cost and handling (handling).

  The carboxylic acids produced biochemically from animal and plant raw materials or by thermochemical treatment of compounds produced biochemically from animal and plant raw materials include sebacic acid, dimer acid, succinic acid, and alkyl succinic acid. Alkenyl succinic acid, itaconic acid, maleic anhydride, maleic acid, fumaric acid, 2,5-furandicarboxylic acid and the like.

  These carboxylic acids or lower alkyl esters thereof may be used alone or in combination of two or more. In addition, trivalent or higher aromatic polycarboxylic acids can be further used within a range not impairing the effects of the present invention. Examples of the trivalent or higher valent aromatic polycarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Two or more kinds may be used in combination. The trivalent or higher aromatic polycarboxylic acid is preferably trimellitic anhydride from the viewpoint of reactivity.

  Conventional alcohols thermochemically produced from petroleum include aliphatic alcohols and etherified diphenols. Examples of the aliphatic alcohol include, for example, ethylene glycol, 1,2-propanediol, 1.3-propanediol, 1.2-butanediol, 1,3-butanediol, 1,4-butanediol, 2, 3-butanediol, 1,4-butenediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 2-ethyl-2-methylpropane-1,3-diol, 2 -Butyl-2-ethylpropane-1,3-diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2,4-dimethyl-1 , 5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,7-heptanediol, 1,8-octanediol, , 9-nonanediol, 1,10-decanediol, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropanoate, diethylene glycol, triethylene glycol, dipropylene glycol and the like. . As the aliphatic alcohol, ethylene glycol, 1,3-propanediol, and neopentyl glycol are preferable from the viewpoints of reactivity with acid and glass transition temperature of the resin.

  Alcohols produced biochemically from animal or plant raw materials or produced by thermochemical treatment of compounds produced biochemically from animal or plant raw materials include ethylene glycol, 1,2-propanediol, 1,3 -Propanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,4-butanediol, glycerin, 2,5-dihydroxymethylfuran.

  These aliphatic alcohols may be used alone or in combination of two or more. In the present invention, an etherified diphenol may be further used together with the aliphatic alcohol. Etherified diphenol is a diol obtained by addition reaction of bisphenol A and alkylene oxide. The alkylene oxide is ethylene oxide or propylene oxide, and the average added mole number of the alkylene oxide is bisphenol A. What is 2-16 mol with respect to 1 mol is preferable. From the viewpoint of environmental load and carbon neutral, it is preferable to use ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol produced biochemically from animal and plant raw materials. Furthermore, a trivalent or higher polyol can be used as long as the effects of the present invention are not impaired. Examples of the trivalent or higher polyol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like. These may be used alone or in combination of two or more. As the trivalent or higher polyol, glycerin is preferable from the viewpoint of environmental load and carbon neutral, and trimethylolpropane is preferable from the viewpoint of reactivity.

  As other components of the polyester raw material, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanecarboxylic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endo, as long as the object of the present invention is not impaired. Alicyclic polycarboxylic acids such as methylenetetrahydrophthalic anhydride, halogen-containing dicarboxylic acids such as heptic acid and tetrabromophthalic anhydride, hydroxycarboxylic acids such as lactic acid, 3-hydroxybutanoic acid, and 3-hydroxy-4-ethoxybenzoic acid Fatty acids obtained from plants such as linseed oil fatty acid and castor oil fatty acid can also be used.

  The polyester resin constituting the present invention is prepared by a known and commonly used production method using the compound (a), a predetermined carboxylic acid component, and an alcohol component as raw materials. As the reaction method, either a transesterification reaction or a direct esterification reaction can be applied. Further, polycondensation can be promoted by a method of increasing the reaction temperature by pressurization, a pressure reduction method, or a method of flowing an inert gas under normal pressure. The second-stage reaction may be non-catalyzed, or may be promoted using a known and commonly used reaction catalyst such as at least one metal compound selected from antimony, titanium, tin, zinc, aluminum and manganese. good. The addition amount of these reaction catalysts is preferably 0.01 to 1.0 part by weight with respect to 100 parts by weight of the total amount of the carboxylic acid component and the alcohol component.

  As a method for producing a polyester resin constituting the present invention other than the above, a method in which the compound (a) produced in a separate apparatus is transferred and reacted with the raw materials used in the second stage in a one-stage reaction, or production Alternatively, the compound (a) may be stored in a storage facility such as a tank, and a necessary amount may be transferred and reacted in a one-stage reaction together with the raw materials used in the second stage.

  The preferable softening point of the polyester resin that can be used in the present invention is 90 ° C to 160 ° C. More preferably, it is 100-150 degreeC. When the softening temperature is less than 90 ° C., the cohesive strength of the resin tends to be extremely reduced, while when it exceeds 160 ° C., the melt flow and low-temperature fixability of the toner using the resin tend to be lowered.

  Fundamental properties desired for electrophotographic toners are fixability and offset resistance. One method for making these contradictory performances compatible is to use a mixture of two or more polyester resins having different softening points as a polyester resin for a toner as a raw material. In the present invention, it is one of preferred embodiments to mix and use two or more kinds of polyester resins having different softening points in order to achieve both the fixing property and offset resistance of the toner obtained.

  The polyester resin constituting the present invention has a glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) of 45 to 80 ° C, more preferably 50 to 75 ° C. When Tg is lower than 45 ° C., the blocking resistance of the toner is lowered, and the toner may agglomerate. On the other hand, when Tg exceeds 80 ° C., the low-temperature fixability tends to decrease.

  It is necessary to introduce an ionic functional group into the polyester resin used in the present invention in order to increase the affinity for water. Examples of the ionic functional group include a carboxyl group and a sulfonyl group. The method for introducing these ionic functional groups is not particularly limited, and can be introduced by a conventionally known method. For example, a method of introducing carboxyl groups by adjusting the ratio of the total amount of hydroxyl groups to the total amount of carboxyl groups in the raw material of the polyester resin used in the present invention, phthalic anhydride, trimellitic anhydride, anhydrous anhydride during or after the synthesis of the polyester resin Examples include a method of introducing a carboxyl group by adding an acid anhydride such as pyromellitic acid or succinic anhydride, a method of using a metal salt of a compound having a sulfonyl group such as 5-sulfoisophthalic acid as a raw material, and the like. Can do.

  The polyester resin preferably has an acid value of 3 to 30 mgKOH / g from the viewpoint of dispersibility in water. More preferably, it is 5-20 mgKOH / g. If the acid value is less than 3 mgKOH / g, the dispersibility in water may be reduced. On the other hand, if the acid value exceeds 30 mgKOH / g, the durability of the resulting resin particles or electrophotographic toner may be inferior.

  The resin particles and the electrophotographic toner of the present invention can be obtained by any known and commonly used means by a conventional method. For example, in the case of resin particles, the resin and, if necessary, various additives can be obtained by melt-kneading at or above the melting point (softening point) of the resin, and then pulverizing and classifying. For example, in the case of an electrophotographic toner, it can be obtained by melting and kneading a resin, a colorant and, if necessary, various additives above the melting point (softening point) of the resin, pulverizing and classifying. it can. However, in order to obtain a small particle size toner having a narrow particle size distribution, which is a part of the problem of the present invention, it is desirable to use means utilizing the phase inversion phenomenon described later.

  The resin particle of the present invention is a compound represented by the above chemical formula [Chemical Formula 1] as described above (wherein X is aliphatic or aromatic, Y is a purified rosin residue, disproportionated rosin. A residue or a hydrogenated rosin residue, where n = 0 to 1.) is made of a polyester resin which is an essential component of the alcohol component.

  In a preferred embodiment of the resin particles of the present invention, the average particle size of the resin particles is preferably 0.01 to 1 μm, more preferably 0.03 to 0.5 μm. Features. If the average particle diameter exceeds 1 μm, the particle diameter distribution of the finally obtained electrophotographic toner may be broadened, or the storage stability may be deteriorated, for example, precipitates may be generated during storage of the resin particle dispersion. . On the other hand, if the average particle size is less than 0.01 μm, the resin particle dispersion has a high viscosity and the solid content concentration must be lowered, which may reduce workability.

  In a preferred embodiment, the resin particles of the present invention are obtained by adding a neutralizing agent and an aqueous medium to a resin solution obtained by dissolving the polyester resin in an organic solvent to cause phase inversion, followed by O / W resin emulsification. It can be obtained by forming particles and further removing the organic solvent from the O / W type resin emulsified particle dispersion.

  In this invention, it is preferable that the solid content concentration at the time of melt | dissolving a polyester resin in an organic solvent is 30 to 80 weight%. More preferably, it is 45 to 70% by weight. If it is lower than 30% by weight, a large amount of organic solvent is used, which is not preferable from the viewpoint of cost and environment. If the solid content concentration exceeds 80% by weight, the viscosity of the solution is increased and the stirring property is lowered, which is not preferable.

  Solvents used for dissolving the polyester resin of the present invention include isopropyl alcohol, n-butanol, 2-ethylhexanol, methyl ethyl ketone, acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, 1,3-oxolane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and the like can be used. From the viewpoint of removing the organic solvent from the resin particle dispersion in a short time, a solvent having a boiling point of 100 ° C. or lower, such as methyl ethyl ketone, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, isopropyl alcohol, is particularly preferable. Two or more of these solvents may be used.

  In the present invention, when obtaining resin particles dispersed in water using a polyester resin having a carboxyl group, it is desirable that the carboxyl group is neutralized by a basic compound, and the addition time is determined by dissolving the polyester resin in an organic solvent. Then, it is desirable to add water to invert the phase. If a polyester resin, an organic solvent, and a basic compound are allowed to coexist at the time of dissolution, it is not preferable because time is required for dissolution. Also, the addition of a basic substance after phase inversion is not preferable because addition of a basic substance after phase inversion with water does not contribute to particle formation.

  As a basic substance that can be used as a neutralizing agent, amine compounds such as ammonia and triethylamine, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate can be used.

  As the usage-amount of the said basic substance, 0.8-1.7 times equivalent is preferable with respect to the quantity of the carboxyl group contained in a polyester resin, and 1.0-1.5 times equivalent is more preferable. If it is lower than 0.8 times equivalent, sufficient hydrophilicity cannot be imparted to the resin, which may cause precipitation in the water dispersion step. Moreover, when it exceeds 1.7 times equivalent, it exists in the tendency for a particle size distribution to become wide.

  The aqueous dispersion of resin particles of the present invention can be obtained by adding the above basic substance to a polyester resin dissolved in a solvent for neutralization, and then adding water to cause phase inversion. The internal temperature during phase inversion is preferably room temperature or higher and lower than the boiling point of the organic solvent or basic compound.

  The aqueous dispersion of the resin particles of the present invention preferably removes the solvent after neutralization and phase inversion. The removal of the organic solvent can be performed by a general method such as heating and decompression. The amount of the remaining organic solvent in the aqueous dispersion of the resin particles of the present invention is desirably 2% or less from the viewpoint of maintaining the stability as the dispersion. More preferably, it is 1% or less. The removed organic solvent can be used again for dissolving the resin.

  Next, the electrophotographic toner of the present invention will be described. The electrophotographic toner of the present invention is an electrophotographic toner containing the resin particles of the present invention, and examples thereof include an electrophotographic toner using the resin particles of the present invention as they are. In addition, since a dispersion in which resin particles having a particle size smaller than the toner size are dispersed can be obtained, the dispersion is mixed with a dispersion in which other resin particles that are separately manufactured are dispersed, and the temperature of the obtained dispersion is obtained. Electroparticles using resin particles obtained by associating resin particles in the dispersion into toner-sized particles by appropriately controlling conditions such as pH, electrolyte concentration, etc., and separating and drying the particles Toner for use.

  The electrophotographic toner of the present invention is an electrophotographic toner comprising at least a polyester resin and a colorant, and is a compound represented by the above chemical formula [Chemical Formula 3] (where X is aliphatic or aromatic). , Y is a purified rosin residue, a disproportionated rosin residue, or a hydrogenated rosin residue, where n = 0 to 1.) includes resin particles made of a polyester resin, which is an essential component of the alcohol component It is characterized by that. Therefore, basically, the description of the resin particles of the present invention described above can be applied to the following electronic toner of the present invention.

  In the electrophotographic toner of the present invention, the resin particles have an average particle size in the range of 0.01 to 1 μm.

  In a preferred embodiment of the electrophotographic toner of the present invention, after adding a neutralizing agent and an aqueous medium to a resin solution obtained by dissolving the polyester resin in an organic solvent to cause phase inversion, an O / W It includes resin particles obtained by forming molded resin emulsified particles and further removing the organic solvent from the O / W resin emulsified particle dispersion.

  Further, in a preferred embodiment of the electrophotographic toner of the present invention, the compound is a compound having two epoxy groups in one molecule represented by the above chemical formula [Chemical Formula 4] (where X is an aliphatic group) Or an epoxy group of n = 0 to 1), which is obtained by addition reaction of one or more selected from purified rosin, disproportionated rosin and hydrogenated rosin.

In a preferred embodiment of the electrophotographic toner of the present invention, the compound represented by the chemical formula [Chemical Formula 3] is blended in an amount of 20% by weight or more as a polyester raw material.

  In a preferred embodiment of the electrophotographic toner of the present invention, the neutralizing agent is contained in an amount of 0.8 to 1.7 times equivalent to the carboxyl group contained in the polyester resin.

  The method for associating the resin particles in the dispersion will be described in more detail. An aqueous dispersion of a colorant prepared separately from a dispersion in which the resin particles of the present invention are dispersed in an aqueous medium or an aqueous dispersion of colored resin particles prepared separately. Colored resin having a larger average particle size by associating the dispersed resin particles and the colorant particles or the colored resin particles by lowering the surface potential of the resin particles by mixing with the body and adding a reverse neutralizer It can be obtained by making a dispersion of particles, then separating the particles and then drying. In this case, additives such as wax, magnetic powder, charge control agent and the like can be used together with the colorant, and an aqueous dispersion of resin particles containing the additive, magnetic powder, charge control agent and the like is added. You can also meet.

  Furthermore, as one aspect of the present invention, when the polyester resin of the present invention is dissolved in an organic solvent, a colorant and / or other additives are added simultaneously or at any point in the process to dissolve or disperse. You can also take the method.

  Further, the organic solvent may be removed after the resin particles are associated with the colorant particles or the colored resin particles. The average particle size of the fine particles in each dispersion used here is preferably 0.01 to 1 μm, more preferably 0.03 to 0.5 μm, from the viewpoint of storage stability and workability. The average particle diameter of the colored resin particles (toner particles) is preferably 3 to 15 μm, more preferably 4 to 10 μm, from the viewpoint of image quality.

  As a method for associating resin particles, colorant particles, etc., after adding a salting-out agent comprising an alkali metal salt, an alkaline earth metal salt, or the like into an aqueous dispersion in which resin particles, colorant particles, etc. are present And a method of heating the dispersion.

  Examples of the salting-out agent used here include chlorine salts, bromine salts, iodine salts, carbonates, sulfates and the like such as potassium, sodium, magnesium, calcium, barium, and aluminum.

  In the filtration / washing step, a filtration treatment for filtering the toner particles from the dispersion of toner particles obtained in the above-mentioned step, and a surfactant, a salting-out agent, etc. remaining from the filtered toner particles are removed. This is a process of performing a cleaning process. Here, examples of the filtration method include a centrifugal separation method, a vacuum filtration method using Nutsche and the like, a filtration method using a filter press and the like, but are not limited thereto.

  In the drying step, examples of the dryer used include a spray dryer, a vacuum freeze dryer, and a vacuum dryer, but are not limited thereto. When the dried toner particles are aggregated, the aggregate can be crushed by a crushing device such as a jet mill or a Henschel mixer.

  As an aqueous dispersion of a separately prepared colorant or an aqueous dispersion of separately prepared colored resin particles, for example, an aqueous dispersion obtained by emulsifying a colorant using a surfactant or the like, and after heating and melting the colorant and the resin Examples thereof include an aqueous dispersion dispersed in water containing a dispersant, and an aqueous dispersion obtained by dissolving a resin in which a colorant is dispersed in an organic solvent and then adding water to perform phase inversion emulsification.

  Any conventionally known colorant can be used in the electrophotographic toner of the present invention. Examples of these colorants include black colorants such as carbon black, aniline black, acetylene black, and iron black, and color colorants such as phthalocyanine, rhodamine, quinacridone, triallylmethane, Various dye / pigment compounds such as anthraquinone, azo, diazo, methine, allylamide, thioindigo, naphthol, isoindolinone, diketopyrrolopyrrole, benzimidazolone, these metal complex compounds, lakes Compounds and the like. These can be used alone or in admixture of two or more.

  If necessary, a positive or negative charge control agent may be added to the electrophotographic toner of the present invention. As a typical example of the charge control agent, in the black toner, nigrosine is used for a positively chargeable toner, and a monoazo dye metal salt is used for a negatively chargeable toner. In full-color toners, quaternary ammonium salts and imidazole metal complexes are used for positively charged toners, and salicylic acid metal complexes and organic boron salts are used for negatively charged toners.

  A release agent may be added to the electrophotographic toner of the present invention. Examples of such release agents include synthetic waxes such as low molecular weight polypropylene and polyethylene, natural waxes such as paraffin wax, carnauba wax, rice wax, montan wax, and beeswax.

  Further, in the toner for developing an electrostatic charge image of the present invention, a magnetic powder may be added as necessary to form a magnetic toner. As the magnetic powder internally added to these toners, any powders of alloys, oxides, compounds and the like containing ferromagnetic elements that are conventionally used in the production of magnetic toners can be used. Examples of these magnetic powders include magnetic iron oxide such as magnetite, maghemite, and ferrite, or a compound of a divalent metal and iron oxide, a metal such as iron, cobalt, nickel, or aluminum, cobalt of these metals, Examples include powders of metal alloys such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures of these powders.

  The toner for electrophotography of the present invention can be mixed with a carrier and used as a two-component developer. As the carrier that can be used with the toner of the present invention, any conventionally known carrier can be used. Examples of the carrier that can be used include magnetic powder such as iron powder, ferrite powder, and nickel powder, and glass beads. These carrier particles may have a surface coated with a resin or the like as required. Examples of the resin covering the carrier surface include styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester copolymer, fluorine-containing resin, silicon-containing resin, and polyamide. Examples thereof include resins, ionomer resins, polyphenylene sulfide resins, and mixtures thereof. Among these, fluorine-containing resins and silicon-containing resins are particularly preferable because they hardly form spent toner.

  An external additive for the purpose of improving fluidity may be added to the electrophotographic toner of the present invention. Examples of these external additives include inorganic fine particles such as silica, alumina and titania, fluororesin fine particles such as polyvinylidene fluoride and polytetrafluoroethylene, acrylic resin produced by emulsion polymerization, and fine particles of styrene-acrylic resin. Can be mentioned.

  The average particle size of the toner particles in the electrophotographic toner of the present invention is preferably 3 to 15 μm, and more preferably 4 to 10 μm from the viewpoint of image quality. The average particle size and particle size distribution of the toner particles can be measured using, for example, a Coulter counter.

  Here, the toner characteristics will be described. In the embodiment of the present invention, the average particle diameter of the toner is preferably 3 to 15 μm, and more preferably 4 to 10 μm. If the particle size is too small, not only the manufacturability becomes unstable, but the inclusion structure control is difficult, the chargeability becomes insufficient, the developability may be lowered, and if it is too large, the resolution of the image is lowered. To do.

  In the embodiment of the present invention, the toner preferably has a volume average particle size distribution index GSDv of 1.30 or less. Further, the ratio (GSDv / GSDp) of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp is preferably 0.95 or more. When the volume distribution index GSDv exceeds 1.30, the resolution of the image may decrease, and the ratio of the volume average particle size distribution index GSDv to the number average particle size distribution index GSDp (GSDv / GSDp) is If it is less than 0.95, the toner chargeability may be reduced, the toner may be scattered or fogged, and image defects may be caused.

  In the embodiment of the present invention, the average particle size of the toner and the values of the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp were measured and calculated as follows. First, with respect to the divided particle size range (channel), the toner particle size distribution measured using a Coulter Multisizer II (manufactured by Beckman-Coulter) is accumulated from the smaller diameter side with respect to the divided particle size range (channel). Draw a distribution and define the particle size to be 16% cumulative as the volume average particle size D16v and the number average particle size D16p. The particle size to be 50% cumulative is the volume average particle size D50v and the number average particle The diameter is defined as D50p. Similarly, particle diameters that are 84% cumulative are defined as volume average particle diameter D84v and number average particle diameter D84p. At this time, the volume average particle size distribution index (GSDv) is defined as D84v / D16v, and the number average particle size index (GSDp) is defined as D84p / D16p. Using these relational expressions, a volume average particle size distribution index (GSDv) and a number average particle size index (GSDp) can be calculated.

  The electrophotographic toner of the present invention can be produced by any developing method or development for developing an electrostatic image formed by conventionally known electrophotography, electrostatic recording or electrostatic printing methods such as copying machines, printers and facsimiles. It can also be applied to devices.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following, all parts represent parts by weight.

  The acid value, glass transition temperature (Tg), and softening temperature (Tm) of the resin in the following examples and comparative examples are as follows.

(Acid value)
The acid value refers to the number of milligrams of potassium hydroxide necessary to neutralize the acid groups contained in 1 g of a sample.

(Glass-transition temperature)
The glass transition temperature is measured by using a differential scanning calorimeter (DSC-6220, manufactured by SII Nanotechnology Inc.) and a baseline extension below Tg when measured at a heating rate of 20 ° C./min, and the vicinity of Tg. The temperature at the intersection of the tangent lines of the endothermic curve.

(Softening temperature)
The softening temperature was measured using a Koka-type flow tester (CFT-500D manufactured by Shimadzu Corporation) with the following measurement conditions: load 30 kg, nozzle diameter 1 mm, nozzle length 10 mm, preheating at 80 ° C. for 5 minutes. When measured at 3 ° C./min and a sample amount of 1 g, it means the temperature when the plunger drop amount of the flow tester is 4 mm.

(Biomass-derived raw material content)
The biomass-derived raw material content was calculated from the following formula.
Biomass-derived raw material content =
(Biomass component charge) x 100 / (Total charge-Theoretical dehydration)

  However, the biomass component charge is calculated as follows. That is, when the biomass component is an acid, the number of moles is obtained by subtracting 17.01 which is a molecular weight corresponding to OH from the molecular weight, and 1.01 which is the molecular weight corresponding to H when the biomass component is alcohol. Multiplied by.

(Method for measuring particle size and particle size distribution of resin particles)
It measured using the laser diffraction type particle size distribution measuring apparatus (LA-700 by Horiba Seisakusho). The sample in the state of dispersion is adjusted so as to have a solid content of about 2 g, and ion exchange water is added thereto to make about 40 mL. This is put into the cell until an appropriate concentration is reached, and after about 2 minutes, the concentration is measured when the concentration in the cell becomes almost stable. The obtained volume average particle diameter for each channel was accumulated from the smaller volume average particle diameter, and the volume average particle diameter (median diameter) was determined to be 50%. For the span as a measure of the breadth of the particle size distribution, a value obtained by subtracting the value of 10% diameter from 90% diameter and dividing by the median diameter was used.

(Measurement method of toner particle size and particle size distribution)
Coulter Multisizer-II type (manufactured by Beckman-Coulter) was used, and ISOTON-II (manufactured by Beckman-Coulter) was used as the electrolyte. As a measurement method, 0.5 to 50 mg of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzenesulfonate, as a dispersant. This was added to 100 ml of the electrolytic solution. The electrolyte in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the particle size distribution of particles of 2 to 60 μm is measured using the Coulter Multisizer-II type with an aperture diameter of 100 μm. Volume average distribution and number average distribution were determined. The number of particles to be measured was 50,000. The particle size distribution of the toner was determined by the following method. For the particle size range (channel) obtained by dividing the measured particle size distribution, a volume cumulative distribution is drawn from the smaller particle size, and the cumulative number particle size of 16% is defined as D16p, and the cumulative volume of 50% is accumulated. The particle size is defined as D50v. Furthermore, the cumulative number particle size that is 84% cumulative is defined as D84p. The volume average particle diameter in the present invention is D50v, and the GSDp under the small diameter side number average particle size index was calculated by the following formula.
Formula: Lower GSDp = {(D84p) / (D16p)} ^0.5

(Residual organic solvent content in the resin particle dispersion)
Gas chromatograph (GC-9A manufactured by Shimadzu Corporation), packed column (G-300 Chemical Substance Evaluation and Research Organization), injection temperature 150 ° C., detector temperature 150 ° C., 1-acetoxy-2-methoxyethane as internal standard substance, resin A particle dispersion diluted with ion-exchanged water was directly introduced to determine the organic solvent concentration.

(Storage stability)
The resin particle dispersion was allowed to stand at room temperature for 90 days, and the storage stability was judged based on whether or not a precipitate was generated.
○: No precipitate, △: Slightly observed precipitate, ×: Observed precipitate clearly

(Production of polyester resin A-1)
Bisphenol A type resin 1175 g and disproportionated rosin (acid value 156 mgKOH / g, derived from biomass) 2281 g as compound (a) epoxy resin and triphenylphosphine 1.7 g as a reaction catalyst were stirred, heated, thermometer, minute It was charged in a stainless steel reaction vessel equipped with a distillation apparatus and a nitrogen gas introduction tube and reacted for 5 hours at 180 ° C. with stirring in a nitrogen atmosphere, and it was confirmed that the acid value reached less than 5 mg KOH / g. Compound (a) Got. The reaction formula is as follows. That is, as shown in the following [Chemical Formula 9], a bisphenol A type epoxy resin and a disproportionated rosin were first reacted to synthesize a compound (a).

  Next, 382 g of ethylene glycol (derived from biomass) and 1481 g of terephthalic acid were charged and subjected to a polycondensation reaction at a reaction temperature of 250 ° C. for 14 hours. When the predetermined acid value was reached, the reaction was terminated to obtain a polyester resin (A-1). . Table 1 shows the characteristic values of the obtained resin. The reaction formula is as follows. That is, as shown in [Chemical Formula 10] below, the conventional reaction was carried out using compound (a) as the alcohol component of the polyester raw material.

(Production of polyester resin A-2)
As an epoxy resin of compound (a), 1095 g of bisphenol A resin and disproportionated rosin (acid value 156 mg KOH / g, derived from biomass) and 1.6 g of triphenylphosphine as a reaction catalyst were stirred, heated, thermometer, minute It was charged in a stainless steel reaction vessel equipped with a distillation apparatus and a nitrogen gas introduction tube and reacted for 5 hours at 180 ° C. with stirring in a nitrogen atmosphere, and it was confirmed that the acid value reached less than 5 mg KOH / g. Compound (a) Got.

  Next, 624 g of 1,3-propanediol (derived from biomass), 802 g of terephthalic acid, and 802 g of isophthalic acid were charged and subjected to a polycondensation reaction at a reaction temperature of 250 ° C. for 10 hours. When the predetermined acid value was reached, the reaction was terminated. (A-2) was obtained. Table 1 shows the characteristic values of the obtained resin.

(Production of polyester resin A-3)
As an epoxy resin of compound (a), 1284 g of bisphenol A resin and disproportionated rosin (acid value 156 mgKOH / g, derived from biomass) and 2373 g of triphenylphosphine as a reaction catalyst were stirred, heated, thermometer, minute It was charged in a stainless steel reaction vessel equipped with a distillation apparatus and a nitrogen gas introduction tube and reacted for 5 hours at 180 ° C. with stirring in a nitrogen atmosphere, and it was confirmed that the acid value reached less than 5 mg KOH / g. Compound (a) Got.

  Next, 282 g of 1,2-propanediol (derived from biomass), 923 g of isophthalic acid, and 359 g of dimer acid (acid value of 193 mg KOH / g, derived from biomass) were charged, and subjected to a polycondensation reaction at a reaction temperature of 250 ° C. for 15 hours to obtain a predetermined acid value. When it reached, the reaction was terminated to obtain a polyester resin (A-3). Table 1 shows the characteristic values of the obtained resin.

(Production of polyester resin B-1)
Polyester resin raw material alcohol component 590g ethylene glycol, bisphenol A propylene oxide 2-mole adduct 2530g, raw material acid component 1308g, isophthalic acid 700g, trimellitic anhydride 378g and tetra-n-butyl titanate 1.7g as reaction catalyst Was charged into a stainless steel reaction vessel equipped with a stirrer, heating device, thermometer, fractionator, and nitrogen gas inlet tube, and subjected to a polycondensation reaction at 250 ° C. for 12 hours with stirring in a nitrogen atmosphere to obtain a predetermined acid value. When it reached, the reaction was terminated to obtain a polyester resin (B-1). Table 1 shows the characteristic values of the obtained resin.

(Production of polyester resin B-2)
Polyester resin raw material alcohol component ethylene glycol 1082g, 1,3-propanediol 813g, raw acid component 3966g terephthalic acid and reaction catalyst 1.7g tetra-n-butyl titanate stirrer, heating device, thermometer, fractional distillation The reaction vessel was charged into a stainless steel reaction vessel equipped with an apparatus and a nitrogen gas introduction tube and subjected to a polycondensation reaction at 250 ° C. for 14 hours under stirring in a nitrogen atmosphere. When the predetermined acid value was reached, the reaction was terminated. -2) was obtained. Table 1 shows the characteristic values of the obtained resin.

(Production of polyester resin B-3)
Polyester resin raw material alcohol component 562 g, bisphenol A ethylene oxide 2-mole adduct 2435 g, raw acid component 1023 g terephthalic acid, isophthalic acid 1535 g and tetra-n-butyl titanate 1.7 g as a reaction catalyst , Charged into a stainless steel reaction vessel equipped with a thermometer, fractionator, and nitrogen gas inlet tube, and subjected to polycondensation reaction for 13 hours at 250 ° C. with stirring in a nitrogen atmosphere. When the predetermined acid value was reached, the reaction was terminated. As a result, a polyester resin (B-3) was obtained. Table 1 shows the characteristic values of the obtained resin.

(Example 1)
In a container equipped with a stirrer, a condenser and a thermometer, 70 parts by weight of coarsely pulverized polyester resin (A-1) and 30 parts by weight of coarsely pulverized polyester resin (A-2) were added, and then 60 parts by weight of methyl ethyl ketone and isopropyl 20 parts by weight of alcohol was added. Nitrogen was supplied and the atmosphere in the system was replaced with nitrogen. Next, while stirring the system, it was heated to 60 ° C. to dissolve the polyester resin. After adding 2.58 parts by weight of 10% aqueous ammonia as a neutralizing agent, 240 parts by weight of ion-exchanged water was added at a rate of 4.8 g / min with stirring using a metering pump. Emulsification was completed when the emulsification system was milky white and the stirring viscosity was reduced.

  Next, the reaction vessel was equipped with a vacuum pump decompression device, stirred under reduced pressure of the reaction vessel inner wall temperature of 50 ° C. and the reaction vessel of 6 kPa [abs], and when the total amount of residual solvent in the resin particle dispersion became less than 1000 ppm Was set to the end point, and the internal pressure of the reaction vessel was kept at normal pressure and cooled to room temperature while stirring. Table 2 shows the characteristic values of the obtained resin particle dispersion (1).

(Examples 2 to 6)
Resin particle dispersions (2) to (6) were prepared in the same manner as in Example 1 except that the blending ratios shown in Table 2 were used. The characteristic values of the obtained resin particle dispersion are shown in Table 2.

(Comparative Examples 1-6)
Resin particle dispersions (7) to (12) were prepared in the same manner as in Comparative Example 1 except that the blending ratios shown in Table 3 were used. The characteristic values of the obtained resin particle dispersion are shown in Table 3.

  From the results of Tables 2 and 3, the resin particle dispersion using the resin of the present invention has a span between 0.8 and 1.2 and a narrow particle size distribution. Further, it can be seen that the dispersion has good storage stability, and a dispersion having a uniform particle size distribution can be obtained even with a small amount of aqueous ammonia.

(Preparation of wax dispersion)
Into 1000 parts of distilled water in which 25 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved, 268 parts of paraffin wax (HNP0190; manufactured by Nippon Seiwa Co., Ltd.) is added and emulsified to disperse the wax dispersion. Obtained.

(Colorant particle dispersion)
To 1000 parts of distilled water in which 56 parts of sodium dodecylbenzenesulfonate (Neogen SC; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is dissolved, 139 parts of carbon black (Regal 330R; manufactured by Cabot Corp.) is added and dispersed as a colorant particle. A particle dispersion was obtained.

(Example 7)
(Manufacture of toner)
In a container equipped with a stirrer, a condenser, and a thermometer, 100 parts by weight (in terms of solid content) of resin particle dispersion (1), 39 parts by weight of colorant dispersion, and 23 parts by weight of wax dispersion are placed. Was adjusted to 30 ° C., and then an aqueous sodium hydroxide solution was added to adjust the pH to 11.0. Next, 240 parts of a 1.2 wt% aqueous magnesium chloride hexahydrate solution was added with stirring. After the addition, the temperature was raised to 90 ° C. and held for 3 hours. The produced particles were filtered. The obtained cake was repeatedly washed with ion-exchanged water until the washing water became neutral, and then dried with a hot air dryer at 40 ° C. to obtain toner particles (1). Toner particles (1) had a volume average particle size of 5.8 μm and a volume average particle size distribution index GSDV of 1.21.

(Example 8)
(Polyester resin A-4) New polyester resin and resin synthesis example for comparative example 1316 g of bisphenol A resin and disproportionated rosin (acid value 156 mgKOH / g, derived from biomass) as an epoxy resin of compound (a) and 2506 g as a reaction catalyst 1.9 g of triphenylphosphine was charged into a stainless steel reaction vessel equipped with a stirrer, a heating device, a thermometer, a fractionator, and a nitrogen gas introduction tube, and reacted at 180 ° C. for 5 hours with stirring in a nitrogen atmosphere. The compound (a) was obtained after confirming that the value reached less than 5 mgKOH / g. The reaction formula is as follows. That is, as shown in [Chemical Formula 11] below, first, a bisphenol A type epoxy resin and a disproportionated rosin were reacted to synthesize a compound (a).

  Next, 273 g of ethylene glycol (derived from biomass) and 1157 g of terephthalic acid were charged and subjected to a polycondensation reaction at a reaction temperature of 250 ° C. for 14 hours. (See Table 1). The reaction formula is as follows. That is, as shown in [Chemical Formula 12] below, the conventional reaction was carried out using compound (a) as the alcohol component of the polyester raw material.

(Polyester resins A-5 and A-6)
Table 4 shows the synthetic formulations. The numerical values in the table indicate parts by weight.

  Polyester resins (A-5) and (A-6: Reference Example) were synthesized in the same manner as in Synthesis Example 1 except that the blending ratios shown in Table 4 were used.

(Polyester resin B-4) Polyester resin synthesis example for comparison 813 g of neopentyl glycol as the alcohol component of the polyester resin, 1082 g of ethylene glycol, 3966 g of terephthalic acid as the acid component, and 4.7 g of tetra-n-butyl titanate as the reaction catalyst , Charged in a stainless steel reaction vessel equipped with a heating device, thermometer, fractionation device, nitrogen gas inlet tube, and subjected to a polycondensation reaction at 250 ° C. for 16 hours with stirring in a nitrogen atmosphere. The reaction was terminated to obtain a polyester resin (B-4).

(Polyester resin B-5)
A polyester resin (B-5) was synthesized in the same manner as in Synthesis Example 3 except that the blending ratio shown in Table 4 was used.

Table 4 shows the ratio of the compound (a), the end point acid value, and the hydroxyl group equivalent, in addition to the synthesis formulation. The biomass content was calculated from the following formula.
Biomass-derived raw material content =
(Biomass component charge) x 100 / (Total charge-Theoretical dehydration)

However, the biomass component charge is calculated as follows. That is, when the biomass component is an acid, the number of moles is obtained by subtracting 17.01 which is a molecular weight corresponding to OH from the molecular weight, and 1.01 which is the molecular weight corresponding to H when the biomass component is alcohol. Multiplied by.

Claims (12)

The following chemical formula [Chemical Formula 1],
Wherein X is aliphatic or aromatic, Y is a purified rosin residue, disproportionated rosin residue, or hydrogenated rosin residue, and n = 0 to 1 Resin particles comprising a polyester resin which is an essential component of the alcohol component.   The resin particles according to claim 1, wherein an average particle diameter of the resin particles is in a range of 0.01 to 1 μm.   After adding a neutralizing agent and an aqueous medium to a resin solution obtained by dissolving the polyester resin in an organic solvent to cause phase inversion, O / W type resin emulsified particles are formed, and further O / W type resin emulsification is performed. 3. The resin particles according to claim 1, wherein the resin particles are obtained by removing an organic solvent from the particle dispersion. The compound has the following chemical formula:
A compound having two epoxy groups in one molecule (wherein X is aliphatic or aromatic and n = 0 to 1) is added to a purified rosin, a disproportionate amount The resin particles according to any one of claims 1 to 3, wherein the resin particles are obtained by an addition reaction of one or more selected from fluorinated rosin and hydrogenated rosin. 5. The resin particles according to claim 1, wherein the compound represented by the chemical formula [Chemical Formula 1] is blended in an amount of 20% by weight or more as a polyester raw material.   The resin particle according to any one of claims 3 to 5, wherein the neutralizing agent is contained in an amount of 0.8 to 1.7 times equivalent to a carboxyl group contained in the polyester resin. . An electrophotographic toner comprising at least a polyester resin and a colorant, wherein the following chemical formula:
Wherein X is aliphatic or aromatic, Y is a purified rosin residue, disproportionated rosin residue, or hydrogenated rosin residue, and n = 0 to 1 An electrophotographic toner comprising resin particles made of a polyester resin which is an essential component of an alcohol component.   The electrophotographic toner according to claim 7, wherein an average particle diameter of the resin particles is in a range of 0.01 to 1 μm.   After adding a neutralizing agent and an aqueous medium to a resin solution obtained by dissolving the polyester resin in an organic solvent to cause phase inversion, O / W type resin emulsified particles are formed, and further O / W type resin emulsification is performed. The toner for electrophotography according to claim 7 or 8, comprising resin particles obtained by removing an organic solvent from the particle dispersion. The compound has the following chemical formula:
A compound having two epoxy groups in one molecule (wherein X is aliphatic or aromatic and n = 0 to 1) is added to a purified rosin, a disproportionate amount 10. The toner for electrophotography according to claim 7, wherein the toner is obtained by addition reaction of one or more selected from fluorinated rosin and hydrogenated rosin. 11. The electrophotographic toner according to claim 7, wherein the compound represented by the chemical formula [Chemical Formula 3] is blended in an amount of 20 wt% or more as a polyester raw material. The electrophotographic image according to any one of claims 9 to 11, wherein the neutralizing agent is contained in an amount of 0.8 to 1.7 times equivalent to a carboxyl group contained in the polyester resin. Toner.